Self-supporting tantalum diselenide nanosheet / PEDOT: PSS thermoelectric composite film and preparation method thereof
Through solution 3D printing technology, the tantalum diselenide nanosheets were combined with PEDOT:PSS to prepare composite films with excellent flexibility and good thermoelectric properties, which solved the problem of solution 3D printing preparation method that was not reported in the prior art and expanded its application prospects in the field of thermoelectric.
Patent Information
- Application Number
- CN202411962197.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-30
- Publication Date
- 2025-04-04
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
No prior art has been reported. The preparation of tantalum diselenide nanosheets/PEDOT:PSS composite thermoelectric films is used to prepare solution 3D printing technology, which limits its application in the field of thermoelectricity.
The supported tantalum disenide nanosheets/PEDOT:PSS thermoelectric composite film was prepared by dispersing the tantalum disenide nanosheets in PEDOT:PSS solution, printing them on a glass substrate using solution 3D printing technology, and then dried, vacuum dried and cold pressed.
The prepared composite film has excellent flexibility and good thermoelectric properties, and has potential applications in wearable devices, curved electronics, flexible sensors and flexible energy harvesting devices.
Smart Images
Figure CN119768021A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of organic-inorganic composite materials, and specifically relates to a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film and a preparation method thereof. Background Art
[0002] Thermoelectric materials are functional materials that can directly realize the mutual conversion between heat energy and electrical energy. The Seebeck effect of the material can be used to convert heat energy into electrical energy. 3D printing technology has the advantages of easy operation, the ability to prepare any shape and mass production, and has broad application prospects in the field of thermoelectrics. However, there are currently no reports on the method of preparing tantalum diselenide nanosheets / PEDOT:PSS composite thermoelectric films using solution 3D printing technology. Summary of the invention
[0003] In view of the shortcomings of the prior art, the present invention provides a method for preparing a tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film. The preparation process of the invention is universal, and the prepared tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film has excellent flexibility and good thermoelectric performance.
[0004] As an organic thermoelectric material, PEDOT:PSS has the characteristics of high electrical conductivity, low thermal conductivity and good film-forming properties. However, its low Seebeck coefficient limits its development. Considering that two-dimensional tantalum diselenide nanosheets have a high Seebeck coefficient, this patent innovatively combines the two through solution 3D printing technology to prepare a tantalum diselenide nanosheet / PEDOT:PSS composite film with excellent flexibility and good thermoelectric properties. This composite film has potential application prospects in the field of thermoelectrics.
[0005] The invention provides a method for preparing a tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film, comprising the following steps: dispersing tantalum diselenide nanosheets in a PEDOT:PSS solution containing 5% by volume of dimethyl sulfoxide to obtain a mixed solution, printing the mixed solution on a glass substrate through a 3D printing technology after being fully stirred, drying the mixed solution at room temperature for 48 hours, and naturally falling off and separating from the glass substrate after soaking the mixed solution in a methanol solution for 30 minutes, then vacuum drying the mixed solution at 60°C for 5 minutes, and cold pressing the mixed solution at 30MPa for 5 minutes to obtain the self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film.
[0006] Furthermore, the tantalum diselenide nanosheets are prepared from tantalum diselenide powder by lithium ion intercalation stripping technology.
[0007] Furthermore, the tantalum diselenide nanosheets are prepared from tantalum diselenide powder by lithium ion intercalation stripping technology, and the steps include: dissolving LiOH·H2O in ethylene glycol, adding ground tantalum diselenide powder, stirring evenly and placing in a reactor to react at 200°C for 24 hours; cooling after the reaction is completed, and centrifuging at 5000rpm for 3min to obtain a precipitate; washing the precipitate with acetone and dispersing it in 200mL deionized water for 1h, and then centrifuging at 1000rpm for 3min to collect the supernatant; freeze-drying the supernatant to obtain tantalum diselenide nanosheets.
[0008] Furthermore, the tantalum diselenide nanosheets are prepared from tantalum diselenide powder by lithium ion intercalation stripping technology, wherein the mass volume ratio of LiOH·H2O:ethylene glycol is (0.1-1) g:60 mL.
[0009] Furthermore, in the method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film, the solid content of the tantalum diselenide nanosheet in the mixed solution is 1wt%-40wt%.
[0010] Furthermore, the method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film is described, wherein the film is fully stirred and then printed on a glass substrate using 3D printing technology, and the stirring time is 12-72 hours.
[0011] Furthermore, in the method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film, the 3D printing technology uses a needle diameter of 0.11-1.1 mm and a line spacing width of 0.2-2.2 mm.
[0012] The present invention also provides a tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film, which is prepared by the above preparation method.
[0013] Compared with the prior art, the present invention has the following advantages:
[0014] 1. The present invention combines tantalum diselenide nanosheets with PEDOT:PSS. PEDOT:PSS is an organic thermoelectric material with the characteristics of high electrical conductivity, low thermal conductivity and good film forming properties. However, its development is limited by its low Seebeck coefficient. Tantalum diselenide nanosheets have a high Seebeck coefficient, so the composite film prepared by combining the two has good thermoelectric properties.
[0015] 2. The tantalum diselenide nanosheets / PEDOT:PSS composite film prepared by the present invention has sufficient flexibility so that the composite film can maintain structural stability without additional support, and has potential application prospects in the fields of wearable devices or curved electronic products, flexible sensors and flexible energy harvesting devices.
[0016] 3. The present invention prepares tantalum diselenide nanosheets / PEDOT:PSS composite films through 3D printing technology. The process has the advantages of convenient operation, mass production, high design freedom, etc., and has universal applicability. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 Schematic diagram of transmission electron microscopy of tantalum diselenide nanosheets of Example 3.
[0018] Figure 2 This is a surface scanning electron microscope image of the flexible self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film of Example 3.
[0019] Figure 3 This is a digital photo showing the flexibility of the flexible self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film of Example 3.
[0020] Figure 4 This is a graph showing the relationship between the resistance change rate and the bending times of the flexible self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film of Example 3.
[0021] Figure 5 This is a relationship diagram of the Seebeck coefficient, electrical conductivity and power factor of the flexible self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film of Example 3 as a function of temperature. DETAILED DESCRIPTION
[0022] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.
[0023] Unless otherwise specified, the experimental reagents and raw materials used in the present invention are commercially available.
[0024] The experimental methods without specific conditions in the following implementations are all selected according to conventional methods and conditions, or according to the product instructions. Unless otherwise specified, the experimental instruments used in the present invention are all conventional experimental instruments in the laboratory.
[0025] Example 1
[0026] This embodiment provides a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film and a preparation method thereof, the preparation steps comprising:
[0027] (1) Preparation of tantalum diselenide nanosheets: 0.1 g of LiOH·H2O was dissolved in 60 mL of ethylene glycol, 0.5 g of tantalum diselenide powder was placed in a mortar and ground for 2 h, then added to the above ethylene glycol solution, stirred evenly, and placed in a 100 mL reactor for reaction at 200°C for 24 h; after the reaction was completed, it was cooled to room temperature with the furnace and centrifuged at 5000 rpm for 3 min to obtain a precipitate; the precipitate was washed with acetone three times and then dispersed in 200 mL of deionized water and ultrasonicated for 1 h, and then centrifuged at 1000 rpm for 3 min to collect the supernatant; the supernatant was freeze-dried to obtain tantalum diselenide nanosheets.
[0028] (2) Preparation of self-supporting tantalum diselenide nanosheets / PEDOT:PSS thermoelectric composite film: Weigh 0.001 g of tantalum diselenide nanosheets and disperse them in 10 mL of PEDOT:PSS and 0.527 mL of dimethyl sulfoxide to obtain a mixed solution with a solid content of 1 wt% of tantalum diselenide nanosheets, and stir for 12 h to obtain a printing slurry; add the printing slurry to a 3D printing device, select a 0.11 mm needle and a 0.22 mm line spacing, and use a printer to print the slurry onto a glass substrate; place it at room temperature for 48 h to dry, and then soak it in a methanol solution for 30 min to naturally fall off and separate from the glass substrate; then vacuum dry it at 60°C for 5 min, and cold press it (30 MPa, 5 min) to obtain a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film.
[0029] Example 2
[0030] This embodiment provides a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film and a preparation method thereof, the preparation steps comprising:
[0031] (1) Preparation of tantalum diselenide nanosheets: 1.0 g of LiOH·H2O was dissolved in 60 mL of ethylene glycol, 0.5 g of tantalum diselenide powder was placed in a mortar and ground for 2 h, then added to the above ethylene glycol solution, stirred evenly, and placed in a 100 mL reactor for reaction at 200°C for 24 h; after the reaction was completed, it was cooled to room temperature with the furnace and centrifuged at 5000 rpm for 3 min to obtain a precipitate; the precipitate was washed with acetone three times and then dispersed in 200 mL of deionized water and ultrasonicated for 1 h, and then centrifuged at 1000 rpm for 3 min to collect the supernatant; the supernatant was freeze-dried to obtain tantalum diselenide nanosheets.
[0032] (2) Preparation of self-supporting tantalum diselenide nanosheets / PEDOT:PSS thermoelectric composite film: Weigh 0.0667 g of tantalum diselenide nanosheets and disperse them in 10 mL of PEDOT:PSS and 0.527 mL of dimethyl sulfoxide to obtain a mixed solution with a solid content of 40 wt% of tantalum diselenide nanosheets, and stir for 72 h to obtain a printing slurry; add the printing slurry to a 3D printing device, select a 1.1 mm needle and a 2.2 mm line spacing, and use a printer to print the slurry onto a glass substrate; after drying at room temperature for 48 h, soak in a methanol solution for 30 min to naturally fall off and separate from the glass substrate; then vacuum dry at 60°C for 5 min, and cold press (30 MPa, 5 min) to obtain a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film.
[0033] Example 3
[0034] This embodiment provides a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film and a preparation method thereof, the preparation steps comprising:
[0035] (1) Preparation of tantalum diselenide nanosheets: 0.48 g of LiOH·H2O was dissolved in 60 mL of ethylene glycol, 0.5 g of tantalum diselenide powder was placed in a mortar and ground for 2 h, then added to the above ethylene glycol solution, stirred evenly, and placed in a 100 mL reactor for reaction at 200°C for 24 h; after the reaction was completed, it was cooled to room temperature with the furnace and centrifuged at 5000 rpm for 3 min to obtain a precipitate; the precipitate was washed with acetone three times and then dispersed in 200 mL of deionized water for 1 h, and then centrifuged at 1000 rpm for 3 min to collect the supernatant; the supernatant was freeze-dried to obtain tantalum diselenide nanosheets.
[0036] (2) Preparation of self-supporting tantalum diselenide nanosheets / PEDOT:PSS thermoelectric composite film: Weigh 0.0111 g of tantalum diselenide nanosheets and disperse them in 10 mL of PEDOT:PSS and 0.527 mL of dimethyl sulfoxide to obtain a mixed solution with a solid content of 10 wt% of tantalum diselenide nanosheets, and stir for 36 hours to obtain a printing slurry; add the printing slurry to a 3D printing device, select a 0.25 mm needle and a 0.5 mm line spacing, and use a printer to print the slurry onto a glass substrate; after drying at room temperature for 48 hours, soak in a methanol solution for 30 minutes to naturally fall off and separate from the glass substrate; then vacuum dry at 60°C for 5 minutes, and undergo cold pressing treatment (30 MPa, 5 minutes) to obtain a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film.
[0037] like Figure 1-Figure 5 As shown, Figure 1This is a transmission electron microscope image of the tantalum diselenide nanosheet prepared in Example 3. It can be seen from the image that the tantalum diselenide nanosheet after peeling has good crystallinity.
[0038] Figure 2 This is a surface scanning electron microscope image of the flexible self-supporting tantalum diselenide nanosheets / PEDOT:PSS thermoelectric composite film prepared in Example 3. It can be seen from the image that the tantalum diselenide nanosheets are uniformly dispersed in the composite film.
[0039] Figure 3 This is a digital photo of the flexible self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film prepared in Example 3. It can be seen from the figure that: the figure shows the shape of the film when it is bent, demonstrating its excellent flexibility.
[0040] Figure 4 The resistance change rate of the flexible self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film prepared in Example 3 changes with the number of bending times. It can be seen from the figure that when the bending radius is 4 mm, after bending 500 times, the resistance change rate of the composite film is 6.8%, indicating that the composite film has good flexibility.
[0041] Figure 5 The thermoelectric performance diagram of the flexible self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film prepared in Example 3 shows that when the temperature is 380K, the Seebeck coefficient is 15.5μV / K; the conductivity is 1086.1S / cm; and the power factor is 26.2μWm -1 K -2 .
[0042] Example 4
[0043] This embodiment provides a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film and a preparation method thereof, the preparation steps comprising:
[0044] (1) Preparation of tantalum diselenide nanosheets: 0.48 g of LiOH·H2O was dissolved in 60 mL of ethylene glycol, 0.5 g of tantalum diselenide powder was placed in a mortar and ground for 2 h, then added to the above ethylene glycol solution, stirred evenly, and placed in a 100 mL reactor for reaction at 200°C for 24 h; after the reaction was completed, it was cooled to room temperature with the furnace and centrifuged at 5000 rpm for 3 min to obtain a precipitate; the precipitate was washed with acetone three times and then dispersed in 200 mL of deionized water for 1 h, and then centrifuged at 1000 rpm for 3 min to collect the supernatant; the supernatant was freeze-dried to obtain tantalum diselenide nanosheets.
[0045] (2) Preparation of self-supporting tantalum diselenide nanosheets / PEDOT:PSS thermoelectric composite film: Weigh 0.025 g of tantalum diselenide nanosheets and disperse them in 10 mL of PEDOT:PSS and 0.527 mL of dimethyl sulfoxide to obtain a mixed solution with a solid content of 20 wt% of tantalum diselenide nanosheets, and stir for 36 hours to obtain a printing slurry; add the printing slurry to a 3D printing device, select a 0.25 mm needle and a 0.5 mm line spacing, and use a printer to print the slurry onto a glass substrate; after drying at room temperature for 48 hours, soak in a methanol solution for 30 minutes to naturally fall off and separate from the glass substrate; then vacuum dry at 60°C for 5 minutes, and undergo cold pressing treatment (30 MPa, 5 minutes) to obtain a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film.
[0046] The formulations of the above Examples 1-4 and the parameters selected in the steps are shown in Table 1:
[0047] Table 1: Formulas for preparing thermoelectric composite films in Examples 1-4 and parameters selected in the steps
[0048]
[0049] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.
Claims
1. A method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film, characterized in that: Tantalum diselenide nanosheets are dispersed in a PEDOT:PSS solution containing 5% volume fraction of dimethyl sulfoxide to obtain a mixed solution, which is fully stirred and printed on a glass substrate by 3D printing technology. The mixed solution is dried at room temperature for 48 hours to obtain a composite material, which is naturally separated from the glass substrate by immersion in a methanol solution for 30 minutes, and then vacuum dried at 60°C for 5 minutes. The self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film is obtained by cold pressing at 30 MPa for 5 minutes.
2. The method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film according to claim 1, characterized in that: The tantalum diselenide nanosheet is prepared from tantalum diselenide powder by lithium ion intercalation stripping technology.
3. The method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film according to claim 2, characterized in that the steps include: LiOH·H2O was dissolved in ethylene glycol, and ground tantalum diselenide powder was added. The mixture was stirred evenly and placed in a reactor to react at 200°C for 24 hours. After the reaction was completed, the mixture was cooled and centrifuged at 5000 rpm for 3 minutes to obtain a precipitate. The precipitate was washed with acetone and dispersed in 200 mL of deionized water for 1 hour, and then centrifuged at 1000 rpm for 3 minutes to collect the supernatant. The supernatant was freeze-dried to obtain tantalum diselenide nanosheets.
4. The method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film according to claim 3, characterized in that: The mass volume ratio of LiOH·H2O:ethylene glycol is (0.1-1) g:60 mL.
5. The method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film according to claim 1, characterized in that: In the mixed solution, the solid content of tantalum diselenide nanosheets is 1wt%-40wt%.
6. The method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film according to claim 1, characterized in that: The mixture is fully stirred and then printed on a glass substrate using 3D printing technology, with a stirring time of 12-72 hours.
7. The method for preparing a self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film according to claim 1, characterized in that: The 3D printing technology uses a needle with a diameter of 0.11-1.1 mm and a line spacing with a width of 0.2-2.2 mm.
8. A self-supporting tantalum diselenide nanosheet / PEDOT:PSS thermoelectric composite film, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 7.