CN113097375A - Flexible silver selenide-based thermoelectric thin film and preparation method thereof - Google Patents
Flexible silver selenide-based thermoelectric thin film and preparation method thereof Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000011669 selenium Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 61
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002042 Silver nanowire Substances 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical group CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 2
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Images
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a flexible silver selenide-based thermoelectric thin film and a preparation method thereof. The method comprises the following steps: mixing a selenium source and a silver source with a surfactant, a solvent and a reducing agent, reacting by using a chemical solution method, mixing the obtained silver selenide-based nano powder with the solvent, then printing a prefabricated film on a substrate by ink jet, drying in vacuum, and directly carrying out heat treatment or carrying out heat treatment after soaking in a binder dispersion liquid. The method is simple and low in cost, and the prepared film has good thermoelectric property, excellent mechanical property and flexibility.
Description
Technical Field
The invention belongs to the field of flexible thermoelectric materials and preparation thereof, and particularly relates to a flexible silver selenide-based thermoelectric thin film and a preparation method thereof.
Background
With the increasing demand of modern society for energy, traditional energy sources such as fossil energy are gradually exhausted, and the development and utilization of green and efficient novel clean energy becomes a preferred way for establishing an energy-saving society.
The thermoelectric material is a functional material which realizes the interconversion between thermal energy and electric energy by utilizing the Seebeck effect and the Peltier effect of a semiconductor material. Because of the advantages of small volume, no noise, no pollution, long service life, high reliability and the like, the thermoelectric material is widely concerned at home and abroad as an environment-friendly material.
The performance of the thermoelectric material mainly depends on the dimensionless thermoelectric figure of merit ZT of the material, and the expression is as follows: ZT ═ S2σ T/κ, where S is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, and T is the absolute temperature. The larger the ZT value of the material is, the higher the thermoelectric conversion efficiency is, and the better the thermoelectric performance is.
The preparation of wearable electronic devices based on flexible thermoelectric materials is more and more popular in the thermoelectric material research field at present. In recent years, research progress of flexible thermoelectric materials has been mainly focused on organic thermoelectric materials. The organic thermoelectric film mainly comprises conductive polymers, is high in flexibility and easy to obtain raw materials, but has a lower ZT value, and the development of the materials is greatly limited. The inorganic thermoelectric film has great advantages in thermoelectric performance, namely higher ZT value, but deficient content of most of the components, like the current commercialized Bi2Te3Although the ZT value is high, the component element Te is rare, the cost is high and the toxicity is high.
The silver selenide is low in cost, non-toxic and environment-friendly, is a phase-change material, can change phase from a low temperature to a high temperature at 407K, and is relatively widely used at the high temperature. Silver selenide in the low-temperature phase is a narrow-band-gap semiconductor, the band gap of the semiconductor is 0.07eV at 0K, and the thermal conductivity of the semiconductor is low. The low-temperature phase silver selenide has an orthogonal structure, belongs to the semiconductor characteristic, has higher conductivity and Seebeck coefficient, and gradually becomes a new favorite in inorganic thermoelectric thin film materials. The methods for preparing silver selenide thermoelectric thin films reported at present are various, but certain methods existLimitations, for example, Chinese patent CN 109293962A discloses a method for preparing Ag with high thermoelectric property2The method for preparing the Se/nylon flexible composite film is characterized in that uniform silver selenide nanowires are synthesized in a wet chemical mode at room temperature, and the silver selenide film with certain flexibility is obtained by taking a flexible nylon filter membrane as a substrate and adopting a suction filtration and hot pressing mode. However, due to the low density (relative density of 70%) of the film and the obvious preferred orientation of the silver selenide crystal grains in the (00l) direction, the thermoelectric performance and the bulk silver selenide performance of the film still have certain gaps. Furthermore, Perez-Taborda et al deposited silver selenide thin films on glass substrates by the pulsed hybrid reactive magnetron sputtering method, by adjusting the stoichiometric ratio of Ag/Se to 2, the power factor was as high as 2440 + -192 μ W/(mK)2) (Jaime Andres Perez-Taborda et al. high thermal zT in n-type silver selective films at room temperature, adv. energy Mater.2018,8,1702024). Although the method can accurately control the stoichiometric ratio of the thin film and has the advantages of industrial friendliness and the like, the method is more and more concerned, but the instrument cost is higher, and the large-scale application is difficult to realize. The Mallick group prepares the high-performance Ag-Se-based thermoelectric film at room temperature by a screen printing method, the ZT value of the Ag-Se-based thermoelectric film has further breakthrough, and the ZT value reaches 1.03 at room temperature (Md Mofasser Mallick et al, New front in printed thermoelectrics: formation of beta-Ag2Se through thermal stimulated discrete absorption leads to high ZT, Journal of Materials Chemistry A,2020,8,16366), but the film prepared by the method has rough surface, uneven slurry dispersion, more holes in the film caused by the heat treatment sintering process and low density. Therefore, the development of a preparation method of the high-performance silver selenide-based film with controllable cost and easy batch production has important significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a flexible silver selenide-based thermoelectric thin film and a preparation method thereof, so as to overcome the defects of poor thermoelectric performance, high cost and the like of the silver selenide-based thermoelectric thin film in the prior art.
The invention provides a preparation method of a flexible silver selenide-based thermoelectric thin film, which comprises the following steps:
(1) mixing a selenium source and a silver source with a surfactant, a solvent and a reducing agent in a molar ratio of 1: 1.8-1: 2.3, reacting by using a chemical solution method, centrifuging and washing to obtain silver selenide-based nano powder, wherein the mass ratio of the surfactant to the solvent is 2.5-7%, the volume ratio of the solvent to the reducing agent is 1.5: 1-2.5: 1, and the mass ratio of the selenium source to the surfactant is 25-27: 500-;
(2) mixing the silver selenide-based nano powder and a dispersing agent in the step (1), performing ultrasonic treatment, performing ink-jet printing on the obtained ink on a substrate to obtain a prefabricated film, and performing vacuum drying to obtain a silver selenide-based prefabricated film;
(3) carrying out heat treatment on the silver selenide-based prefabricated film in the step (2) in a reducing atmosphere to obtain a flexible silver selenide-based thermoelectric film; or soaking the silver selenide-based thermoelectric thin film in the step (2) in a sodium chloride solution, then soaking the silver selenide-based thermoelectric thin film in a binder dispersion liquid, drying the soaked thin film, and carrying out heat treatment in a reducing atmosphere to obtain the flexible silver selenide-based thermoelectric thin film, wherein the binder accounts for 0.5-50% of the mass percent of the silver selenide-based nano powder in the step (2).
Preferably, in the above method, the selenium source in step (1) comprises selenium dioxide, sodium selenite or selenourea.
Preferably, in the above method, the silver source in step (1) comprises silver nitrate or silver carbonate.
Preferably, in the above method, the surfactant in step (1) is polyvinylpyrrolidone PVP.
Preferably, in the above method, the solvent in the step (1) is N, N-dimethylformamide DMF; the reducing agent is oleic acid OA.
Preferably, in the above method, the size of the silver selenide-based nanopowder in the step (1) is less than or equal to 450 nm.
Preferably, in the method, the reaction temperature in the step (1) is 80-200 ℃, and the reaction time is 6-18 h.
Preferably, in the above method, the centrifugation and washing process in step (1) is as follows: centrifuging the reacted solution at 6000-.
Preferably, in the above method, the dispersant in step (2) is water, absolute ethyl alcohol or ethylene glycol; the total solid content of the ink is controlled to be 0.2-40%.
Preferably, in the above method, the substrate in the step (2) is a polyimide substrate. The cleaning method comprises the following cleaning steps of sequentially placing the materials into isopropanol, methanol and deionized water, respectively carrying out ultrasonic cleaning for 10-20min, and then placing the materials into an oven for drying.
Preferably, in the method, the ultrasonic treatment time in the step (2) is 60-120 min.
Preferably, in the above method, the inkjet printing in step (2) has the following process parameters: the substrate temperature is 40-60 ℃, the nozzle temperature is 30-50 ℃, and the ink drop distance is 10-20 μm.
Preferably, in the above method, the inkjet printing in step (2) is performed by an inkjet printer.
Preferably, in the method, the vacuum drying temperature in the step (2) is 40-70 ℃, and the vacuum drying time is 4-15 h.
Preferably, in the above method, the process parameters of the heat treatment in step (3) are as follows: the reducing atmosphere is argon-hydrogen mixed gas, the composition of the argon-hydrogen mixed gas is 5% of hydrogen and 95% of argon, the heating rate is 2-5 ℃/min, the heat treatment temperature is 200-450 ℃, and the heat preservation time is 10-120 min.
Preferably, in the above method, the binder in step (3) is a low-dimensional material with a high aspect ratio, and the low-dimensional material with a high aspect ratio includes tellurium nanowires, selenium nanowires, silver nanowires or carbon nanotubes.
The invention also provides the flexible silver selenide-based thermoelectric thin film prepared by the method.
The invention also provides application of the flexible silver selenide-based thermoelectric thin film prepared by the method.
The invention prepares silver selenide-based nano particles by a chemical solution method, then selects a proper dispersant to prepare ink with better stability, and adopts an ink-jet printing technology and combines a heat treatment process to obtain the flexible silver selenide-based thermoelectric film. The film has good thermoelectric performance, excellent flexibility, controllable size, high preparation precision, low cost, easy processing into flexible thermoelectric devices, and wide application prospect in the fields of flexible electronics, wearable equipment and the like.
Advantageous effects
(1) Advantages of the chemical solution process of the invention: the method has low equipment requirement, and the synthesized nano powder has high purity, controllable components and good dispersibility; silver selenide nano powder with higher thermoelectric performance can be prepared by optimizing the initial proportion of each element and the morphology of the powder;
(2) the advantages of the ink are as follows: the ink prepared by the invention has excellent performance and stable property, the particle size of the thermoelectric powder serving as a solute can be controlled below 450nm according to different apertures of the spray heads, the rheological property of the ink can be adjusted by regulating and controlling the solid content and the content of the additive, so that the ink is suitable for the spray heads of different models and has wide compatibility;
(3) advantages of inkjet printing: the ink-jet printing process used by the invention is simple and clear, has low cost and is suitable for large-scale industrial production; the prepared film has good flexibility, can be bent, and can be applied to the field of wearable electronic devices; the size of the film is controllable, the film is easy to process and form, and the patterning design of the thermoelectric device is facilitated;
(4) the performance advantage is as follows: the silver selenide and the composite thermoelectric film thereof can be prepared based on the invention, wherein the prepared silver selenide/carbon nano tube composite thermoelectric film combines the advantages of silver selenide and carbon nano tube, and the thermoelectric property of the material is obviously improved.
Drawings
FIG. 1 is Ag prepared in example 12A field emission scanning electron microscope image (a), a transmission electron microscope image (b) and an element surface scanning image (c-d) of the Se nano powder.
Fig. 2 is an X-ray diffraction pattern of silver selenide powders of different Ag and Se ratios prepared in examples 1, 2 and 3.
FIG. 3 is Ag prepared by ink-jet printing as in example 12Scanning electron microscope image of field emission of Se thermoelectric film.
FIG. 4 shows Ag in example 12Photo of Se thermoelectric film, wherein (a) is Ag prepared by ink-jet printing2Se thermoelectric film photo, Ag2Flexible display of Se-based thermoelectric thin films.
Fig. 5 is a graph of thermoelectric performance of silver selenide thermoelectric films of different Ag and Se ratios prepared in examples 1, 2 and 3.
FIG. 6 is Ag prepared in example 42A field emission scanning electron microscope image of the Se/carbon nanotube composite thermoelectric film.
FIG. 7 is Ag prepared in example 12Se thermoelectric film and Ag prepared in example 42Thermoelectric property diagram of Se/carbon nanotube composite film.
FIG. 8 shows different Ag materials prepared in example 52Thermoelectric property diagram of Se solid content film.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The medicines used in the embodiment of the invention, namely selenium dioxide, silver nitrate, polyvinylpyrrolidone PVP, N-dimethylformamide DMF and oleic acid OA, are all produced by Aladdin technologies and technologies Limited.
Example 1
Ag2Preparation of the Se flexible thermoelectric thin film:
1) weighing 0.5g of PVP and dissolving the PVP in 20mL of DMF, adding 26.3mg of selenium dioxide and 82.9mg of silver nitrate while stirring, adding 10mL of OA, magnetically stirring at room temperature for 8-10 min, pouring the mixed solution into a 50mL reaction kettle, heating to 120 ℃, and preserving heat for 12 h. After the reaction is completed, cooling the reaction kettle to room temperature, and centrifuging the solution after the reaction at the rotating speed of 8000r/minRemoving the upper layer solution, centrifuging and washing the obtained black powder, sequentially adding absolute ethyl alcohol and acetone into a centrifuge tube, centrifuging at 8000r/min for 5min, washing for three times, and drying the centrifuged powder at 60 deg.C under vacuum for 6h to obtain Ag2Se nano powder. Fig. 1 shows a field emission scanning electron microscope image and a transmission electron microscope image of the silver selenide nano powder synthesized by the embodiment, and it can be seen from the images: the synthesized silver selenide nano particles are uniform in appearance, the size is 100-200 nm, and the silver and the selenium elements are uniformly distributed. FIG. 2 shows Ag synthesized in this example2The X-ray diffraction pattern of Se nanopowder can be seen from the figure: synthetic Ag2The main phase of the Se nano powder is a low-temperature silver selenide phase and is consistent with a standard card (PDF #24-1041) thereof.
2) 0.025g of Ag2Se nano powder is dispersed in 10mL of absolute ethyl alcohol, and ultrasonic treatment is carried out for 60min to form suspension with better stability. Then, selecting flexible polyimide as a substrate, printing a silver selenide thermoelectric film with Ag/Se 2 by using an ink-jet printer (model DMP-2850), wherein the temperature of a substrate for ink-jet printing is set to be 40 ℃, the temperature of a spray head is set to be 30 ℃, the distance between ink drops is 20 mu m, then drying the printed film for 12h under the vacuum condition of 60 ℃, putting the dried film into a horizontal tube furnace, heating to 450 ℃ at the heating rate of 5 ℃/min under the atmosphere of argon-hydrogen mixture (5% of hydrogen and 95% of argon), preserving heat for 10min, and cooling along with the furnace to obtain the Ag2A Se thermoelectric film. FIG. 3 shows Ag in this example2The field emission scanning electron microscope image of the Se thermoelectric film shows that Ag is2The Se particles are closely contacted with each other, and the compactness is better.
In this example, Ag2The Se thermoelectric film has good flexibility as shown in fig. 4. The conductivity of the film measured by adopting a Loresta-GX high-precision four-probe instrument MCP-T700 is 54.6S/cm. A Seebeck coefficient testing system is self-established in a laboratory on the basis of a slope method, and potential difference delta V generated by the film under different temperature differences delta T is recorded by using a Peltier patch, an infrared thermal imager (FOTRIC 226) and a nanovoltmeter (Keithley 2182A). When the sample is tested, the infrared thermal imager is used for monitoring the surface temperature of the sample and recording the temperature difference delta T between the two ends of the sample. At the same time use the handkerchiefThe Peltier thermoelectric patches are fixed on the test board, and are respectively connected with opposite currents to enable one of the two Peltier patches to serve as a cold end and the other to serve as a hot end, so that temperature difference is established. The film sample was placed on peltier patches at the cold and hot ends, respectively, and the sample and the Keithley 2182A nanovoltmeter were connected by silver wire to record the potential difference Δ V across the sample. Calculating the prepared Ag by using the formula S ═ delta V/delta T2The Seebeck coefficient of the Se thin film is-87.2 mu V/K, and the power factor at room temperature is 41.5 mu W/(mK)2) As shown in fig. 5.
Example 2
Ag1.9Preparation of the Se flexible thermoelectric thin film:
ag was obtained in the same manner as in example 1 except that the amount of silver nitrate used in step (1) of example 1 was changed to 77.2mg according to example 11.9Se nanopowder, Ag synthesized in this example is shown in FIG. 21.9The X-ray diffraction pattern of Se nanopowder can be seen from the figure: synthetic Ag1.9The main phase of the Se nano powder is a low-temperature silver selenide phase and is consistent with a standard card (PDF #24-1041) thereof.
Mixing Ag with water1.9Preparing Ag from Se nano powder1.9The specific process of the Se thermoelectric film is the same as that of the example 1.
The conductivity of the film measured by adopting a Loresta-GX high-precision four-probe instrument MCP-T700 is 28.8S/cm. A Seebeck coefficient testing system is self-established in a laboratory on the basis of a slope method, and potential difference delta V generated by the film under different temperature differences delta T is recorded by using a Peltier patch, an infrared thermal imager (FOTRIC 226) and a nanovoltmeter (Keithley 2182A). When the sample is tested, the infrared thermal imager is used for monitoring the surface temperature of the sample and recording the temperature difference delta T between the two ends of the sample. Meanwhile, the Peltier thermoelectric patches are fixed on a test board, and opposite currents are respectively connected to enable one of the two Peltier thermoelectric patches to serve as a cold end and the other to serve as a hot end, so that temperature difference is established. The film sample was placed on peltier patches at the cold and hot ends, respectively, and the sample and the Keithley 2182A nanovoltmeter were connected by silver wire to record the potential difference Δ V across the sample. Calculating the prepared Ag by using the formula S ═ delta V/delta T1.9Seebeck coefficient of Se thin film of-96.9 μ V/K, whichThe power factor at room temperature is 27 muW/(mK)2) As shown in fig. 5.
Example 3
Ag2.1Preparation of the Se flexible thermoelectric thin film:
ag was obtained in the same manner as in example 1 except that the amount of silver nitrate used in step (1) of example 1 was changed to 85.6mg according to example 12.1Se nano powder. FIG. 2 shows Ag synthesized in this example2.1The X-ray diffraction pattern of Se nanopowder can be seen from the figure: synthetic Ag2.1The main phase of the Se nano powder is a low-temperature silver selenide phase and is consistent with a standard card (PDF #24-1041) thereof.
Mixing Ag with water2.1Preparing Ag from Se nano powder2.1The specific process of the Se thermoelectric film is the same as that of the example 1.
The conductivity of the film measured by adopting a Loresta-GX high-precision four-probe instrument MCP-T700 is 48.3S/cm. A Seebeck coefficient testing system self-built by utilizing a laboratory based on a slope method records potential difference delta V generated by a film under different temperature differences delta T by adopting a Peltier, an infrared thermal imager (FOTRIC 226) and a nanovoltmeter (Keithley 2182A), and the prepared Ag is calculated by utilizing a formula S ═ delta V/delta T2.1The Seebeck coefficient of the Se thin film is-81.3 mu V/K, and the power factor at room temperature is 31.9 mu W/(mK)2) As shown in fig. 5.
Example 4
Ag2Preparing the Se/carbon nanotube composite thermoelectric film:
1) 1.0g of PVP is weighed and dissolved in 40mL of DMF, then 117.8mg of selenium dioxide and 137.2mg of silver nitrate are added with stirring, then 20mL of OA is added, magnetic stirring is carried out for 8-10 min at room temperature, then the solution is poured into a 100mL reaction kettle, and the temperature is heated to 120 ℃ and kept for 12 h. After the reaction is completed, cooling the reaction kettle to room temperature, centrifuging the solution after the reaction for 10min at the rotating speed of 8000r/min, removing the upper layer solution, centrifuging and washing the obtained black powder, then sequentially adding absolute ethyl alcohol and acetone into a centrifuge tube, centrifuging for 5min at the rotating speed of 8000r/min, washing for three times respectively, and finally drying the centrifuged powder for 6h at the temperature of 60 ℃ under the vacuum condition to obtain Ag2Se nano powder.
2) 0.050g of Ag2Se nano powder is dispersed in 20mL of absolute ethyl alcohol, and ultrasonic treatment is carried out for 60min to form suspension with better stability. Then, a flexible polyimide was selected as a substrate, and a silver selenide thermoelectric thin film of Ag/Se 2 was printed using an inkjet printer (model DMP-2850) in which the substrate temperature for inkjet printing was set to 40 ℃, the head temperature was set to 30 ℃, the droplet pitch was 20 μm, and then the printed thin film was dried under vacuum at 60 ℃ for 6 hours.
3) 0.250g of sodium dodecyl sulfate was weighed out and dissolved in 50mL of deionized water, and magnetically stirred at room temperature for 60 min. 0.025g of carbon nanotube powder was added to the solution, and ultrasonication was performed for 60min to obtain a uniform and stable carbon nanotube dispersion. Soaking the silver selenide thermoelectric film prepared in the last step in 0.6mol/L sodium chloride solution for 1h at room temperature, then soaking the film in carbon nano tube dispersion for 60min, drying the soaked film at 60 ℃ under vacuum condition for 12h, then placing the film in a horizontal tube furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed (5% of hydrogen and 95% of argon) atmosphere, preserving heat for 10min, and cooling along with the furnace to obtain the Ag thermoelectric film2Se/carbon nanotube composite thermoelectric thin film material. FIG. 6 shows Ag prepared in this example2The field emission scanning electron microscope image of the Se/carbon nanotube composite thermoelectric film proves that the Ag is obtained by ink-jet printing2The Se film is really compounded with the carbon nano tube after being soaked in the carbon nano tube dispersion liquid.
The conductivity of the film measured by adopting a Loresta-GX high-precision four-probe instrument MCP-T700 is 106.15S/cm. A Seebeck coefficient testing system self-built by utilizing a laboratory based on a slope method records potential difference delta V generated by a film under different temperature differences delta T by adopting a Peltier, an infrared thermal imager (FOTRIC 226) and a nanovoltmeter (Keithley 2182A), and the prepared Ag is calculated by utilizing a formula S ═ delta V/delta T2The Seebeck coefficient of the Se/carbon nano tube composite film is-113.4 mu V/K, and the power factor at room temperature is 136.5 mu W/(mK)2) As shown in fig. 7. FIG. 7 compares n-type Ag2Se thermoelectric film and Ag2The electrical properties of the Se/carbon nanotube composite thermoelectric film, as can be seen from the figure, Ag2Se thin filmAfter the carbon nano tube is compounded, the electrical property of the film is obviously improved.
Example 5
Different Ag2Preparation of thermoelectric thin film with Se solid content:
ag preparation according to example 1 procedure2Se nano powder, weighing Ag with the same mass20.025g of Se nano powder is respectively dispersed in 10mL and 5mL of absolute ethyl alcohol, and ultrasonic treatment is carried out for 60min to form suspension with better stability. Then, selecting flexible polyimide as a substrate, printing the Ag/Se-2 silver selenide thermoelectric thin film by using an ink-jet printer (model DMP-2850), wherein the temperature of the ink-jet printed substrate is set to be 40 ℃, the temperature of a spray head is set to be 30 ℃, the distance between ink drops is 20 mu m, then drying the printed thin film at 60 ℃ under a vacuum condition for 12h, placing the dried thin film in a horizontal tube furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed (5% hydrogen and 95% argon) atmosphere, preserving heat for 10min, and cooling along with the furnace to obtain Ag with solid content of 2.5mg/mL and 5mg/mL2A Se thermoelectric film.
Ag with solid content of 2.5mg/mL and 5mg/mL is measured by adopting Loresta-GX high-precision four-probe instrument MCP-T7002The electrical conductivity of the Se thermoelectric film is 54.6 and 165.0S/cm respectively. The Seebeck coefficient testing system self-built by utilizing a laboratory based on a slope method records potential difference delta V generated by the films under different temperature differences delta T by adopting a Peltier, an infrared thermal imager (FOTRIC 226) and a nanovoltmeter (Keithley 2182A), the Seebeck coefficients of the two prepared films are respectively-87.2 and-126.0 mu V/K by utilizing a formula S ═ delta V/delta T, and power factors at room temperature are respectively 41.5 and 261.9 mu W/(mK)2) As shown in fig. 8. FIG. 8 compares Ag at different solids contents2The electrical properties of the Se thermoelectric film, as can be seen in the figure, improve Ag2After the solid content of the Se ink is increased, the electrical property of the film is remarkably improved.
Md Mofasser Mallick(Md Mofasser Mallick,Leonard Franke,Uli Lemmer,et al.New frontier in printed thermoelectrics:Formation ofβ-Ag2Se through thermally stimulated dissociative adsorption leads to high ZT[J]Journal of Materials Chemistry A,2020,8.) et al use screen printingThe Ag-Se-based thermoelectric film has the conductivity of about 460S/cm at room temperature, the Seebeck coefficient of nearly-200 mu V/K and the power factor of 1700 mu W/(mK)2). Although exhibiting superior thermoelectric properties, the thin films subjected to thermoelectric property characterization were printed on glass substrates and thus were not flexible.
In summary, the method of the invention adopts a chemical solution method to synthesize silver selenide-based nano powder, and then obtains the flexible silver selenide-based and the composite thermoelectric film thereof based on the ink-jet printing technology, the compactness is better, compared with the prior art, the film prepared by the invention has the advantages that the Seebeck coefficient and the conductivity reach excellent values after compounding and improving the solid content, the film has good thermoelectric property, the flexibility is realized, the size of the film is controllable, the mass production is easy, and the application prospect is good.
The above examples are merely illustrative for clarity and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of a flexible silver selenide-based thermoelectric thin film comprises the following steps:
(1) mixing a selenium source and a silver source with a surfactant, a solvent and a reducing agent in a molar ratio of 1: 1.8-1: 2.3, reacting by using a chemical solution method, centrifuging and washing to obtain silver selenide-based nano powder, wherein the mass ratio of the surfactant to the solvent is 2.5-7%, the volume ratio of the solvent to the reducing agent is 1.5: 1-2.5: 1, and the mass ratio of the selenium source to the surfactant is 25-27: 500-;
(2) mixing the silver selenide-based nano powder and a dispersing agent in the step (1), performing ultrasonic treatment, performing ink-jet printing on the obtained ink on a substrate to obtain a prefabricated film, and performing vacuum drying to obtain a silver selenide-based prefabricated film;
(3) carrying out heat treatment on the silver selenide-based prefabricated film in the step (2) in a reducing atmosphere to obtain a flexible silver selenide-based thermoelectric film; or soaking the silver selenide based prefabricated film in the step (2) in a sodium chloride solution, then placing the film in a binder dispersion liquid for soaking, drying the soaked film, and carrying out heat treatment in a reducing atmosphere to obtain the flexible silver selenide based composite thermoelectric film, wherein the mass percentage of the binder relative to the silver selenide based nano powder in the step (2) is 0.5-50%.
2. The method according to claim 1, wherein the selenium source in step (1) comprises selenium dioxide, sodium selenite or selenourea; the silver source comprises silver nitrate or silver carbonate; the surface active agent is polyvinylpyrrolidone PVP; the solvent is N, N-dimethylformamide DMF; the reducing agent is oleic acid OA.
3. The method as claimed in claim 1, wherein the silver selenide-based nanopowder in step (1) has a size of 450nm or less.
4. The method according to claim 1, wherein the reaction temperature in the step (1) is 80-200 ℃ and the reaction time is 6-18 h.
5. The method according to claim 1, wherein the dispersing agent in the step (2) is water, absolute ethyl alcohol or ethylene glycol; the total solid content in the ink is controlled to be 0.2-40 percent; the substrate is a polyimide substrate.
6. The method according to claim 1, wherein the ultrasonic treatment time in the step (2) is 60-120 min; the technological parameters of the ink-jet printing are as follows: the substrate temperature is 40-60 ℃, the nozzle temperature is 30-50 ℃, and the ink drop distance is 10-20 μm.
7. The method according to claim 1, wherein the process parameters of the heat treatment in the step (3) are as follows: the reducing atmosphere is argon-hydrogen mixed gas, the composition of the argon-hydrogen mixed gas is 5% of hydrogen and 95% of argon, the heating rate is 2-5 ℃/min, the heat treatment temperature is 200-450 ℃, and the heat preservation time is 10-120 min.
8. The method of claim 1, wherein the binder in step (3) is a low dimensional material with a high aspect ratio, the low dimensional material with a high aspect ratio comprising tellurium nanowires, selenium nanowires, silver nanowires or carbon nanotubes.
9. A flexible silver selenide based thermoelectric film prepared according to the method of claim 1.
10. Use of a flexible silver selenide-based thermoelectric film prepared according to the method of claim 1.
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| CN113277485A (en) * | 2021-05-19 | 2021-08-20 | 重庆大学 | Preparation method of thermoelectric composite material and thermoelectric composite material |
| CN114226210A (en) * | 2021-12-16 | 2022-03-25 | 华东师范大学 | Silver selenide thermoelectric composite film and preparation method and application thereof |
| CN115274998A (en) * | 2022-07-11 | 2022-11-01 | 上海应用技术大学 | Preparation method of flexible Cu-Se nanowire/methyl cellulose composite thermoelectric film |
| CN117812985A (en) * | 2024-03-01 | 2024-04-02 | 中北大学 | Flexible photo-thermal electric detection device based on spraying method and preparation method thereof |
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| WO2018220168A2 (en) * | 2017-06-02 | 2018-12-06 | Nexdot | Ink comprising encapsulated nanoparticles |
| CN111252802A (en) * | 2020-01-21 | 2020-06-09 | 重庆大学 | Silver-based chalcogenide Ag2Preparation method of X thermoelectric material |
| JP2020194926A (en) * | 2019-05-29 | 2020-12-03 | 国立研究開発法人産業技術総合研究所 | Thermoelectric conversion material, thermoelectric conversion element using the same, thermoelectric power generation module, and peltier cooler |
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| WO2018220168A2 (en) * | 2017-06-02 | 2018-12-06 | Nexdot | Ink comprising encapsulated nanoparticles |
| JP2020194926A (en) * | 2019-05-29 | 2020-12-03 | 国立研究開発法人産業技術総合研究所 | Thermoelectric conversion material, thermoelectric conversion element using the same, thermoelectric power generation module, and peltier cooler |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113277485A (en) * | 2021-05-19 | 2021-08-20 | 重庆大学 | Preparation method of thermoelectric composite material and thermoelectric composite material |
| CN114226210A (en) * | 2021-12-16 | 2022-03-25 | 华东师范大学 | Silver selenide thermoelectric composite film and preparation method and application thereof |
| CN115274998A (en) * | 2022-07-11 | 2022-11-01 | 上海应用技术大学 | Preparation method of flexible Cu-Se nanowire/methyl cellulose composite thermoelectric film |
| CN115274998B (en) * | 2022-07-11 | 2024-07-02 | 上海应用技术大学 | Preparation method of flexible Cu-Se nanowire/methylcellulose composite thermoelectric film |
| CN117812985A (en) * | 2024-03-01 | 2024-04-02 | 中北大学 | Flexible photo-thermal electric detection device based on spraying method and preparation method thereof |
| CN117812985B (en) * | 2024-03-01 | 2024-05-14 | 中北大学 | Flexible photo-thermal electric detection device based on spraying method and preparation method thereof |
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