CN115483341A - Preparation method of flexible N-type nylon-based silver selenide thermoelectric film - Google Patents
Preparation method of flexible N-type nylon-based silver selenide thermoelectric film Download PDFInfo
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- KDSXXMBJKHQCAA-UHFFFAOYSA-N disilver;selenium(2-) Chemical compound [Se-2].[Ag+].[Ag+] KDSXXMBJKHQCAA-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000004677 Nylon Substances 0.000 title claims abstract description 55
- 229920001778 nylon Polymers 0.000 title claims abstract description 55
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- 239000012528 membrane Substances 0.000 claims abstract description 74
- 239000010408 film Substances 0.000 claims abstract description 66
- 239000003365 glass fiber Substances 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 22
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 26
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 13
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- 238000003756 stirring Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
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- 238000002490 spark plasma sintering Methods 0.000 description 15
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- 229910052711 selenium Inorganic materials 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a preparation method of a flexible N-type nylon-based silver selenide thermoelectric film, which comprises the steps of synthesizing silver selenide particles by a solvothermal method, uniformly dispersing the silver selenide particles in ethylene glycol, uniformly dripping the silver selenide particles on a glass fiber filter membrane, and performing discharge plasma sintering (SPS) treatment to obtain a uniform and compact flexible nylon-based silver selenide film. The thin film prepared by the method has excellent thermoelectric performance, the adopted discharge plasma sintering (SPS) process can regulate and control the microscopic morphology and the carrier transmission characteristic of the thin film, the silver content in the thin film is reduced, and an ordered fiber structure is formed, so that the carrier concentration is reduced, the carrier mobility is improved, the Seebeck coefficient and the conductivity are simultaneously enhanced, the method has simple process, short preparation period, safety and no pollution, and the obtained thin film has excellent thermoelectric performance and good flexibility.
Description
The technical field is as follows:
the invention relates to the technical field of new energy materials, in particular to a preparation method of a flexible N-type nylon-based silver selenide thermoelectric film.
Background art:
with the rise of the internet of things era, products such as wearable electronic equipment and the like are rapidly developed, and the wearable electronic equipment has wide application prospects in the fields of medical equipment, environment monitoring, intelligent clothes and the like. In recent years, the trend of miniaturization and flexibility of wearable electronic devices has pushed the development of flexible thermoelectric thin film devices. The flexible thermoelectric film material has the characteristics of light weight, good mechanical flexibility, low cost and the like, and provides potential for development and application of future wearable electronic equipment.
Silver selenide has intrinsic high conductivity and Seebeck coefficient at room temperature, has excellent thermoelectric property, and is expected to meet the application requirement of flexible devices. But limited by the preparation method, the thermoelectric performance of the flexible film prepared by cold pressing, hot pressing, printing, thermal evaporation and other methods is far less than that of the silver selenide-based block. Therefore, a silver selenide-based film with excellent performance and good flexibility is prepared by adopting a more effective technology.
The invention content is as follows:
the invention aims to provide a preparation method of a flexible N-type nylon-based silver selenide thermoelectric film, which comprises the steps of synthesizing silver selenide particles by a solvothermal method, uniformly dispersing the silver selenide particles in ethylene glycol, uniformly coating the silver selenide particles on a glass fiber filter membrane in a dropwise manner, and performing discharge plasma sintering (SPS) treatment to obtain a uniform and compact flexible nylon-based silver selenide film with excellent thermoelectric performance. The method has the advantages of simple process, short preparation period, safety and no pollution, and the obtained film has excellent thermoelectric property and good flexibility.
The invention is realized by the following technical scheme:
a preparation method of a flexible N-type nylon-based silver selenide thermoelectric film comprises the following steps:
(1) Mixing the components in a molar ratio of (2.1-2.5): 1, respectively dissolving silver nitrate and selenium powder in ethylenediamine, stirring, pouring into a reaction kettle, placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5 hours, alternately and centrifugally washing the obtained product with deionized water and ethanol for 2-3 times, and then ultrasonically dispersing the washed silver selenide particles into 10mL of ethylene glycol to obtain uniform silver selenide dispersion liquid; the concentration of the silver selenide is 25-35mg/mL;
(2) Uniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a glass fiber filter membrane under the vacuum filtration auxiliary condition, wherein the dripping amount of the silver selenide dispersion liquid is 1-2mL/cm 2 After the liquid is pumped to dryness, drying the liquid in a vacuum oven at 60 ℃ to obtain a silver selenide film adhered on the glass fiber filter membrane;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, forming by discharge plasma sintering (SPS), wherein the sintering temperature is 100-200 ℃, the sintering time is 1-9min, and the pressure is 30-50MPa, removing the nylon filter membrane on the back of the glass fiber filter membrane, and wiping off glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film.
Preferably, the molar ratio of silver nitrate to selenium powder in the step (1) is 2.3:1, the concentration of the silver selenide is 28-32mg/mL.
Preferably, the dropping amount of the silver selenide dispersion liquid of the step (2) is 1.2mL/cm 2 。
Preferably, the sintering temperature of the Spark Plasma Sintering (SPS) process in the step (3) is 130-200 ℃, the sintering time is 1-7min, and the pressure is 30MPa.
The invention has the following beneficial effects:
1) The silver selenide particles synthesized by the solvothermal method can be uniformly dispersed in ethylene glycol, can be uniformly dripped on a glass fiber filter membrane, and is subjected to discharge plasma sintering (SPS) treatment to obtain a uniform and compact flexible nylon-based silver selenide film.
2) The flexible N-type nylon-based silver selenide thermoelectric film is prepared by adopting a Spark Plasma Sintering (SPS) process for the first time, the microstructure and the silver content of the film are regulated and controlled by optimizing the sintering process, the silver content in the film is reduced, and an ordered fiber structure is formed, so that the carrier concentration is reduced, the carrier mobility is improved, the Seebeck coefficient and the conductivity are simultaneously enhanced, and the thermoelectric performance is further improved. The method has the advantages of simple process, short preparation period, safety, no pollution, simplicity, controllability and the like, and compared with preparation methods such as cold pressing, hot pressing, printing, thermal evaporation and the like, the thin film prepared by the method has more excellent thermoelectric property and better mechanical flexibility.
Description of the drawings:
FIG. 1 is a surface scanning electron micrograph of a silver selenide thin film adhered to a glass fiber filter obtained in step (2) of example 1 of the present invention.
Fig. 2 is a surface scanning electron microscope photograph of the flexible N-type nylon-based silver selenide thermoelectric thin film obtained in step (3) of example 1 of the present invention.
Fig. 3 is a scanning electron microscope photomicrograph of a cross-section of the flexible N-type nylon-based silver selenide thermoelectric thin film obtained in example 1 of the present invention.
Fig. 4 is a graph showing the relationship between the electrical conductivity and the power factor of the flexible N-type nylon-based silver selenide thermoelectric thin film obtained in example 1 of the present invention as a function of temperature.
Fig. 5 is a graph showing the relationship between the resistance and the bending radius of the flexible N-type nylon-based silver selenide thermoelectric thin film obtained in example 1 of the present invention.
FIG. 6 is a scanning electron micrograph of a cross-section of a silver selenide film adhered to a glass fiber filter according to comparative example 1 of the present invention.
Fig. 7 is a graph showing the relationship between the electrical conductivity and the power factor of the flexible N-type nylon-based silver selenide thermoelectric thin film obtained in comparative example 1 of the present invention as a function of temperature.
Fig. 8 is a graph showing the relationship between the electrical conductivity and the power factor of the flexible N-type nylon-based silver selenide thermoelectric thin film obtained in example 2 of the present invention as a function of temperature.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: preparation method of flexible N-type nylon-based silver selenide thermoelectric film
(1) Mixing the components in a molar ratio of 2.3:1, dissolving silver nitrate and selenium powder in 7.5mL and 10mL of ethylenediamine respectively, stirring for 30min, pouring into a 25mL reaction kettle, and placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5h; the obtained product is sequentially subjected to alternate centrifugal washing of deionized water and ethanol for 2-3 times, and then the washed silver selenide particles are ultrasonically dispersed into 10mL of glycol to obtain uniform silver selenide dispersion liquid; the concentration of the silver selenide is 29mg/mL;
(2) Uniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a 20mm-5mm glass fiber filter membrane under the vacuum filtration auxiliary condition, wherein the dripping amount of the silver selenide dispersion liquid is 1.2mL/cm 2 After the liquid is drained, drying the liquid in a vacuum oven at 60 ℃ to obtain a silver selenide film adhered on the glass fiber filter membrane, wherein a scanning electron microscope photo of the surface of the film is shown in figure 1;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, and forming by discharge plasma sintering (SPS), wherein the sintering temperature is 200 ℃, the sintering time is 5min, and the pressure is 30MPa, then removing the nylon filter membrane on the back of the glass fiber filter membrane, and then wiping off the glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film, wherein a scanning electron microscope photo of the surface is shown in figure 2, a scanning electron microscope photo of the cross section is shown in figure 3, the conductivity and the power factor are shown in figure 4, and the relation between the resistance and the bending radius is shown in figure 5. As shown in fig. 1 and 2, under the simultaneous action of the temperature and the pressure of the discharge plasma sintering (SPS) process, silver selenide particles are extruded and stacked together, crystal grains grow, and the thin film becomes more compact, so that the silver selenide particles have higher conductivity. As can be seen from FIG. 4, the silver selenide thermoelectric thin film attached to the nylon substrate has better mechanical flexibility, and the resistance of the thin film is still almost unchanged when the bending radius is 2.5mm, which indicates that the prepared thin film has better flexibility.
Comparative example 1:
(1) Mixing the components in a molar ratio of 2.3:1, dissolving silver nitrate and selenium powder in 7.5mL and 10mL of ethylenediamine respectively, stirring for 30min, pouring into a 25mL reaction kettle, and placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5h; the obtained product is sequentially subjected to alternate centrifugal washing of deionized water and ethanol for 2-3 times, and then the washed silver selenide particles are ultrasonically dispersed into 10mL of glycol to obtain uniform silver selenide dispersion liquid; the concentration of the silver selenide is 29mg/mL;
(2) Uniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a 20mm-5 mm glass fiber filter membrane under the condition of vacuum filtration assistance, wherein the dripping amount of the silver selenide dispersion liquid is 1.2mL/cm 2 After the liquid is pumped to dryness, drying the liquid in a vacuum oven at 60 ℃ to obtain a silver selenide film adhered on the glass fiber filter membrane;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, performing cold press molding under the pressure of 30MPa by using a tablet press, removing the nylon filter membrane on the back of the glass fiber filter membrane, and wiping off glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film. The scanning electron micrograph of the cross section is shown in fig. 6 (comparing fig. 6 with fig. 3 in example 1, it can be seen that the composition and morphology of the film are changed by the discharge plasma sintering (SPS) treatment, an ordered fiber texture is formed, and the carrier transport property of the silver selenide film is changed), and the conductivity and the power factor are shown in fig. 7.
As can be seen from the example 1 and the comparative example 1, the product obtained in the example 1 has obviously enhanced conductivity and power factor due to the change of the carrier concentration and the mobility of the thin film caused by plastic deformation, and has better application prospect.
Comparative example 2:
reference to "Ultrahigh Performance of n-Type Ag 2 Preparation of silver selenide nanometer by using synthetic method in Se Films for Flexible Thermoelectric Power Generators (Cong Jiang and Yufei Ding, DOI: 10.1021/acsami.9b21069)And then preparing the nylon-based silver selenide thermoelectric film according to the sintering method of the invention.
(1) Pure selenium dioxide (0.1 g) and beta-cyclodextrin (0.1 g) were added to a beaker containing 10mL of deionized water, stirred for 10min to give a clear solution, which was immediately poured into another beaker containing ascorbic acid solution (20mL, 0.028M) with continuous stirring, and the mixture quickly changed from colorless to yellow. A brick red suspension formed immediately thereafter, indicating the formation of amorphous selenium. After 4h of reaction, the product was washed by alternate centrifugation with deionized water and ethanol and collected, then redispersed in ethanol and aged for 2h without stirring. In the process, the mixture changes from brick red to metal gray, and selenium nanowires are obtained.
(2) And (2) taking 20mL of ethylene glycol dispersion liquid of the selenium nanowire as a template, reacting with silver nitrate at 40 ℃ for 2h, wherein the molar ratio of the silver nitrate to the selenium powder is 2.3:1, centrifuging and collecting to obtain a silver selenide nano structure, and dispersing the silver selenide nano wire in 10ml of absolute ethyl alcohol.
(3) Uniformly dripping the obtained silver selenide nanowire dispersion liquid on a glass fiber filter membrane of 20mm x 5mm under the condition of vacuum filtration assistance, wherein the dripping amount of the silver selenide dispersion liquid is 1.2mL/cm 2 And after the liquid is pumped to be dry, drying in a vacuum oven at 60 ℃ to obtain the silver selenide film adhered on the glass fiber filter membrane.
(4) The obtained silver selenide film adhered to the glass fiber filter membrane is placed between two nylon filter membranes, and is formed through discharge plasma sintering (SPS), the sintering temperature is 200 ℃, the sintering time is 5min, and the pressure is 30MPa, then the nylon filter membrane on the back of the glass fiber filter membrane is removed, and then glass fiber filter membrane fragments on the surface of the silver selenide film are wiped off, so that the flexible N-type nylon-based silver selenide thermoelectric film is obtained. The power factor of the alloy at 30 ℃ is only 471.03 mu W/(mK) 2 ). The silver selenide dispersion prepared by the method has poor dispersibility, and the finally prepared silver selenide film has uneven thickness and larger resistance, so the performance is poor.
As can be seen from example 1 and comparative example 2, in example 1, since the silver selenide particles synthesized by the solvothermal method can be uniformly dispersed in ethylene glycol, the silver selenide particles can be uniformly drop-coated on the glass fiber filter membrane, and then the nylon-based silver selenide thin film can be uniformly and densely obtained through discharge plasma sintering (SPS) treatment, and has excellent thermoelectric properties and good flexibility.
Example 2:
(1) Mixing the components in a molar ratio of 2.3:1, dissolving silver nitrate and selenium powder in 7.5mL and 10mL of ethylenediamine respectively, stirring for 30min, pouring into a 25mL reaction kettle, and placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5h; the obtained product is sequentially subjected to alternate centrifugal washing of deionized water and ethanol for 2-3 times, and then the washed silver selenide particles are ultrasonically dispersed into 10mL of glycol to obtain uniform silver selenide dispersion liquid; the concentration of the silver selenide is 29mg/mL;
(2) Uniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a 20mm-5mm glass fiber filter membrane under the vacuum filtration auxiliary condition, wherein the dripping amount of the silver selenide dispersion liquid is 1.2mL/cm 2 After the liquid is pumped to dryness, drying the liquid in a vacuum oven at 60 ℃ to obtain a silver selenide film adhered on the glass fiber filter membrane;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, forming by discharge plasma sintering (SPS), wherein the sintering temperature is 130 ℃, the sintering time is 1min, and the pressure is 30MPa, removing the nylon filter membrane on the back of the glass fiber filter membrane, and then wiping off glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film. The conductivity and power factor are shown in fig. 8.
Example 3:
(1) Mixing the components in a molar ratio of 2.3:1, dissolving silver nitrate and selenium powder in 7.5mL and 10mL of ethylenediamine respectively, stirring for 30min, pouring into a 25mL reaction kettle, and placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5h; the obtained product is sequentially subjected to alternate centrifugal washing of deionized water and ethanol for 2-3 times, and then the washed silver selenide particles are ultrasonically dispersed into 10mL of glycol to obtain uniform silver selenide dispersion liquid; the concentration of the silver selenide is 29mg/mL;
(2) Under the condition of vacuum filtration assistanceUniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a glass fiber filter membrane of 20mm-5mm, wherein the dripping amount of the silver selenide dispersion liquid is 1.2mL/cm 2 After the liquid is pumped to dryness, drying the liquid in a vacuum oven at 60 ℃ to obtain a silver selenide film adhered on the glass fiber filter membrane;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, forming by discharge plasma sintering (SPS), wherein the sintering temperature is 150 ℃, the sintering time is 1min, and the pressure is 30MPa, removing the nylon filter membrane on the back of the glass fiber filter membrane, and then wiping off glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film. The power factor of the mixed solution at 30 ℃ is 2920.01 mu W/(mK) 2 )。
Example 4:
(1) Mixing the components in a molar ratio of 2.3:1, dissolving silver nitrate and selenium powder in 7.5mL and 10mL of ethylenediamine respectively, stirring for 30min, pouring into a 25mL reaction kettle, and placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5h; the obtained product is sequentially subjected to alternate centrifugal washing of deionized water and ethanol for 2-3 times, and then the washed silver selenide particles are ultrasonically dispersed into 10mL of glycol to obtain uniform silver selenide dispersion liquid; the concentration of the silver selenide is 29mg/mL;
(2) Uniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a 20mm-5mm glass fiber filter membrane under the vacuum filtration auxiliary condition, wherein the dripping amount of the silver selenide dispersion liquid is 1.2mL/cm 2 After the liquid is pumped to dryness, drying the liquid in a vacuum oven at 60 ℃ to obtain a silver selenide film adhered on the glass fiber filter membrane;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, forming by discharge plasma sintering (SPS), wherein the sintering temperature is 200 ℃, the sintering time is 1min, and the pressure is 30MPa, removing the nylon filter membrane on the back of the glass fiber filter membrane, and then wiping off glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film. The power factor of the mixed solution at 30 ℃ is 3038.33 mu W/(mK) 2 )。
Example 5:
(1) Mixing the components in a molar ratio of 2.3:1, dissolving silver nitrate and selenium powder in 7.5mL and 10mL of ethylenediamine respectively, stirring for 30min, pouring into a 25mL reaction kettle, and placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5h; the obtained product is sequentially subjected to alternate centrifugal washing of deionized water and ethanol for 2-3 times, and then the washed silver selenide particles are ultrasonically dispersed into 10mL of glycol to obtain uniform silver selenide dispersion liquid; the concentration of the silver selenide is 29mg/mL;
(2) Uniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a 20mm-5 mm glass fiber filter membrane under the condition of vacuum filtration assistance, wherein the dripping amount of the silver selenide dispersion liquid is 1.2mL/cm 2 After the liquid is pumped to dryness, drying the liquid in a vacuum oven at 60 ℃ to obtain a silver selenide film adhered on the glass fiber filter membrane;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, forming by discharge plasma sintering (SPS), wherein the sintering temperature is 200 ℃, the sintering time is 3min, and the pressure is 30MPa, then removing the nylon filter membrane on the back of the glass fiber filter membrane, and then wiping off glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film. The power factor of the material at 30 ℃ is 3862.3 mu W/(mK) 2 )。
Example 6:
(1) Mixing the components in a molar ratio of 2.3:1, dissolving silver nitrate and selenium powder in 7.5mL and 10mL of ethylenediamine respectively, stirring for 30min, pouring into a 25mL reaction kettle, and placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5h; the obtained product is sequentially subjected to alternate centrifugal washing of deionized water and ethanol for 2-3 times, and then the washed silver selenide particles are ultrasonically dispersed into 10mL of glycol to obtain a uniform silver selenide dispersion liquid, wherein the concentration of silver selenide is 29mg/mL;
(2) Uniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a 20mm-5mm glass fiber filter membrane under the vacuum filtration auxiliary condition, wherein the dripping amount of the silver selenide dispersion liquid is 1.2mL/cm 2 After the liquid is pumped to dryness, drying in a vacuum oven at 60 ℃ to obtain the glass adhered with the glassA silver selenide film on the fiber filter membrane;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, forming by discharge plasma sintering (SPS), wherein the sintering temperature is 200 ℃, the sintering time is 7min, and the pressure is 30MPa, removing the nylon filter membrane on the back of the glass fiber filter membrane, and then wiping off glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film. The power factor of the mixed solution at 30 ℃ is 2722.1 mu W/(mK) 2 )。
Claims (5)
1. A preparation method of a flexible N-type nylon-based silver selenide thermoelectric film is characterized by comprising the following steps:
(1) Mixing the components in a molar ratio of (2.1-2.5): 1, respectively dissolving silver nitrate and selenium powder in ethylenediamine, stirring, pouring into a reaction kettle, placing the reaction kettle in a forced air drying oven for reaction at 180 ℃ for 5 hours, alternately and centrifugally washing the obtained product with deionized water and ethanol for 2-3 times, and then ultrasonically dispersing the washed silver selenide particles into 10mL of ethylene glycol to obtain uniform silver selenide dispersion liquid; the concentration of the silver selenide is 25-35mg/mL;
(2) Uniformly dripping the silver selenide dispersion liquid obtained in the step (1) on a glass fiber filter membrane under the vacuum filtration auxiliary condition, wherein the dripping amount of the silver selenide dispersion liquid is 1-2mL/cm 2 After the liquid is pumped to dryness, drying the liquid in a vacuum oven at 60 ℃ to obtain a silver selenide film adhered on the glass fiber filter membrane;
(3) And (3) placing the silver selenide film adhered to the glass fiber filter membrane obtained in the step (2) between two nylon filter membranes, sintering and forming by discharging plasma, wherein the sintering temperature is 100-200 ℃, the sintering time is 1-9min, and the pressure is 30-50MPa, removing the nylon filter membrane on the back of the glass fiber filter membrane, and wiping off glass fiber filter membrane fragments on the surface of the silver selenide film to obtain the flexible N-type nylon-based silver selenide thermoelectric film.
2. The method for preparing a flexible N-type nylon-based silver selenide thermoelectric film as claimed in claim 1, wherein the molar ratio of silver nitrate to selenium powder in the step (1) is 2.3:1.
3. the method for preparing a flexible N-type nylon-based silver selenide thermoelectric thin film as claimed in claim 1, wherein the concentration of silver selenide in step (1) is 28-32mg/mL.
4. The method for preparing a flexible N-type nylon-based silver selenide thermoelectric thin film as claimed in claim 1 or 2, wherein in the step (2), the dropping amount of the silver selenide dispersion is 1.2mL/cm 2 。
5. The method for preparing a flexible N-type nylon-based silver selenide thermoelectric film as claimed in claim 1 or 2, wherein the sintering temperature of the discharge plasma sintering process in the step (3) is 130-200 ℃, the sintering time is 1-7min, and the pressure is 30MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118510365A (en) * | 2024-05-08 | 2024-08-16 | 武汉大学 | Thermoelectric cotton wire with inorganic silver selenide-silver alternating structure and preparation method thereof |
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| CN118510365A (en) * | 2024-05-08 | 2024-08-16 | 武汉大学 | Thermoelectric cotton wire with inorganic silver selenide-silver alternating structure and preparation method thereof |
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