CN113802372B - Ag nano particle coated SnS/C flexible thermoelectric fiber membrane and preparation method thereof - Google Patents

Ag nano particle coated SnS/C flexible thermoelectric fiber membrane and preparation method thereof Download PDF

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CN113802372B
CN113802372B CN202111095493.8A CN202111095493A CN113802372B CN 113802372 B CN113802372 B CN 113802372B CN 202111095493 A CN202111095493 A CN 202111095493A CN 113802372 B CN113802372 B CN 113802372B
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CN113802372A (en
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张荔
刘祎
杨艳玲
侯小江
冯雷
叶晓慧
锁国权
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Shaanxi University of Science and Technology
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    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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Abstract

The invention provides an Ag nano particle coated SnS/C flexible thermoelectric fiber membrane and a preparation method thereof, wherein the method comprises the following steps: step 1, pre-oxidized SnCl 2 Vulcanizing the/PVP fiber membrane at 230-280 ℃ to obtain an SnS/PVP fiber membrane; step 2, carbonizing the SnS/PVP fiber membrane at 500-800 ℃ to obtain an SnS/C flexible fiber membrane; and 3, sequentially soaking the SnS/C flexible fiber membrane in 5-15% of silver ammonia solution and 5-10% of L-ascorbic acid solution to obtain the SnS/C flexible thermoelectric fiber membrane coated with the Ag nano particles. The Ag nano particles provide good conductivity for the SnS/C flexible thermoelectric fiber film, so that the thermoelectric property of the composite material is improved.

Description

Ag nano particle coated SnS/C flexible thermoelectric fiber membrane and preparation method thereof
Technical Field
The invention belongs to the field of flexible nano energy thermoelectric materials, and particularly relates to an Ag nano particle coated SnS/C flexible thermoelectric fiber membrane and a preparation method thereof.
Background
During the combustion of fossil fuels and the like, only about 30-40% of the energy is effectively utilized, while the remaining 60-70% of the energy is wasted in the form of waste heat. Therefore, with the increasing severity of energy and environmental problems, the development of new and efficient green clean energy technologies is urgently needed. The thermoelectric conversion technology can directly convert waste heat into electric energy for recycling, secondary pollution such as carbon dioxide is not generated in the process, and various natural heat energy sources such as solar energy and geothermal energy can be effectively utilized for electric energy conversion. The thermoelectric device made of thermoelectric material has the advantages of small volume, wide applicable temperature range, no moving parts, noise and the like, and has great development prospect in the fields of thermoelectric power generation, refrigeration, flexibility and the like.
Thermoelectric materials with thermoelectric figure of merit (ZT) now available for commercialization are mainly concentrated on Bi containing rare and noble elements 2 Te 3 And GeTe, they generally have problems of high price, oxidation resistance, thermal stability and environmental friendliness, and the like, so it is important to develop a thermoelectric material which is cheap and green, and has excellent thermoelectric performance and good stability. With the great development of wearable devices, flexible thermoelectric materials are attracting attention.
In recent years, snSe thermoelectric materials attract extensive attention due to low price, green color and excellent thermoelectric property. The SnS has the characteristics of abundant element content and low cost and is another focus of thermoelectric materials because the crystal structure of the SnS is similar to that of SnSe, but the SnS has the problem of low carrier mobility, so that the SnS has poor electrical property.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the SnS/C flexible thermoelectric fiber film coated with the Ag nano particles and the preparation method thereof, wherein the Ag nano particles provide good conductivity for the SnS/C flexible thermoelectric fiber film, so that the thermoelectric property of the composite material is improved.
The invention is realized by the following technical scheme:
a preparation method of an Ag nano particle coated SnS/C flexible thermoelectric fiber membrane comprises the following steps:
step 1, pre-oxidized SnCl 2 Vulcanizing the/PVP fiber membrane at 230-280 ℃ to obtain an SnS/PVP fiber membrane;
step 2, carbonizing the SnS/PVP fiber membrane at 500-800 ℃ to obtain an SnS/C flexible fiber membrane;
and 3, sequentially soaking the SnS/C flexible fiber membrane in 5-15% of silver ammonia solution and 5-10% of L-ascorbic acid solution to obtain the SnS/C flexible thermoelectric fiber membrane coated with the Ag nano particles.
Preferably, the pre-oxidized SnCl described in step 1 2 The PVP fiber membrane is obtained by the following steps:
SnCl 2 The PVP fiber membrane is calcined for 2 to 4 hours at the temperature of 230 to 280 ℃ to obtain the pre-oxidized SnCl 2 a/PVP fibrous membrane.
Further, the SnCl 2 the/PVP fiber membrane is obtained by the following process:
according to the formula (0.9-1.8): 0.5 mass ratio of SnCl 2 ·2H 2 Dissolving O and polyvinylpyrrolidone in an organic solvent to obtain a mixed solution, performing electrostatic spinning on the mixed solution, removing the residual organic solvent, and drying to obtain SnCl 2 a/PVP fibrous membrane.
Further, the voltage of the mixed solution during electrostatic spinning is 16-18kv, and the speed is 0.5-1.5mL/min.
Further, the mixed solution is dried in a vacuum drying oven after electrostatic spinning, and then dried to obtain SnCl 2 a/PVP fibrous membrane.
Preferably, in step 1, the SnCl is pre-oxidized 2 And vulcanizing the/PVP fiber membrane for 2-4h at the temperature to obtain the SnS/PVP fiber membrane.
Preferably, in step 1, the pre-oxidized SnCl is subjected to 2 The PVP fiber membrane and thiourea are calcined at the temperature, and the thiourea and the SnCl after preoxidation 2 The mass ratio of the/PVP fiber membrane is (5-10): 1, obtaining the SnS/PVP fiber membrane.
Preferably, in the step 2, the SnS/PVP fiber membrane is carbonized at the temperature for 4-8h to obtain the SnS/C flexible fiber membrane.
Preferably, in the step 3, the SnS/C flexible fiber membrane is sequentially soaked in the silver ammonia solution and the L-ascorbic acid solution for 5-60min and 5-60min.
The Ag nano particle coated SnS/C flexible thermoelectric fiber membrane is prepared by the preparation method of the Ag nano particle coated SnS/C flexible thermoelectric fiber membrane.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of an Ag nano particle coated SnS/C flexible thermoelectric fiber membrane, which comprises the steps of pre-oxidizing SnCl 2 And finally, sequentially soaking the SnS/C flexible fiber membrane in a silver ammonia solution and an L-ascorbic acid solution, and synthesizing the SnS/C flexible thermoelectric fiber membrane coated with Ag nano particles with different loading amounts by adjusting the concentrations of the silver ammonia solution and the L-ascorbic acid solution. The invention provides flexibility through the carbon skeleton, the Ag nano particles provide conductivity, and the SnS/C flexible fiber membrane coated with the Ag nano particles is constructed, so that the flexibility and the thermoelectric property of the fiber membrane are further improved. The Ag nano particles provide good conductivity for the SnS/C flexible thermoelectric fiber membrane, so that the thermoelectric property of the material is improved, and important material support is provided for further exploring the photoelectric property of the SnS/C flexible thermoelectric fiber membrane coated by the Ag nano particles and the application of the related field.
Furthermore, the invention can use DMF as organic solvent and SnCl 2 ·2H 2 The SnCl is prepared by using an electrostatic spinning process and taking O as a tin source and PVP as a binder 2 a/PVP flexible fiber membrane.
Drawings
FIG. 1a is an XRD pattern of the original SnS/C fiber film of examples 1-2 of the present invention.
FIG. 1b is an XRD pattern of the Ag-loaded SnS/C fiber film of examples 1-2 of the present invention.
Figure 2 is a SEM of original SnS/C fibrous membrane of example 1 of the invention.
FIG. 3 is an SEM of a raw SnS/C fiber membrane of example 2 of the invention.
FIG. 4 is an SEM of an SnS/C fiber membrane loaded with 5wt% Ag of example 1 of the present invention.
FIG. 5 is an SEM of an SnS/C fiber membrane loaded with 5wt% Ag of example 2 of the present invention.
FIG. 6 is an SEM of a SnS/C fiber membrane loaded with 10wt% Ag according to example 1 of the present invention.
FIG. 7 is an SnS/C fibrous membrane SEM loaded with 10wt% Ag in example 2 of the present invention.
Fig. 8a shows the conductivity of the composite fiber membrane of examples 1-3 of the present invention at room temperature as a function of the concentration of different silver ammonia solutions.
FIG. 8b is the Seebeck coefficient of the composite fiber membrane of examples 1 to 3 according to the present invention at room temperature as a function of the concentration of different silver ammonia solutions.
FIG. 8c is a graph of power factor at room temperature as a function of silver ammonia solution concentration for composite fiber membranes of examples 1-3 of the present invention.
Detailed Description
The invention will be described in detail with reference to the drawings, which are provided for the purpose of illustration and not for the purpose of limitation.
The invention discloses a preparation method of an Ag nano particle coated SnS/C flexible thermoelectric fiber membrane, which comprises the following steps:
the method comprises the following steps: 0.9-1.8g of SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF (dimethyl formamide) solvent, and dissolving the O in a colorless solution on a magnetic stirrer;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the second step into an injector, and preparing SnCl by using electrostatic spinning equipment 2 The electrostatic spinning voltage is 16-18kv, and the speed is 0.5-1.5mL/min;
step four: snCl 2 The PVP fiber membrane is dried in a vacuum drying oven to remove residual solvent, and is pre-oxidized in a muffle furnace after being dried, so that a linear polymer chain is converted into a heat-resistant trapezoidal annular structure to stabilize the fiber appearance and lay a foundation for next carbonization, wherein the pre-oxidation temperature is 230-280 ℃, and the time is 2-4 hours;
step five: will contain SnCl after pre-oxidation 2 Placing ceramic boat with/PVP fiber membrane in the gas upstream of the tube furnace, placing ceramic boat containing thiourea in the gas downstream of the tube furnace, and reacting with SnCl 2 Sulfurizing PVP fiber membrane at 230-280 deg.C for 2-4 hr, and mixing thiourea with SnCl after pre-oxidation 2 The mass ratio of the PVP fiber membrane is (5-10): 1, and Ar/H gas is introduced 2 The volume ratio is 95;
step six: will contain SnS/PPutting the VP fiber membrane ceramic boat into a tube furnace, carbonizing at 500-800 deg.C for 4-8H, introducing Ar/H gas 2 The volume ratio is 95;
step seven: soaking SnS/C flexible fiber membrane in 5-15wt% ammoniated silver solution and 5-10wt% L-ascorbic acid solution for 5-60min and 5-60min, and reducing Ag by L-ascorbic acid +2 Reducing the Ag into an Ag simple substance to obtain the Ag nano particle coated SnS/C flexible fiber membrane.
Example 1
The method comprises the following steps: 0.9g of SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF, and dissolving the O on a magnetic stirrer until the O is a colorless solution;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the step two into an injector, and preparing SnCl by using electrostatic spinning equipment 2 a/PVP fibrous membrane, wherein the voltage is 18kv and the speed is 1mL/min;
step four: snCl 2 Drying the PVP fiber membrane in a vacuum drying oven to remove residual solvent, and pre-oxidizing in a muffle furnace at 280 ℃ for 2h to stabilize the fiber morphology;
step five: will contain SnCl after pre-oxidation 2 Putting ceramic boat with PVP fiber membrane into the gas upstream of the tube furnace, putting ceramic boat containing thiourea into the gas downstream of the tube furnace, thiourea and pre-oxidized SnCl 2 The mass ratio of the/PVP fiber membrane is 5:1 and to SnCl 2 vulcanizing/PVP fiber membrane at 280 ℃ for 2H by introducing Ar/H gas 2 The ratio is 95;
step six: putting the ceramic boat filled with the SnS/PVP fiber membrane into a tube furnace, carbonizing at 650 ℃ for 8H, introducing Ar/H gas 2 And the ratio is 95.
Step seven: sequentially soaking the SnS/C flexible fiber membrane in 5wt% silver ammonia solution and 5wt% L-ascorbic acid solution for 20min to obtain the SnS/C flexible fiber membrane coated with the Ag nano particles.
Example 2
The method comprises the following steps: 0.9g of SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF, and dissolving the O on a magnetic stirrer until the O is colorless solution;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the step two into an injector, and preparing SnCl by using electrostatic spinning equipment 2 a/PVP fibrous membrane, wherein the voltage is 18kv and the speed is 1mL/min;
step four: snCl 2 Drying the PVP fiber membrane in a vacuum drying oven to remove residual solvent, and pre-oxidizing in a muffle furnace at 280 ℃ for 2h to stabilize the fiber morphology;
step five: will contain SnCl after pre-oxidation 2 Putting ceramic boat with PVP fiber membrane into the gas upstream of the tube furnace, putting ceramic boat containing thiourea into the gas downstream of the tube furnace, thiourea and pre-oxidized SnCl 2 The mass ratio of the/PVP fiber membrane is 5:1 and to SnCl 2 vulcanizing/PVP fiber membrane at 280 ℃ for 2H by introducing Ar/H gas 2 The ratio is 95;
step six: putting the ceramic boat filled with the SnS/PVP fibrous membrane into a tube furnace, carbonizing for 8 hours at 650 ℃, and introducing Ar/H gas 2 The ratio is 95;
step seven: and sequentially soaking the SnS/C flexible fiber membrane in a 10wt% silver ammonia solution and a 5wt% L-ascorbic acid solution for 20min to obtain the SnS/C flexible fiber membrane coated with the Ag nano particles.
Example 3
The method comprises the following steps: 0.9g of SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF, and dissolving the O on a magnetic stirrer until the O is a colorless solution;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the step two into an injector, and preparing the solution by using electrostatic spinning equipmentPreparation of SnCl 2 a/PVP fibrous membrane, wherein the voltage is 18kv and the speed is 1mL/min;
step four: snCl 2 Drying the PVP fiber membrane in a vacuum drying oven to remove residual solvent, and pre-oxidizing in a muffle furnace at 280 ℃ for 2h to stabilize the fiber morphology;
step five: will contain SnCl after pre-oxidation 2 Placing ceramic boat with PVP fiber membrane in the gas upstream of the tube furnace, placing ceramic boat with thiourea in the gas downstream of the tube furnace, thiourea and SnCl after pre-oxidation 2 The mass ratio of the/PVP fiber membrane is 5:1 and to SnCl 2 vulcanizing/PVP fiber membrane at 280 ℃ for 2H by introducing Ar/H gas 2 The ratio is 95;
step six: putting the ceramic boat filled with the SnS/PVP fiber membrane into a tube furnace, carbonizing at 650 ℃ for 8H, introducing Ar/H gas 2 The ratio is 95;
step seven: and sequentially soaking the SnS/C flexible fiber membrane in 15wt% of silver ammonia solution and 5wt% of L-ascorbic acid solution for 20min to obtain the SnS/C flexible fiber membrane coated with the Ag nano particles.
Example 4
The method comprises the following steps: 0.9g of SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF, and dissolving the O on a magnetic stirrer until the O is colorless solution;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the step two into an injector, and preparing SnCl by using electrostatic spinning equipment 2 a/PVP fibrous membrane, wherein the voltage is 18kv and the speed is 1mL/min;
step four: snCl 2 Drying the PVP fiber membrane in a vacuum drying oven to remove residual solvent, and pre-oxidizing in a muffle furnace at 280 ℃ for 2h to stabilize the fiber morphology;
step five: will contain SnCl after pre-oxidation 2 The ceramic boat with PVP fiber membrane is placed in the gas upstream of the tube furnace, the ceramic boat containing thiourea is placed in the gas downstream of the tube furnace, sulfurUrea and pre-oxidized SnCl 2 The mass ratio of the/PVP fiber membrane is 5:1 and to SnCl 2 vulcanizing/PVP fiber membrane at 250 ℃ for 3H by introducing Ar/H gas 2 The ratio is 95;
step six: putting the ceramic boat filled with the SnS/PVP fiber membrane into a tube furnace, carbonizing at 650 ℃ for 8H, introducing Ar/H gas 2 The ratio is 95;
step seven: and sequentially soaking the SnS/C flexible fiber film in 15wt% of silver ammonia solution and 10wt% of L-ascorbic acid solution for 10min to obtain the SnS/C flexible fiber film coated with the Ag nano particles.
Example 5
The method comprises the following steps: 1.35g SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF, and dissolving the O on a magnetic stirrer until the O is colorless solution;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the step two into an injector, and preparing SnCl by using electrostatic spinning equipment 2 A PVP fibre membrane, wherein the voltage is 16kv and the rate is 1.5mL/min;
step four: snCl 2 Drying the PVP fiber membrane in a vacuum drying oven to remove residual solvent, and pre-oxidizing in a muffle furnace at 250 ℃ for 4 hours after drying to stabilize the shape of the fiber;
step five: will contain SnCl after pre-oxidation 2 Putting ceramic boat with PVP fiber membrane into the gas upstream of the tube furnace, putting ceramic boat containing thiourea into the gas downstream of the tube furnace, thiourea and pre-oxidized SnCl 2 The mass ratio of the/PVP fiber membrane is 8:1 and to SnCl 2 Sulfurizing PVP fiber membrane at 230 deg.C for 4 hr under Ar/H gas 2 The ratio is 95;
step six: putting the ceramic boat filled with the SnS/PVP fiber membrane into a tube furnace, carbonizing at 750 ℃ for 6H, introducing Ar/H gas 2 The ratio is 95;
step seven: and sequentially soaking the SnS/C flexible fiber membrane in a 10wt% silver ammonia solution and a 8wt% L-ascorbic acid solution for 60min to obtain the SnS/C flexible fiber membrane coated with the Ag nano particles.
Example 6
The method comprises the following steps: 1.8g SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF, and dissolving the O on a magnetic stirrer until the O is a colorless solution;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the second step into an injector, and preparing SnCl by using electrostatic spinning equipment 2 a/PVP fibrous membrane, wherein the voltage is 18kv and the speed is 1mL/min;
step four: snCl 2 Drying the PVP fiber membrane in a vacuum drying oven to remove residual solvent, and pre-oxidizing in a muffle furnace at 280 ℃ for 2h to stabilize the fiber morphology;
step five: will contain SnCl after pre-oxidation 2 Putting ceramic boat with PVP fiber membrane into the gas upstream of the tube furnace, putting ceramic boat containing thiourea into the gas downstream of the tube furnace, thiourea and pre-oxidized SnCl 2 The mass ratio of the/PVP fiber membrane is 10 2 vulcanizing/PVP fiber membrane at 280 ℃ for 2H by introducing Ar/H gas 2 The ratio is 95;
step six: putting the ceramic boat filled with the SnS/PVP fiber membrane into a tube furnace, carbonizing at 550 ℃ for 8H, introducing Ar/H gas 2 The ratio is 95;
step seven: and (3) sequentially soaking the SnS/C flexible fiber membrane in a 10wt% silver ammonia solution and a 5wt% L-ascorbic acid solution for 5min to obtain the SnS/C flexible fiber membrane coated with the Ag nano particles.
Example 7
The method comprises the following steps: 1.35g SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF, and dissolving the O on a magnetic stirrer until the O is a colorless solution;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the second step into an injector, and preparing SnCl by using electrostatic spinning equipment 2 a/PVP fibrous membrane, wherein the voltage is 18kv and the speed is 1mL/min;
step four: snCl 2 Drying the PVP fiber membrane in a vacuum drying oven to remove residual solvent, and pre-oxidizing in a muffle furnace at 280 ℃ for 2h to stabilize the fiber morphology;
step five: will contain SnCl after pre-oxidation 2 Putting ceramic boat with PVP fiber membrane into the gas upstream of the tube furnace, putting ceramic boat containing thiourea into the gas downstream of the tube furnace, thiourea and pre-oxidized SnCl 2 The mass ratio of the/PVP fiber membrane is 8:1, to SnCl 2 vulcanizing/PVP fiber membrane at 250 ℃ for 3H by introducing Ar/H gas 2 The ratio is 95;
step six: putting the ceramic boat with SnS/PVP fiber membrane in a tube furnace, carbonizing at 700 deg.C for 6H, introducing Ar/H gas 2 The ratio is 95;
step seven: sequentially soaking the SnS/C flexible fiber membrane in 10wt% of silver ammonia solution and 5wt% of L-ascorbic acid solution for 40min to obtain the SnS/C flexible fiber membrane coated with the Ag nano particles.
Example 8
The method comprises the following steps: 0.9g of SnCl 2 ·2H 2 Dispersing O as a tin source in 5mL of DMF, and dissolving the O on a magnetic stirrer until the O is a colorless solution;
step two: adding 0.5g of PVP into the solution obtained in the first step, and stirring on a magnetic stirrer until the PVP is completely dissolved;
step three: putting the solution obtained in the step two into an injector, and preparing SnCl by using electrostatic spinning equipment 2 A PVP-fibre membrane, wherein the voltage is 16kv and the rate is 1mL/min;
step four: snCl 2 The PVP fiber membrane is dried in a vacuum drying oven to remove residual solvent, and is pre-oxidized in a muffle furnace at 260 ℃ for 4 hours after being dried to stabilize the fiber shape;
step five: will be provided with pre-oxidationRear SnCl 2 Placing ceramic boat with PVP fiber membrane in the gas upstream of the tube furnace, placing ceramic boat with thiourea in the gas downstream of the tube furnace, thiourea and SnCl after pre-oxidation 2 The mass ratio of the/PVP fiber membrane is 5:1 and to SnCl 2 vulcanizing/PVP fiber membrane at 280 ℃ for 2H by introducing Ar/H gas 2 The ratio is 95;
step six: putting the ceramic boat with SnS/PVP fiber membrane in a tube furnace, carbonizing at 600 deg.C for 8 hr, introducing Ar/H gas 2 The ratio is 95;
step seven: and (3) sequentially soaking the SnS/C flexible fiber membrane in a 10wt% silver ammonia solution and a 5wt% L-ascorbic acid solution for 30min to obtain the SnS/C flexible fiber membrane coated with the Ag nano particles.
According to the invention, XRD analysis and SEM characterization are carried out on the SnS/C flexible thermoelectric fiber membrane, the successful loading of Ag nano particles on SnS/C fibers is proved, and the conductivity is improved through the test of the conductivity of the fiber membrane.
FIG. 1a is an XRD (X-ray diffraction) spectrum of an original SnS/C fiber membrane, and the comparison of the XRD spectrum and a standard card shows that the prepared fiber membrane is a SnS pure phase; FIG. 1b is an XRD spectrum of the SnS/C fiber membrane loaded with Ag in examples 1-2 of the present invention, and it can be seen from the XRD spectrum that Ag nanoparticles are successfully loaded on the SnS/C fiber membrane after being soaked in silver ammonia solution and L-ascorbic acid solution.
Fig. 4, 5, 6 and 7 are SEM images of the silver ammonia solution soaked in different concentrations, respectively, and it can be seen from the images that as the concentration of the silver ammonia solution increases, the particle size of the Ag nanoparticles increases and the loading amount increases, compared with the original SnS/C fiber membrane of fig. 2 and 3.
Fig. 8a, 8b and 8c are graphs showing the changes of the conductivity, the Seebeck coefficient and the power factor of the composite fiber membranes of examples 1 to 3 of the invention with the concentrations of different silver ammonia solutions at room temperature, respectively. With the increase of the concentration of the silver ammonia solution, the conductivity of the composite fiber membrane is also increased, but the Seebeck coefficient is reduced, and finally the power factor of the composite membrane reaches the maximum under the condition of 5 percent of silver ammonia solution.

Claims (2)

1. A preparation method of an Ag nanoparticle coated SnS/C flexible thermoelectric fiber membrane is characterized by comprising the following steps:
step 1, according to (0.9-1.8): 0.5 mass ratio of SnCl 2 •2H 2 Dissolving O and polyvinylpyrrolidone in DMF to obtain a mixed solution, performing electrostatic spinning on the mixed solution at a voltage of 16-18kv and a speed of 0.5-1.5mL/min, drying in a vacuum drying oven, and drying to obtain SnCl 2 /PVP fiber membrane, snCl 2 the/PVP fiber membrane is calcined at 230-280 ℃ for 2-4h to obtain the pre-oxidized SnCl 2 PVP fiber membrane, according to 1: (5-10) mass ratio of the pre-oxidized SnCl 2 Vulcanizing the/PVP fiber membrane and thiourea at 230-280 ℃ for 2-4h to obtain a SnS/PVP fiber membrane;
step 2, carbonizing the SnS/PVP fibrous membrane at 500-800 ℃ for 4-8h in one step to obtain an SnS/C flexible fibrous membrane;
and 3, sequentially soaking the SnS/C flexible fiber membrane in a 5% silver ammonia solution and a 5% -10% L-ascorbic acid solution for 5-60min to obtain the Ag nano particle coated SnS/C flexible thermoelectric fiber membrane.
2. The Ag nano particle coated SnS/C flexible thermoelectric fiber membrane prepared by the preparation method of the Ag nano particle coated SnS/C flexible thermoelectric fiber membrane of claim 1.
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