CN113540335B - S-doped SnSe/CNTs composite flexible film and preparation method thereof - Google Patents
S-doped SnSe/CNTs composite flexible film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an S-doped SnSe/CNTs composite flexible film and a preparation method thereof, belonging to the technical field of nano energy thermoelectric materials. The preparation method comprises the following steps: na is mixed with 2 SeO 3 And SnCl 2 ·2H 2 Dissolving O in a solvent A to obtain a solution A, dissolving a monomer S in the solution A to obtain a solution B, and ultrasonically dispersing CNTs in the solution B to obtain a solution C; carrying out solvothermal reaction on the solution C to obtain a product system, and drying the product system after centrifugal cleaning to obtain a dried product D; ultrasonically dispersing the dried product D in a solvent B, carrying out vacuum filtration to obtain a film E, drying to obtain an S-doped SnSe/CNTs composite flexible film, wherein the S-doped SnSe/CNTs composite flexible film is SnSe 1‑x S x the/CNTs composite flexible film has x more than 0 and less than or equal to 0.05. The S-doped SnSe/CNTs composite flexible film prepared by the preparation method improves the conductivity while maintaining the flexibility of the composite film.
Description
Technical Field
The invention belongs to the technical field of nano energy thermoelectric materials, and relates to an S-doped SnSe/CNTs composite flexible film and a preparation method thereof.
Background
In the combustion process of fossil fuels such as coal, oil, and natural gas, only about 30% to 40% of energy can be effectively utilized, and the remaining 60% to 70% of energy is discharged in the form of waste heat and wasted. With the increasing severity of energy and environmental problems, the development of new and efficient green and clean energy technology is urgent. The thermoelectric conversion technology can directly convert waste heat into electric energy for recycling, secondary pollution of carbon dioxide, nitrogen dioxide, carbon monoxide, sulfur dioxide and the like cannot be generated in the process, and various natural heat energy sources such as solar energy, geothermal energy and the like can be effectively utilized for electric energy conversion. In addition, the urgent need for environmentally friendly, stable, long-life power supplies has driven the explosion of the market for miniaturized and integrated electronic products (including wearable and medical implantable devices). Flexible thermoelectric materials and devices are receiving increasing attention because they are capable of converting heat directly into electrical energy through integration with a heat source. However, the flexible inorganic thermoelectric thin film lacks mechanical flexibility, and therefore, it is necessary to design a flexible thermoelectric material that can maintain thermoelectric conversion efficiency and also has a certain flexibility.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an S-doped SnSe/CNTs composite flexible film and a preparation method thereof, which improve the conductivity while maintaining the flexibility of the composite film.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of an S-doped SnSe/CNTs composite flexible film, which comprises the following steps:
1) Na is mixed with 2 SeO 3 And SnCl 2 ·2H 2 Dissolving O in solvent A to obtain solution A, and dissolving O in solvent A to obtain solution A 2- Ion content and Se 2- X is more than 0 and less than or equal to 0.05, the monomer S is dissolved in the solution A to obtain solution B, and the CNTs are ultrasonically dispersed in the solution B to obtain solution C; 2) Carrying out solvothermal reaction on the solution C to obtain a product system, and drying the product system after centrifugal cleaning to obtain a dried product D; 3) Ultrasonically dispersing the dried product D in a solvent B, carrying out vacuum filtration to obtain a film E, and drying the film E to obtain SnSe 1-x S x And x is more than 0 and less than or equal to 0.05 to obtain the S-doped SnSe/CNTs composite flexible film.
Preferably, snCl 2 ·2H 2 The reaction feed ratio of O to CNTs is 1-10 mmol: 0.1-0.5 mg;
Na 2 SeO 3 ，SnCl 2 ·2H 2 the molar ratio of the O to the elemental S in the reaction is 1-x:1, x is more than 0 and less than or equal to 0.05.
Preferably, snCl 2 ·2H 2 The reaction feeding ratio of the O to the solvent A and the solvent B is 1-10 mmol:40mL of: 10mL.
Preferably, solvent a is ethylene glycol and solvent B is ethanol.
Preferably, the reaction parameters of the solvothermal reaction include: the temperature is 180-230 ℃, and the time is 12-36 h.
Preferably, the drying operating parameters of the dried product D comprise: the time is 8-12 h, and the temperature is 70 ℃.
Preferably, the suction filtration time of the vacuum filtration is 0.5-2 h.
Preferably, the drying treatment of the film E comprises: the drying time is 5-8 h, and the drying temperature is 60-80 ℃.
The invention discloses an S-doped SnSe/CNTs composite flexible film prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the S-doped SnSe/CNTs composite flexible film provided by the invention adopts the combination of the solvothermal method and the vacuum filtration technology to prepare the S-doped SnSe/CNTs composite flexible film, and the synthesis process is simple and easy to operate. According to the invention, the electrical conductivity of the film is improved by adding the CNTs, and the thermoelectric property of the S-doped SnSe/CNTs film is effectively improved; an S-doped SnSe material is obtained in the synthesis process through a solvothermal method, the carrier transmission capability of the material is improved, a new idea is provided for the synthesis of SnSe, and the problem of agglomeration of CNTs can be reduced and the dispersibility is improved through solvothermal reaction. The thickness of the S-doped SnSe/CNTs thin-film thermoelectric material can be effectively controlled through a vacuum filtration method, and the flexibility and the stability of the SnSe thin-film thermoelectric material can be further improved. Therefore, the preparation method can effectively solve the problem of poor flexibility of the SnSe thin film thermoelectric material and improve the conductivity of the SnSe thin film.
The invention discloses an S-doped SnSe/CNTs composite flexible film prepared by the preparation method, wherein the CNTs have excellent electrical property, so that the electrical conductivity of the system can be effectively improved, and the electrical conductivity is excellent at room temperature.
Furthermore, related tests show that the conductivity of the S-doped SnSe/CNTs composite flexible film with the novel micro-plate structure can reach 10-15S/cm.
Drawings
FIG. 1 is an SEM image of an S-doped SnSe/CNTs composite flexible thin film at 1500 times magnification;
FIG. 2 is an SEM image of a S-doped SnSe/CNTs composite flexible film magnified by 35000 times.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Moreover, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of an S-doped SnSe/CNTs composite flexible film, which comprises the following steps:
step 1, adding Na 2 SeO 3 And 1 to 10mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in the presence of S 2- Ion content and Se 2- Dissolving the monomer S in the solution A to obtain a solution B, wherein the ion ratio is 1-x: x, x is more than 0 and less than or equal to 0.05;
step 2, weighing 0.1-0.5 mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at the temperature of 180-230 ℃ for 12-36 h, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 8-12 h at the temperature of 70 ℃ to obtain a dried product D;
step 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration for 0.5-2 h to obtain a film E;
step 5, drying the film E in a drying oven for 5-8 h at the drying temperature of 60-80 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x And x is more than 0 and less than or equal to 0.05, namely the S-doped SnSe/CNTs composite flexible film.
The preparation method is adoptedSnSe of novel micro-plate structure 1-x S x the/CNTs composite flexible film has x more than 0 and less than or equal to 0.05 and excellent conductivity. The Seebeck coefficient/resistance analysis system test shows that the conductivity of the material can reach 10-15S/cm at room temperature.
The invention is further illustrated by the following specific figures and examples:
example 1
Step 1, adding Na 2 SeO 3 And 1mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in the presence of S 2- Ion content and Se 2- X, x =0.01, dissolving S in solution a to give solution B;
step 2, weighing 0.1mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at the temperature of 200 ℃ for 36 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 8 hours at the temperature of 70 ℃ to obtain a dried product D;
step 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, and carrying out vacuum filtration for 0.5 time to obtain a film E;
step 5, drying the film E in a drying oven for 5 hours at the drying temperature of 60 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x And x =0.01, namely the S-doped SnSe/CNTs composite flexible film.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The test of a Seebeck coefficient/resistance analysis system shows that the electrical conductivity of the/CNTs composite flexible film can reach 12.3S/cm at room temperature.
Example 2
Step 1, adding Na 2 SeO 3 And 5mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in the presence of S 2- Ion content and Se 2- Ion ratio of 1-x: x, x =0.02, S is dissolved in solventObtaining a solution B in the solution A;
step 2, weighing 0.2mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at the temperature of 210 ℃ for 30 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 9 hours at the temperature of 70 ℃ to obtain a dried product D;
step 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for 1h to obtain a film E;
step 5, drying the film E in a drying oven for 6 hours at the drying temperature of 70 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x And (2) the/CNTs composite flexible film, wherein x =0.02, namely the S-doped SnSe/CNTs composite flexible film.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 13.5S/cm through the test of a Seebeck coefficient/resistance analysis system.
Example 3
Step 1, adding Na 2 SeO 3 And 3mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in S 2- Ion content and Se 2- Dissolving S in the solution A to obtain a solution B, wherein the ion ratio is 1-x: x, and x = 0.03;
step 2, weighing 0.5mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at 230 ℃ for 12 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 8 hours at 70 ℃ to obtain a dried product D;
and 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for 2h to obtain a film E.
Step 5, drying the film E in a drying oven for 8 hours at the drying temperature of 70 DEG CTo obtain the final SnSe with a novel micro-plate structure 1-x S x And x =0.03, namely the S-doped SnSe/CNTs composite flexible film.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 11.3S/cm through the test of a Seebeck coefficient/resistance analysis system.
Example 4
Step 1, adding Na 2 SeO 3 And 2mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in the presence of S 2- Ion content and Se 2- Dissolving S in the solution A to obtain a solution B, wherein the ion ratio is 1-x: x, and x = 0.01;
step 2, weighing 0.4mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at 220 ℃ for 24 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 10 hours at 70 ℃ to obtain a dried product D;
and 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for 1h to obtain a film E.
Step 5, drying the film E in a drying oven for 8 hours at the drying temperature of 80 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x The composite flexible film of the/CNTs is the S-doped SnSe/CNTs composite flexible film with x = 0.01.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 14.3S/cm through the test of a Seebeck coefficient/resistance analysis system.
Example 5
Step 1, adding Na 2 SeO 3 And 9mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in the presence of S 2- Ion content and Se 2- Ion ratio of 1-xX, x =0.05, dissolving S in solution a to obtain solution B;
step 2, weighing 0.3mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at 190 ℃ for 18h, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 12h at 70 ℃ to obtain a dried product D;
and 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for 2h to obtain a film E.
Step 5, drying the film E in a drying oven for 8 hours at the drying temperature of 70 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x And x =0.05, namely the S-doped SnSe/CNTs composite flexible film.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 13.6S/cm through the test of a Seebeck coefficient/resistance analysis system.
Example 6
Step 1, adding Na 2 SeO 3 And 8mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in S 2- Ion content and Se 2- Dissolving S in the solution A to obtain a solution B, wherein the ion ratio is 1-x: x, and x = 0.03;
step 2, weighing 0.5mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at 180 ℃ for 36 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 8 hours at 70 ℃ to obtain a dried product D;
and 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for 2h to obtain a film E.
Step 5, placing the film E in a drying ovenDrying for 8h at 70 deg.C to obtain SnSe with novel final microplate structure 1-x S x The composite flexible film of the/CNTs is the S-doped SnSe/CNTs composite flexible film with x = 0.03.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 12.5S/cm through the test of a Seebeck coefficient/resistance analysis system.
Example 7
Step 1, adding Na 2 SeO 3 And 6mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in the presence of S 2- Ion content and Se 2- X, x =0.02, dissolving S in solution a to obtain solution B;
step 2, weighing 0.2mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at the temperature of 200 ℃ for 20 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 12 hours at the temperature of 70 ℃ to obtain a dried product D;
and 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for 1h to obtain the film E.
Step 5, drying the film E in a drying oven for 6 hours at the drying temperature of 60-80 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x The composite flexible film of the/CNTs is the S-doped SnSe/CNTs composite flexible film with x = 0.02.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 13.1S/cm through the test of a Seebeck coefficient/resistance analysis system.
Example 8
Step 1, adding Na 2 SeO 3 And 6mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in S 2- Ion containingAmount and Se 2- Dissolving S in the solution A to obtain a solution B, wherein the ion ratio is 1-x: x, and x = 0.04;
step 2, weighing 0.4mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at the temperature of 200 ℃ for 36 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 8 hours at the temperature of 70 ℃ to obtain a dried product D;
and 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for 2h to obtain a film E.
Step 5, drying the film E in a drying oven for 8 hours at the drying temperature of 60 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x The flexible composite film of/CNTs, =0.04, namely the S-doped SnSe/CNTs composite flexible film.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 10.8S/cm through the test of a Seebeck coefficient/resistance analysis system.
Example 9
Step 1, adding Na 2 SeO 3 And 8mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in the presence of S 2- Ion content and Se 2- Dissolving S in the solution A to obtain a solution B, wherein the ion ratio is 1-x: x, and x = 0.01;
step 2, weighing 0.2mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at 180 ℃ for 36 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 10 hours at 70 ℃ to obtain a dried product D;
and 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for 1.5h to obtain the film E.
Step 5, drying the film E in a drying oven for 6 hours at the drying temperature of 70 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x The composite flexible film of the/CNTs is the S-doped SnSe/CNTs composite flexible film with x = 0.01.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 11.3S/cm through the test of a Seebeck coefficient/resistance analysis system.
Example 10
Step 1, adding Na 2 SeO 3 And 10mmol of SnCl 2 ·2H 2 Dissolving O in 40mL of ethylene glycol solution at a molar ratio of 1-x:1 to obtain a solution A, and dissolving the solution A in S 2- Ion content and Se 2- Dissolving S in the solution A to obtain a solution B, wherein the ion ratio is 1-x: x, and x = 0.04;
step 2, weighing 0.5mg of CNTs, and ultrasonically dispersing the CNTs in the solution B to obtain a solution C;
step 3, putting the solution C into a reaction kettle, carrying out a solvothermal reaction at 230 ℃ for 36 hours, centrifugally cleaning an obtained product system after the reaction is finished to obtain a product D, and drying the product D in a vacuum drying oven for 8 hours at 70 ℃ to obtain a dried product D;
and 4, ultrasonically dispersing the dried product D in 10mL of ethanol solution, carrying out vacuum filtration, and carrying out suction filtration for h to obtain a film E.
Step 5, drying the film E in a drying oven for 8 hours at the drying temperature of 80 ℃ to obtain the final SnSe with the novel micro-plate structure 1-x S x And x =0.04, namely the S-doped SnSe/CNTs composite flexible film.
SnSe of novel micro-plate structure prepared by the embodiment 1-x S x The electrical conductivity of the/CNTs composite flexible film can reach 12.5S/cm through the test of a Seebeck coefficient/resistance analysis system.
Referring to FIG. 1, it can be seen that SnSe is obtained by vacuum filtration 1-x S x the/CNTs composite flexible film (S-doped SnSe/CNTs composite flexible film) has better density;
referring to FIG. 2, it can be seen that the SnSe is produced 1-x S x CNTs in the/CNTs composite flexible thin film (S-doped SnSe/CNTs composite flexible thin film) are uniformly dispersed in the system, which is beneficial to the improvement of the conductivity of the system.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of an S-doped SnSe/CNTs composite flexible film is characterized by comprising the following steps:
1) Mixing Na 2 SeO 3 And SnCl 2 ·2H 2 Dissolving O in a solvent A to obtain a solution A, dissolving a monomer S in the solution A to obtain a solution B, and ultrasonically dispersing CNTs in the solution B to obtain a solution C;
2) Carrying out solvent thermal reaction on the solution C to obtain a product system, and drying the product system after centrifugal cleaning to obtain a dried product D;
3) Ultrasonically dispersing the dried product D in a solvent B, carrying out vacuum filtration to obtain a film E, and drying the film E to obtain an S-doped SnSe/CNTs composite flexible film;
the obtained S-doped SnSe/CNTs composite flexible film is SnSe 1-x S x the/CNTs composite flexible film has x more than 0 and less than or equal to 0.05.
2. The preparation method of the S-doped SnSe/CNTs composite flexible film according to claim 1, wherein SnCl 2 ·2H 2 The reaction charge ratio of O and CNTs is 1-10 mmol: 0.1-0.5 mg;
Na 2 SeO 3 ，SnCl 2 ·2H 2 the molar ratio of the O to the elemental S in the reaction is 1-x:1, x is more than 0 and less than or equal to 0.05.
3. The preparation method of the S-doped SnSe/CNTs composite flexible film according to claim 1, wherein SnCl 2 ·2H 2 The reaction feeding ratio of the O to the solvent A and the solvent B is 1-10 mmol:40mL of: 10mL.
4. The method for preparing an S-doped SnSe/CNTs composite flexible film according to claim 1, wherein solvent A is ethylene glycol and solvent B is ethanol.
5. The method for preparing an S-doped SnSe/CNTs composite flexible film according to claim 1, wherein the reaction parameters of the solvothermal reaction comprise: the temperature is 180-230 ℃, and the time is 12-36 h.
6. The method for preparing S-doped SnSe/CNTs composite flexible thin film according to claim 1, wherein the drying parameters of the dried product D include: the time is 8-12 h, and the temperature is 70 ℃.
7. The preparation method of the S-doped SnSe/CNTs composite flexible film according to claim 1, characterized in that the vacuum filtration time is 0.5-2 h.
8. The method for preparing the S-doped SnSe/CNTs composite flexible film according to claim 1, wherein the drying treatment of the film E comprises: the drying time is 5-8 h, and the drying temperature is 60-80 ℃.
9. An S-doped SnSe/CNTs composite flexible film prepared by the preparation method of any one of claims 1 to 8.
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