A PEDOT:PSS / VN 0.52 O 0.26 Preparation method of thermoelectric composite film

Abstract

The present invention discloses a VN 0.52 O 0.26 The method of combining nanoparticles with PEDOT:PSS thermoelectric nanocomposite film is used to prepare VN by pyrolysis of urea to generate ammonia and react with NaVO3 at high temperature. 0.52 O 0.26 Nanoparticles, constructing P-type PEDOT:PSS and N-type VN 0.52 O 0.26 The pn junction barrier of the nanoparticle organic-inorganic composite and the energy filtering effect between the nanoparticles and the organic PEDOT interface are used to improve the conductivity, Seebeck coefficient and power factor of the thermoelectric composite film. The organic-inorganic thermoelectric nanocomposite film prepared has a Seebeck coefficient of 62.75μV / K and a power factor of 474.424μWm at 90°C. ‑1 K ‑2 .

Description

Technical Field

[0001] The present invention belongs to the technical field of thermoelectric materials, and more specifically relates to a flexible, low-cost VN 0.52 O 0.26 Preparation method of PEDOT:PSS thermoelectric composite film. Background Art

[0002] The thermoelectric conversion efficiency of thermoelectric materials is determined by the thermoelectric figure of merit (ZT): ZT = σS 2 T / κ, where σ, S, κ, and T represent electrical conductivity, Seebeck coefficient, thermal conductivity, and absolute temperature, respectively. A good thermoelectric material should possess high electrical conductivity, a high Seebeck coefficient, and low thermal conductivity. A material's electrical conductivity is related to its Fermi level position and density of states. Manipulating the Fermi level position of a material by doping can significantly improve its electrical conductivity. Manipulating the Fermi level position, the density of states distribution, and creating energy-filtering interfaces can optimize the material's carrier concentration and even break the constraints between thermoelectric parameters, thereby achieving high-performance organic thermoelectric materials.

[0003] Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), namely PEDOT:PSS, is a p-type conductive polymer that can only achieve stable hole conduction. Many thermoelectric and bioelectronic devices require complementary hole-conducting materials and electron-conducting (i.e., n-type) materials. To this end, the present invention adds VN to PEDOT:PSS. 0.52 O 0.26 Nanoparticles, constructing n-type VN 0.52 O 0.26 PN junction of nanoparticles and p-type polymer ink PEDOT:PSS. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for preparing VN by using NaVO3 and urea. 0.52 O 0.26 Preparation method of nanoparticles, and adding VN to poly (3,4-ethylenedioxythiophene): poly (styrene sulfonic acid), namely PEDOT:PSS 0.52 O 0.26 Nanoparticles prepare thermoelectric nanocomposite films to achieve n-type VN 0.52 O 0.26 The complementary use of nanoparticles to p-type polymer ink PEDOT:PSS enables the preparation of power generation products that can reduce carbon emissions.

[0005] According to a first aspect of the present invention, the present invention provides a PEDOT:PSS / VN 0.52 O 0.26 Preparation method of thermoelectric composite membrane, using urea and NaVO3 to prepare VN by molten salt method 0.52 O0.26 Nanoparticles, VN 0.52 O 0.26 The nanoparticles were mixed with PEDOT:PSS aqueous solution and prepared by drop coating method. 0.52 O 0.26 Thermoelectric composite membrane; the salt used in the molten salt method contains NaCl and KCl.

[0006] The specific steps include:

[0007] a. Clean and dry the quartz tube and two crucibles in the chemical vapor deposition (CVD) furnace;

[0008] b. Mix NaVO3 with NaCl and KCl and grind them finely in an agate mortar, then place them in a crucible;

[0009] c. Grind urea in an agate mortar, and finally take an appropriate amount of urea into the crucible;

[0010] d. Open the argon gas connection to the CVD furnace and place the crucible containing urea into the low-temperature zone of the CVD furnace; the temperature of the low-temperature zone is 180-200 degrees Celsius;

[0011] e. The crucible containing NaVO3 in step b is placed in a CVD furnace;

[0012] f. Tighten the CVD furnace flange;

[0013] g. Close the furnace cover, set the temperature program for the low and high temperature zones of the CVD furnace, press the start button, and start firing the sample;

[0014] h. After the sample is fired, wait until the temperature in the furnace drops to room temperature and take out the sample to obtain VN 0.52 O 0.26 , means calculated according to the molar ratio V:N:O=1:0.52:0.26;

[0015] i. Place the sample in a beaker, add deionized water, centrifuge, and remove the lower layer of solution; re-stir and disperse the solution, centrifuge, and remove the upper layer of liquid, and measure VN 0.52 O 0.26 Concentration of aqueous solution;

[0016] j. PEDOT:PSS aqueous solution was filtered using a PVDF porous membrane as a substrate, and 5% by volume of dimethyl sulfoxide (DMSO) was added to the PEDOT:PSS aqueous solution; wherein DMSO can be replaced by DMF or ethylene glycol;

[0017] k. Prepare the test tube, clean and dry it; add VN into the test tube. 0.52 O 0.26After drying, add PEDOT:PSS aqueous solution to the test tube, put the test tube into the ultrasonic machine and ultrasonicate to mix the solution evenly; calculate the weight of the substance and control VN 0.52 O 0.26 The weight percentage of PEDOT:PSS is 0.5%-90%;

[0018] l. The prepared mixed solution is dropped onto a glass substrate and allowed to stand to form a film;

[0019] m. Place the glass substrate in a CVD furnace, dry and anneal, and then drop a layer of DMSO on the film for surface modification. Then place it in a CVD furnace again, dry and vacuum anneal to obtain PEDOT:PSS / VN 0.52 O 0.26 Thermoelectric composite film;

[0020] PEDOT:PSS / VN 0.52 O 0.26 Thermoelectric composite film performance test: the electrode is made of silver paste, the electrode is led out with a lead, and the film is packaged to complete the preparation.

[0021] Preferably, in step a, first rinse the quartz tube with deionized water, wipe the water stains on the outer wall of the quartz tube dry, and put it into the CVD furnace. Put a crucible with a length of 10 cm and a width of 3 cm into a 500 ml beaker and ultrasonicate it with acetone, alcohol, and deionized water for more than 3 times in sequence, and then put it into a dryer for drying. Then put the dried crucible into the central temperature zone of the furnace. Set the furnace temperature to: rise from room temperature to 500 degrees in 30 minutes, keep warm for 30 minutes, rise to 1000 degrees in 30 minutes, keep warm for 30 minutes, end the program, and let the CVD furnace cool down naturally. Take out the crucible in the furnace and observe whether there is white substance in the quartz tube. If so, rinse the quartz tube again and burn the furnace clean according to the program set before the furnace.

[0022] Preferably, in step b, the total weight of NaCl and KCl is mixed with NaVO3 in a weight ratio of 1:1, and the two salts of NaCl and KCl are in a molar ratio of Na:K of 1:1. The total weight of the mixed sample is 2g. The ground sample is placed in a crucible with a length of 10 cm and a width of 3 cm and flattened. It is necessary to wear a mask and rubber gloves during operation. NaVO3 has a damaging effect on the skin and respiratory tract. Be careful not to touch the skin directly during operation. The mixed sample needs to be ground for about 3 hours. Grinding the sample finely can make the sample react more fully. The present invention uses low melting point additives: NaCl and KCl to reduce VN 0.52 O 0.26The present invention uses urea as a nitrogen source and utilizes the temperature gradient of a dual-zone CVD furnace to transport ammonia generated by urea at 180-200 degrees into a mixture of NaVO3, NaCl, and KCl under an argon flow, allowing the ammonia and NaVO3 to fully react in the high-temperature molten salt.

[0023] Preferably, in step c, the agate mortar and grinding rod are cleaned and dried, 15 g of urea is placed in the agate mortar and ground for 20 minutes, and the ground urea is transferred to a crucible. Fine grinding of urea enables thermal decomposition of ammonia and reaction with NaVO3 during firing.

[0024] Preferably, in step d, before sample is put into CVD furnace, quartz tube should be first vacuumized, then screw stove right side cock, then pass into argon gas, gas flow is adjusted to 100sccm, open the cock on stove left side, argon gas is passed in quartz tube, when the pressure in stove is balanced with the external environment, screw the knob on stove left side, open mechanical pump, open the cock on stove right side, the argon gas in stove is discharged.Then screw the knob on stove right side, close mechanical pump, unplug the pipe connected to mechanical pump, open the knob on stove left side, argon gas is passed in quartz tube, when the pressure in quartz tube is balanced with the external environment, unscrew the cock on stove right side, and open the lid on stove right side quartz tube, with elongated iron rod, the crucible equipped with urea is put into CVD furnace left side low temperature zone.

[0025] Preferably, in step e, placing the crucible containing the NaVO3 and salt mixture in the center of the high temperature zone of the CVD furnace is conducive to keeping the crucible in a uniform temperature range.

[0026] Preferably, in step f, the flange on the right side of the furnace is closed and the knob is turned on. Argon is used as a protective gas to isolate the air and prevent the air from reacting with the mixture at high temperature.

[0027] Preferably, in step g, the lid of the CVD furnace is closed and the temperature is set as follows:

[0028] The high temperature zone heating program is set as follows: the high temperature zone temperature is raised from room temperature to 110 degrees in 30 minutes, kept warm for 20 minutes, then raised to 600 degrees at a heating rate of 1.5 degrees per minute, kept warm for 5 hours, and then the furnace is allowed to cool naturally. The high temperature zone temperature can be set between 590-610 degrees. VN with good crystallinity and stable composition is prepared. 0.52 O 0.26 Nanoparticles.

[0029] The low temperature zone heating program is set as follows: the low temperature zone temperature is raised from room temperature to 100 degrees in 30 minutes, kept warm for 20 minutes, then raised to 200 degrees at a heating rate of 1.5 degrees per minute, kept warm for 5 hours, and then the furnace is allowed to cool naturally. Urea is pyrolyzed at 200 degrees to produce ammonia. The present invention uses the ammonia produced by urea to react with NaVO3 to produce VN 0.52 O 0.26 .VN 0.52 O 0.26 Nanoparticle crystal properties XRD curves such as Figure 1 (a) shows that the cubic phase VN 0.52 O 0.26 (PDF:No.37-1178) Peak matching, Figure 1 (b) is VN 0.52 O 0.26 Nanoparticles ranging in size from 50-500nm.

[0030] Preferably, in step h, after the sample is fired, wait until the temperature in the furnace drops to room temperature, tighten the stopcock on the left side of the CVD, turn off the argon gas, and take out the sample from the right side of the furnace.

[0031] Preferably, in step i, the prepared VN 0.52 O 0.26 Place in a beaker, add deionized water, ultrasonicate and centrifuge at 8000 rpm, repeat ultrasonication and centrifugation 6 times, collect the lower layer solution. Re-stir the lower layer solution, ultrasonicate, centrifuge at 1000 rpm for 10 minutes, collect the upper layer solution, dilute the upper layer solution VN 0.52 O 0.26 Nanoparticles to a certain concentration (preferably 1.64 mg / ml, which is beneficial to VN 0.52 O 0.26 / PEDOT:PSS weight ratio).

[0032] Preferably, in step j, the PEDOT:PSS solution is filtered using a PVDF porous membrane syringe filter with a pore size of 450 nm. 2000 μL of the PEDOT:PSS filtrate is placed in a 5 ml test tube, 50 μL of DMSO is added, and the mixture is sonicated for 10 minutes to mix uniformly.

[0033] Preferably, the specific configuration method of step k is as follows: prepare a small test tube, clean the test tube and dry it. Add VN 0.52 O 0.26 Aqueous solution, then add appropriate amount of DMSO. 0.52 O 0.26 The test tube containing the aqueous solution was dried, and then the PEDOT:PSS solution in step j was added to the dried test tube to control VN 0.52 O 0.26The weight percentage of PEDOT:PSS was 1%wt, and ultrasonication was performed for 10 min.

[0034] Prepare a 1mL test tube, clean it and dry it. Add VN 0.52 O 0.26 Aqueous solution (e.g. 6.4 μl, 1.64 mg / ml), then 25 μl of DMSO was added. 0.52 O 0.26 The test tube containing the aqueous solution was dried, and 1000 μl of the PEDOT:PSS solution in step j was added to the dried test tube. 0.52 O 0.26 The weight ratio of PEDOT / PSS was 1% wt, and ultrasonication was performed for 10 min.

[0035] Preferably, in step 1, 120 microliters of the prepared solution is drop-coated on a 1 cm x 1 cm glass substrate. The solution is then allowed to stand on a flat surface, covered with a large cover to prevent airborne dust from drifting onto the substrate during the standstill process and affecting the thermoelectric properties of the film. The sample is allowed to stand for 6 hours, allowing the sample to be evenly spread on the substrate, resulting in a uniform and smooth film. The glass substrate is then ultrasonically treated in a solution of detergent, acetone, water, and alcohol for 20 minutes, followed by vacuum drying at 60 degrees Celsius for at least 60 minutes.

[0036] Preferably, in step m, the sample is placed in a CVD furnace, the flange on the right side of the furnace is closed, and the plug is unscrewed. The temperature in the right temperature zone of the furnace is raised to 90°C over 30 minutes and maintained in an argon atmosphere for 6 hours. After the film is dried, 6 μL of DMSO is added for surface modification. The film is then placed back in the CVD furnace and annealed at 140°C in an argon atmosphere for 30 minutes. The sample is then removed and thermoelectric properties measured.

[0037] According to a second aspect of the present invention, the present invention provides a PEDOT:PSS / VN 0.52 O 0.26 Thermoelectric composite films are used to prepare wearable thermoelectric devices. Thermoelectric composite films have broad application prospects, such as thermoelectric power generation, thermoelectric cooling, and can also be used in wearable electronic devices such as chargers and smart watches, which generate electricity using human body heat.

[0038] The present invention proposes a method for preparing VN by using NaVO3 and urea. 0.52 O 0.26 The preparation method of nanoparticles can be used to prepare thermoelectric nanocomposite films and thermoelectric products that can reduce carbon emissions! Using urea pyrolysis as a nitrogen source, VN is prepared by combining chemical vapor deposition with molten salt method. 0.52 O 0.26Nanoparticle material is the innovation of this invention, which is mixed with P-type organic thermoelectric material to form a PEDOT:PSS / VN 0.52 O 0.26 The energy filtering effect of the composite film PN junction interface improves the Seebeck coefficient of the thermoelectric film, in order to achieve the complementarity of organic and inorganic materials in mechanical properties, thermal properties and electrical properties, and develop high thermoelectric figure of merit and flexible composite films.

[0039] This invention realizes for the first time the use of molten salt method to prepare VN with good crystallinity. 0.52 O 0.26 Nanoparticles can be produced by this method at a significantly reduced cost. Compared to other methods, the present invention has significant differences and outstanding advantages:

[0040] 1. The NaCl and KCl salts in the method of the present invention are used as catalysts rather than reactants, and are not consumed or changed in the reaction, thereby preparing VN with good crystallinity and relatively uniform morphology. 0.52 O 0.26 Nanoparticles. The present invention uses argon as a protective gas to prevent the sample from being oxidized during the firing process.

[0041] 2. The method of the present invention provides a simple and efficient preparation method for organic-inorganic thermoelectric composite membranes. 0.52 O 0.26 Nanoparticles improve the thermoelectric performance of the thermoelectric composite film. At the same time, this method has low requirements for the overall preparation process equipment, which greatly reduces the production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 For VN 0.52 O 0.26 Characterization of the crystal properties and surface morphology of nanoparticles, as well as the morphology of composite films formed with PEDOT:PSS, in which VN 0.52 O 0.26 The weight ratio of nanoparticles to PEDOT:PSS is 1%. 0.52 O 0.26 Nanoparticle XRD curve, (b) VN 0.52 O 0.26 SEM image of nanoparticle surface morphology, (c) VN 0.52 O 0.26 SEM image of the surface morphology of the / PEDOT:PSS (1% wt) composite film, (d) VN 0.52 O 0.26 / PEDOT:PSS (1% wt) composite film cross-section SEM image;

[0043] Figure 2 For different weight ratios VN 0.52 O0.26 / PEDOT:PSS composite film conductivity change trend with temperature;

[0044] Figure 3 For different weight ratios VN 0.52 O 0.26 / PEDOT:PSS composite film seebeck variation trend with temperature;

[0045] Figure 4 For different weight ratios VN 0.52 O 0.26 / PEDOT:PSS composite film power factor variation trend with temperature;

[0046] Figure 5 The conductivity, Seebeck coefficient, and power factor change with VN at a temperature of 90 degrees. 0.52 O 0.26 The trend of increasing weight ratio of nanoparticles. DETAILED DESCRIPTION

[0047] The PEDOT:PSS required in the present invention was purchased from Heraeus (model PH1000, concentration 1.1-1.2 mg / ml), and NaVO3, urea, NaCl, and KCl were purchased from China National Pharmaceutical Group.

[0048] The required chemical vapor deposition furnace (CVD) was purchased from Hefei Kejing Materials Technology Co., Ltd., and the thermoelectric tester was purchased from Beijing Coreo Technology Co., Ltd.

[0049] The heating furnace heats the sample to the set test temperature. Simultaneously, the thermocouple heater within the bottom electrode activates, maintaining the temperature difference between the upper and lower electrodes at the set value through dynamic PID temperature control. Two thermocouple probes measure temperatures T1 and T2, while also measuring the potential difference dE between the two contact points, thus measuring the Seebeck coefficient. Subsequently, forward and reverse currents flow between the upper and lower electrodes, with the two thermocouple probes acting as voltage probes to measure the voltage between the two contact points, thus achieving a four-terminal resistance test.

[0050] PEDOT:PSS / VN was prepared as follows 0.52 O 0.26 Thermoelectric composite film specifically includes the following steps:

[0051] a. Clean and dry the quartz tube and two crucibles in the chemical vapor deposition (CVD) furnace; in step a, first rinse the quartz tube with deionized water, wipe the water stains on the outer wall of the quartz tube, and put it into the CVD furnace. Put a crucible with a length of 10 cm and a width of 3 cm into a 500 ml beaker and ultrasonicate it with acetone, alcohol, and deionized water for more than 3 times, and then put it into a dryer to dry. Then put the dried crucible into the central temperature zone of the furnace. Set the furnace temperature to: from room temperature to 500 degrees in 30 minutes, keep warm for 30 minutes, rise to 1000 degrees in 30 minutes, keep warm for 30 minutes, end the program, and let the CVD furnace cool down naturally. Take out the crucible in the furnace and observe whether there is white substance in the quartz tube. If so, rinse the quartz tube again and burn the furnace clean according to the program set before the furnace;

[0052] b. Mix NaVO₃ with NaCl and KCl, then finely grind in an agate mortar. Place the mixture in a crucible. In step b, mix the combined weight of NaCl and KCl with NaVO₃ in a 1:1 weight ratio, with a 1:1 molar ratio of Na:K. The total weight of the mixed sample is 2 g. Place the ground sample in a crucible 10 cm long and 3 cm wide and flatten it. Wear a mask and rubber gloves during this procedure. NaVO₃ can be harmful to the skin and respiratory tract, so be careful not to come into direct contact with skin. Grind the mixed sample for approximately 3 hours. Fine grinding will ensure a more complete reaction.

[0053] c. Grind urea in an agate mortar and pestle, then transfer an appropriate amount of urea to a crucible. In step c, clean and dry the agate mortar and pestle, add 15g of urea to the mortar, grind for 20 minutes, and transfer the ground urea to the crucible. Finely ground urea allows for thermal decomposition of ammonia during firing, allowing it to react with NaVO3.

[0054] d. The argon gas connected to the CVD furnace is turned on, and the crucible containing urea is placed in the low-temperature zone of the CVD furnace; the temperature in the low-temperature zone is 180-200 degrees Celsius; in step d, before the sample is placed in the CVD furnace, the quartz tube should be evacuated first, then the right-side cock of the furnace is tightened, and argon gas is introduced, with the gas flow rate adjusted to 100 sccm. The cock on the left side of the furnace is opened, and argon gas is introduced into the quartz tube. When the pressure in the furnace is balanced with the external environment, the knob on the left side of the furnace is tightened, the mechanical pump is turned on, and the cock on the right side of the furnace is opened to discharge the argon gas in the furnace. Then the knob on the right side of the furnace is tightened, the mechanical pump is turned off, the pipe connected to the mechanical pump is unplugged, the knob on the left side of the furnace is opened, and argon gas is introduced into the quartz tube. When the pressure in the quartz tube is balanced with the external environment, the cock on the right side of the furnace is unscrewed, and the lid on the quartz tube on the right side of the furnace is opened. The crucible containing urea is placed in the low-temperature zone on the left side of the CVD furnace with a slender iron rod.

[0055] e. Place the crucible containing NaVO3 in step b into the CVD furnace; place the crucible containing the NaVO3 and salt mixture into the center of the high temperature zone of the CVD furnace to facilitate making the crucible in a uniform temperature range.

[0056] f. Tighten the CVD furnace flange; close the flange on the right side of the furnace and turn the knob. Argon is used as a shielding gas to isolate the air and prevent it from reacting with the mixture at high temperatures.

[0057] g. Close the furnace cover, set the temperature program for the low and high temperature zones of the CVD furnace, press the start button, and start firing the sample; the high temperature zone heating program is set as follows: the high temperature zone temperature rises from room temperature to 110 degrees in 30 minutes, holds for 20 minutes, then rises to 600 degrees at a rate of 1.5 degrees per minute, holds for 5 hours, and then allows the furnace to cool naturally. The high temperature zone temperature can be set between 590-610 degrees. VN with good crystallinity and stable composition is prepared. 0.52 O 0.26 Nanoparticles. The low temperature zone heating program is set as follows: the low temperature zone temperature is raised from room temperature to 100 degrees within 30 minutes, kept warm for 20 minutes, then raised to 200 degrees at a heating rate of 1.5 degrees per minute, kept warm for 5 hours, and then the furnace is allowed to cool naturally. Urea is pyrolyzed at 200 degrees to produce ammonia. The present invention uses the ammonia produced by urea to react with NaVO3 to produce VN 0.52 O 0.26 .

[0058] h. After the sample is fired, wait until the temperature in the furnace drops to room temperature and take out the sample to obtain VN 0.52 O 0.26 , which means that the molar ratio of V:N:O is 1:0.52:0.26; after the sample is burned, wait until the temperature in the furnace drops to room temperature, tighten the stopcock on the left side of the CVD, turn off the argon gas and take out the sample from the right side of the furnace.

[0059] i. Place the sample in a beaker, add deionized water, centrifuge, and remove the lower layer of solution; re-stir and disperse the solution, centrifuge, and remove the upper layer of liquid, and measure VN 0.52 O 0.26 The concentration of the aqueous solution. 0.52 O 0.26 Place in a beaker, add deionized water, sonicate, and centrifuge at 8000 rpm. Repeat sonication and centrifugation six times, collecting the lower layer. Re-stir the lower layer, sonicate, and centrifuge at 1000 rpm for 10 minutes. Collect the upper layer and dilute it to a concentration of 1.64 mg / ml.

[0060] j. Filter the PEDOT:PSS aqueous solution through a PVDF porous membrane. Add 5% by volume of dimethyl sulfoxide (DMSO) to the PEDOT:PSS solution. Specifically, filter the PEDOT:PSS solution through a 450 nm pore-size PVDF porous membrane syringe filter. Transfer 2000 μL of the PEDOT:PSS filtrate to a 5 mL test tube, add 50 μL of DMSO, and sonicate for 10 minutes to homogenize the mixture.

[0061] k. Prepare several 1ml test tubes, clean and dry them; add different volumes of VN into the test tubes. 0.52 O 0.26 The aqueous solution was prepared and the water in the aqueous solution was dried; after drying, the PEDOT:PSS aqueous solution was added to the test tube, and the test tube was placed in an ultrasonic machine to mix the solution evenly; specifically, a 1 mL small test tube was prepared, the small test tube was cleaned and dried. 6.4 μL of VN was added to the small test tube. 0.52 O 0.26 Then add 25 microliters of DMSO. 0.52 O 0.26 The test tube containing the aqueous solution was dried, and 1000 μl of the PEDOT:PSS solution in step j was added to the dried test tube. 0.52 O 0.26 The weight ratio of PEDOT / PSS was 1% wt, and ultrasonication was performed for 10 min.

[0062] 1. Apply the prepared mixed solution dropwise onto a glass substrate and let it sit to form a film. Specifically, apply 120 μL of the prepared solution dropwise onto a 1 cm x 1 cm glass substrate. Allow to sit on a flat table, covered with a large hood to prevent airborne dust from drifting onto the substrate and affecting the film's thermoelectric properties. Allow the sample to sit for 6 hours to evenly distribute the sample across the substrate, resulting in a uniform, smooth film. The glass substrate is ultrasonically treated in a solution of detergent, acetone, water, and alcohol for 20 minutes, followed by vacuum drying at 60°C for at least 60 minutes.

[0063] m. Place the glass substrate in a CVD furnace, dry and anneal, and then drop a layer of DMSO on the film for surface modification. Then place it in a CVD furnace again, dry and vacuum anneal to obtain PEDOT:PSS / VN 0.52 O 0.26Thermoelectric composite film: Specifically, place the rested sample into a CVD furnace, close the flange on the right side of the furnace, and unscrew the plug. Raise the temperature in the right temperature zone of the furnace to 90°C over 30 minutes and maintain it in an argon atmosphere for 6 hours. After drying the film, add 6 μl of DMSO for surface modification. Then, place the film back into the CVD furnace and anneal it at 140°C in an argon atmosphere for 30 minutes. Remove the sample and measure its thermoelectric properties.

[0064] Figure 1 (c) is VN 0.52 O 0.26 Top view SEM image of / PEDOT:PSS (1% wt) composite film, Figure 1 (d) is VN 0.52 O 0.26 / PEDOT:PSS (1% wt) composite film cross-section SEM image. 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 1wt% reached 1250S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 30.424μV / K at 30℃ and 62.75μV / K at 90℃. Figure 3 As shown in Figure 2, the power factor reaches 115.731 μWm at 30°C and 90°C respectively. -1 K -2 and 474.424 μWm -1 K -2 ,like Figure 4 As shown in .

[0065] Example 1 VN 0.52 O 0.26 / PEDOT:PSS (0.5% wt)

[0066] Steps AI and VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0067] J. Filter the PEDOT:PSS solution through a 450 nm PVDF porous membrane syringe filter. Place 2000 μL of the PEDOT:PSS filtrate into a 5 mL test tube, add 50 μL of DMSO, and sonicate for 10 minutes to homogenize the mixture.

[0068] K. Prepare a 1 mL test tube, clean it and dry it. Add 3.2 μL of VN into the test tube. 0.52 O 0.26 Aqueous solution (1.64 mg / ml), and then 25 microliters of DMSO was added. 0.52O 0.26 The test tube containing the aqueous solution was dried, and 1000 μl of the PEDOT:PSS solution in step j was added to the dried test tube. 0.52 O 0.26 The weight ratio of PEDOT / PSS was 0.5% wt, and ultrasonication was performed for 10 min.

[0069] Steps L and M are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0070] It was found through measurement that VN 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 0.5% wt reached 4071S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 25.59μV / K at 30℃ and 30.42μV / K at 90℃. Figure 3 As shown in Figure 2, the power factor reaches 266.585 μWm at 30°C and 90°C respectively. -1 K -2 and 350.704 μWm -1 K -2 ,like Figure 4 As shown in .

[0071] Example 2 VN 0.52 O 0.26 / PEDOT:PSS (4% wt)

[0072] Steps AJ and VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0073] K. Prepare a 1 mL test tube, clean it and dry it. Add 26.67 μL of VN into the test tube. 0.52 O 0.26 Aqueous solution (1.64 mg / ml), and then 25 microliters of DMSO was added. 0.52 O 0.26 The test tube containing the aqueous solution was dried, and 1000 μl of the PEDOT:PSS solution in step j was added to the dried test tube. 0.52 O 0.26 The weight ratio of PEDOT / PSS was 4% wt, and ultrasonication was performed for 10 min.

[0074] Steps L and M are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0075] It was found through measurement that VN 0.52 O 0.26 The conductivity of the 4%wt PEDOT:PSS thermoelectric composite film reached 497.5S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 27.353μV / K at 30℃ and 38.468μV / K at 90℃. Figure 3 As shown in Figure 2, the power factor reaches 37.226 μWm at 30°C and 90°C respectively. -1 K -2 and 65.587 μWm -1 K -2 ,like Figure 4 As shown in .

[0076] Example 3 VN 0.52 O 0.26 / PEDOT:PSS (10% wt)

[0077] The steps are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0078] I. Prepared VN 0.52 O 0.26 Place the solution in a beaker, add deionized water, sonicate, and centrifuge at 8000 rpm. Collect the lower layer solution. Repeat six times. Re-stir the lower layer solution, sonicate, and centrifuge at 1000 rpm for 10 minutes. Collect the upper layer solution and measure its concentration to 1.64 mg / ml.

[0079] J. Filter the PEDOT:PSS solution using a 450 nm syringe filter. Take 400 μl of the filtered PEDOT:PSS and place it in a 1 ml test tube. Add 10 μl of DMSO and sonicate for 10 minutes to mix the mixture evenly.

[0080] The specific preparation method of K. is as follows: prepare a 1mL test tube, clean the test tube and dry it. Add 28.45 microliters of VN into the test tube. 0.52 O 0.26 Aqueous solution (1.64 mg / ml), and then 10 microliters of DMSO was added. 0.52 O 0.26 The test tube containing the aqueous solution was dried, and 400 μl of the PEDOT:PSS (VN) prepared in step J was added to the dried test tube. 0.52 O 0.26 The weight ratio is 10% wt), and ultrasonication is performed for 10 minutes.

[0081] Steps L and M are the same as VN0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0082] It was found through measurement that VN 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 10wt% reached 434.2S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 24.13μV / K at 30℃ and 35.01μV / K at 90℃. Figure 3 As shown in Figure 2, the power factor reaches 25.276 μWm at 30°C and 90°C respectively. -1 K -2 and 51.531 μWm -1 K -2 ,like Figure 4 As shown in .

[0083] Example 4 VN 0.52 O 0.26 / PEDOT:PSS (30% wt)

[0084] Steps AH are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0085] I. Prepared VN 0.52 O 0.26 Place the solution in a beaker, add deionized water, sonicate, and centrifuge at 8000 rpm. Collect the lower layer solution. Repeat six times. Re-stir the lower layer solution, sonicate, and centrifuge at 1000 rpm for 10 minutes. Collect the upper layer solution and measure its concentration to 16.4 mg / ml.

[0086] J. Filter the PEDOT:PSS solution using a 450 nm syringe filter. Take 400 μl of the filtered PEDOT:PSS and place it in a 1 ml test tube. Add 10 μl of DMSO and sonicate for 10 minutes to mix the mixture evenly.

[0087] The specific preparation method of K. is as follows: prepare a 1mL test tube, clean the test tube and dry it. Add 10.97 microliters of VN into the test tube. 0.52 O 0.26 Aqueous solution (16.4 mg / ml), and then 10 microliters of DMSO was added. 0.52 O 0.26 The test tube containing the aqueous solution was dried, and 400 μl of PEDOT:PSS (VN 0.52 O 0.26The weight ratio is 30% wt), and ultrasonication is performed for 10 minutes.

[0088] Steps L and M are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0089] It was found through measurement that VN 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 30wt% reached 448.5S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 32.64μV / K at 30℃ and 41.49μV / K at 90℃. Figure 3 As shown in Figure 2, the power factor reaches 47.774 μWm at 30°C and 90°C respectively. -1 K -2 and 72.262 μWm -1 K -2 ,like Figure 4 As shown in .

[0090] Example 5 VN 0.52 O 0.26 / PEDOT:PSS (60% wt)

[0091] Steps AH are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0092] I. Lieutenant General prepared VN 0.52 O 0.26 Place the solution in a beaker, add deionized water, sonicate, and centrifuge at 8000 rpm. Collect the lower layer. Repeat six times. Re-stir the lower layer, sonicate, and centrifuge at 1000 rpm for 10 minutes. Collect the upper layer, and measure its concentration to 16.4 mg / ml.

[0093] J. Filter the PEDOT:PSS solution using a 450 nm syringe filter. Take 400 μl of the filtered PEDOT:PSS and place it in a 1 ml test tube. Add 10 μl of DMSO and sonicate for 10 minutes to mix the mixture evenly.

[0094] The specific configuration method of K. is as follows: prepare a 1mL test tube, clean it and dry it. 0.52 O 0.26 The volume ratio of the aqueous solution in PEDOT is 60 wt%. 38.4 μl of VN was added to the test tube. 0.52 O 0.26Aqueous solution (16.4 mg / ml), and then 10 microliters of DMSO was added. 0.52 O 0.26 The test tubes containing the aqueous solution were dried, and 400 μl of PEDOT:PSS (VN 0.52 O 0.26 The weight ratio is 60% wt), and ultrasonication is carried out for 10 minutes.

[0095] Steps L and M are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0096] It was found through measurement that VN 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 60wt% reached 1080.1S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 24.25μV / K at 30℃ and 27.58μV / K at 90℃. Figure 3 As shown in the figure, the power factor reaches 63.503μWm at 30℃ and 90℃ respectively. -1 K -2 and 78.314 μWm -1 K -2 ,like Figure 4 As shown in .

[0097] Example 6 VN 0.52 O 0.26 / PEDOT:PSS (70% wt)

[0098] Steps AH are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0099] I. Lieutenant General prepared VN 0.52 O 0.26 Place the solution in a beaker, add deionized water, sonicate, and centrifuge at 8000 rpm. Collect the lower layer solution. Repeat six times. Re-stir the lower layer solution, sonicate, and centrifuge at 1000 rpm for 10 minutes. Collect the upper layer solution and measure its concentration to 16.4 mg / ml.

[0100] J. Filter the PEDOT:PSS solution using a 450 nm syringe filter. Take 400 μl of the filtered PEDOT:PSS and place it in a 1 ml test tube. Add 10 μl of DMSO and sonicate for 10 minutes to mix the mixture evenly.

[0101] The specific configuration method of K. is as follows: prepare a 1mL test tube, clean it and dry it. 0.52 O 0.26 The volume ratio of the aqueous solution in PEDOT is 70 wt%. 59.75 μl of VN 0.52 O 0.26 Aqueous solution (16.4 mg / ml), and then 10 microliters of DMSO was added. 0.52 O 0.26 The test tubes containing the aqueous solution were dried, and 400 μl of PEDOT:PSS (VN 0.52 O 0.26 The weight ratio is 70% wt), and ultrasonication is performed for 10 minutes.

[0102] Steps L and M are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0103] It was found through measurement that VN 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 70wt% reached 2427.6S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 18.48μV / K at 30℃ and 22.16μV / K at 90℃. Figure 3 As shown in the figure, the power factor reaches 82.895μWm at 30℃ and 90℃ respectively. -1 K -2 and 112.497 μWm -1 K -2 ,like Figure 4 As shown in .

[0104] Example 7 VN 0.52 O 0.26 / PEDOT:PSS (80% wt)

[0105] Steps AH are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0106] I. Lieutenant General prepared VN 0.52 O 0.26 Place the solution in a beaker, add deionized water, sonicate, and centrifuge at 8000 rpm. Collect the lower layer. Repeat six times. Re-stir the lower layer, sonicate, and centrifuge at 1000 rpm for 10 minutes. Collect the upper layer, and measure its concentration to 16.4 mg / ml.

[0107] J. Filter the PEDOT:PSS solution using a 450 nm syringe filter. Take 400 μl of the filtered PEDOT:PSS and place it in a 1 ml test tube. Add 10 μl of DMSO and sonicate for 10 minutes to mix the mixture evenly.

[0108] The specific configuration method of K. is as follows: prepare a 1mL test tube, clean it and dry it. 0.52 O 0.26 The volume ratio of the aqueous solution in PEDOT is 80 wt%. 102.4 μl of VN 0.52 O 0.26 Aqueous solution (16.4 mg / ml), and then 10 microliters of DMSO was added. 0.52 O 0.26 The test tubes containing the aqueous solution were dried, and 400 μl of PEDOT:PSS (VN 0.52 O 0.26 The weight ratio is 80% wt), and ultrasonication is performed for 10 minutes.

[0109] Steps L and M are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0110] It was found through measurement that VN 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 80wt% reached 1909S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 22.46μV / K at 30℃ and 30.95μV / K at 90℃. Figure 3 As shown in the figure, the power factor reaches 96.301μWm at 30℃ and 90℃ respectively. -1 K -2 and 178.908 μWm -1 K -2 ,like Figure 4 As shown in .

[0111] Example 8 VN 0.52 O 0.26 / PEDOT:PSS (90% wt)

[0112] Steps AH are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0113] I. Lieutenant General prepared VN 0.52 O 0.26Place the solution in a beaker, add deionized water, sonicate, and centrifuge at 8000 rpm. Collect the lower layer. Repeat six times. Re-stir the lower layer, sonicate, and centrifuge at 1000 rpm for 10 minutes. Collect the upper layer, and measure its concentration to 16.4 mg / ml.

[0114] J. Filter the PEDOT:PSS solution using a 450 nm syringe filter. Take 400 μl of the filtered PEDOT:PSS and place it in a 1 ml test tube. Add 10 μl of DMSO and sonicate for 10 minutes to mix the mixture evenly.

[0115] The specific configuration method of K. is as follows: prepare a 1mL test tube, clean it and dry it. 0.52 O 0.26 The volume ratio of the aqueous solution in PEDOT is 90 wt%. 230.48 μl of VN was added to the test tube. 0.52 O 0.26 Aqueous solution (16.4 mg / ml), and then 10 microliters of DMSO was added. 0.52 O 0.26 The test tubes containing the aqueous solution were dried, and 400 μl of PEDOT:PSS (VN 0.52 O 0.26 The weight ratio is 90% wt), and ultrasonication is performed for 10 minutes.

[0116] Steps L and M are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0117] It was found through measurement that VN 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 90wt% reached 570.8S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 23.82μV / K at 30℃ and 27.89μV / K at 90℃. Figure 3 As shown in the figure, the power factor reaches 32.394μWm at 30℃ and 90℃ respectively. -1 K -2 and 42.489 μWm -1 K -2 ,like Figure 4 As shown in .

[0118] Example 9 VN 0.52 O 0.26 / PEDOT:PSS (0% wt)

[0119] The example consists of three steps, J, L and M are the same as VN 0.52 O 0.26 / PEDOT:PSS (1% wt) preparation steps.

[0120] J. Filter the PEDOT:PSS solution through a 450 nm PVDF porous membrane syringe filter. Place 2000 μL of the PEDOT:PSS filtrate into a 5 mL test tube. Add 100 μL of DMSO and sonicate for 10 minutes to homogenize the mixture.

[0121] L. Apply a 120 μL droplet of the PEDOT:PSS solution to a 1 cm x 1 cm glass substrate. Allow to rest on a flat surface, covered with a large hood to prevent airborne dust from drifting onto the substrate and affecting the film's thermoelectric properties. Allow the sample to rest for 6 hours to evenly distribute the sample across the substrate, resulting in a uniform, smooth film. Ultrasonicate the glass substrate in a solution of detergent, acetone, water, and alcohol for 20 minutes, then vacuum dry at 60°C for at least 60 minutes.

[0122] M. Place the rested sample into the CVD furnace, close the flange on the right side of the furnace, and remove the plug. Raise the temperature in the right zone of the furnace to 90°C over 30 minutes and maintain in an argon atmosphere for 6 hours. After drying the film, add 6 μl of DMSO for surface modification. Then, place the film back into the CVD furnace and anneal at 140°C in an argon atmosphere for 30 minutes. Remove the sample and measure its thermoelectric properties.

[0123] It was found through measurement that VN 0.52 O 0.26 The conductivity of the PEDOT:PSS thermoelectric composite film with a weight ratio of 0wt% reached 966.2S / cm. Figure 2 As shown in , the Seebeck coefficient reaches 23.04μV / K at 30℃ and 28.69μV / K at 90℃. Figure 3 As shown in Figure 2, the power factor reaches 51.297 μWm at 30°C and 90°C respectively. -1 K -2 and 75.905 μWm -1 K -2 ,like Figure 4 As shown in .

[0124] Summary: By comparing VN in organic-inorganic composite membranes 0.52 O 0.26 Nanoparticle weight ratio, found VN 0.52 O 0.26The PEDOT:PSS (1% wt) composite film has the highest thermoelectric performance, with a Seebeck coefficient of 62.75 μV / K and a power factor of 474.424 μWm at 90°C. -1 K -2 This is mainly due to VN 0.52 O 0.26 When the weight ratio of nanoparticles is 1%wt, the nanoparticles are evenly wrapped by PEDOT:PSS, forming an interfacial conductive channel that is conducive to carrier transport, with less agglomeration effect and weaker carrier scattering. The conductivity of the organic-inorganic composite film (1%wt) is increased to 1250S / cm compared to the pure PEDOT:PSS organic film. 0.52 O 0.26 As the number of nanoparticles increases, the agglomeration effect of the nanoparticles increases the carrier scattering effect, and the conductivity decreases. 0.52 O 0.26 As the number of nanoparticles increases, the agglomeration effect becomes more obvious and a network structure appears. PEDOT and network VN 0.52 O 0.26 The nanoparticles will simultaneously participate in electrical conduction, and the conductivity of the composite film is enhanced compared to the pure PEDOT:PSS film.

[0125] P-type PEDOT:PSS and N-type VN 0.52 O 0.26 Nanoparticles form a pn junction barrier of organic-inorganic composite. The interface effect and pn junction barrier filter low-energy electrons and allow high-energy electrons to pass through. 0.52 O 0.26 / PEDOT:PSS (weight ratio 1% wt) composite film has a Seebeck coefficient of 62.75μV / K at 90 degrees, while the Seebeck coefficient of pure PEDOT:PSS organic film at 90 degrees is 28.69μV / K, which is much lower than the Seebeck coefficient of the composite film with a weight ratio of 1% wt. With the increase of nanoparticles, the built-in electric field is enhanced, but the disordered structure caused by agglomeration also increases the carrier scattering effect, resulting in a decrease in the Seebeck coefficient. When the weight ratio reaches 30% wt, the built-in electric field reaches its strongest point, with a Seebeck coefficient of 41.49μV / K at 90 degrees, but at this time agglomeration affects carrier transport, conductivity decreases, and power factor decreases. With the continued increase of nanoparticles, a network structure appears, the built-in electric field effect weakens, and the Seebeck coefficient of the composite film is close to that of pure PEDOT:PSS. Due to the higher conductivity of the high weight ratio composite film, the power factor of the high weight ratio composite film is improved compared to the power factor of pure PEDOT:PSS. Figure 5 As shown, when the temperature is 90 degrees, the conductivity, Seebeck coefficient, and power factor change with VN 0.52 O 0.26 The trend of increasing weight ratio of nanoparticles.

[0126] In summary, VN 0.52 O 0.26 / PEDOT:PSS (weight ratio 1%wt) composite film has the best thermoelectric performance.

[0127] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A PEDOT:PSS / VN 0.52 O 0.26 Preparation method of thermoelectric composite membrane, using urea and NaVO3 to prepare VN by molten salt method 0.52 O 0.26 Nanoparticles, VN 0.52 O 0.26 The nanoparticles were mixed with PEDOT:PSS aqueous solution and the PEDOT:PSS / VN was prepared by drop coating method. 0.52 O 0.26 Thermoelectric composite membrane; the molten salt method contains NaCl and KCl.

2. The method according to claim 1, wherein: The specific steps include: a. Clean and dry the quartz tube and two crucibles in the chemical vapor deposition furnace; b. Mix NaVO3 with NaCl and KCl and grind them finely in an agate mortar, then place them in a crucible; c. Grind urea in an agate mortar, and finally take an appropriate amount of urea into the crucible; d. Open the argon gas connection inside the chemical vapor deposition furnace and place the crucible containing urea into the low-temperature zone of the chemical vapor deposition furnace; the temperature of the low-temperature zone is 180-200 degrees Celsius; e. The crucible containing NaVO3 in step b is placed in a chemical vapor deposition furnace; f. Tighten the flange cover of the chemical vapor deposition furnace; g. Close the furnace cover, set the temperature program for the low and high temperature zones of the chemical vapor deposition furnace, press the start button, and start firing the sample; h. After the sample is fired, wait until the temperature in the furnace drops to room temperature and take out the sample to obtain VN 0.52 O 0.26 ; i. VN 0.52 O 0.26 The sample was placed in a beaker, deionized water was added, and the solution was centrifuged to remove the lower layer. The solution was stirred and dispersed again, and the upper layer was centrifuged to measure VN. 0.52 O 0.26 Concentration of aqueous solution; j. PEDOT:PSS aqueous solution was filtered using a PVDF porous membrane as a substrate, and DMSO, DMF or ethylene glycol was added to the PEDOT:PSS aqueous solution; k. Prepare the test tube, clean and dry it; add VN into the test tube. 0.52 O 0.26 After drying, add PEDOT:PSS aqueous solution to the test tube, put the test tube into the ultrasonic machine and ultrasonicate to mix the solution evenly; calculate the weight of the substance and control VN 0.52 O 0.26 The weight percentage of PEDOT:PSS is 0.5%-90%; l. The prepared mixed solution is dropped onto a glass substrate and allowed to stand to form a film; m. Place the glass substrate in a chemical vapor deposition furnace, dry and anneal, and then drop a layer of DMSO on the film for surface modification. Then place it in a chemical vapor deposition furnace again, dry and vacuum anneal to obtain PEDOT:PSS / VN 0.52 O 0.26 Thermoelectric composite film.

3. The method according to claim 2, wherein: In step b, the total weight of NaCl and KCl is mixed with NaVO3 in a weight ratio of 1:1, and the molar ratio of NaCl and KCl is Na:K of 1:

1.

4. The method according to claim 2 or 3, characterized in that: In step g, close the lid of the CVD furnace and set the temperature as follows: The high temperature zone heating program is set as follows: the high temperature zone temperature is raised from room temperature to 110 degrees in 30 minutes, kept warm for 20 minutes, then raised to 600 degrees at a heating rate of 1.5 degrees per minute, kept warm for 5 hours, and then the furnace is cooled naturally; VN with good crystallinity and stable composition is prepared 0.52 O 0.26 Nanoparticles; The low temperature zone heating program is set as follows: the low temperature zone temperature is raised from room temperature to 100 degrees within 30 minutes, kept warm for 20 minutes, then raised to 200 degrees at a heating rate of 1.5 degrees per minute, kept warm for 5 hours, and then the furnace is allowed to cool down naturally.

5. The method according to claim 2 or 3, characterized in that: In step i, the prepared VN 0.52 O 0.26 Place the solution in a beaker, add deionized water, sonicate, and centrifuge at 8000 rpm. Repeat the sonication and centrifugation 6 times to collect the lower layer solution. Stir the lower layer solution again, sonicate, and centrifuge at 1000 rpm for 10 minutes. Collect the upper layer solution and dilute the upper layer solution to a concentration of 1.64 mg / ml.

6. The method according to claim 2 or 3, characterized in that: VN 0.52 O 0.26 and PEDOT:PSS weight percentage is 1%.

7. A PEDOT:PSS / VN prepared by the method of claim 1 0.52 O 0.26 The use of the thermoelectric composite film is characterized by: Used for thermoelectric power generation, thermoelectric refrigeration or wearable electronic devices.

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