CN108281553B - Tungsten oxide nanorod coated with poly (3, 4-ethylenedioxythiophene), and preparation method and application thereof - Google Patents
Tungsten oxide nanorod coated with poly (3, 4-ethylenedioxythiophene), and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a tungsten oxide nano rod coated by poly 3, 4-ethylenedioxythiophene, a preparation method and application thereof. The process steps are simple, the conditions are mild, and uniform and neutral tungsten oxide nanorods coated by poly (3, 4-ethylenedioxythiophene) can be obtained; the tungsten oxide nanorod has a higher Fermi level or work function, and can effectively reduce the corrosion of the PSS to the anode substrate, so that the efficiency and the service life of the perovskite solar cell are improved; and the energy level of the perovskite solar cell is closer to that of the perovskite material, and the perovskite solar cell can be used as a hole transport layer of the perovskite solar cell, so that photoproduction holes can be effectively extracted and transported, and the energy conversion efficiency of the perovskite solar cell is further improved.
Description
Technical Field
The invention belongs to the field of photovoltaic materials, relates to a hole transport layer material of a perovskite solar cell, and particularly relates to a tungsten oxide nanorod coated with poly (3, 4-ethylenedioxythiophene), a preparation method and application of the tungsten oxide nanorod coated with the poly (3, 4-ethylenedioxythiophene).
Background
The perovskite solar cell has the characteristics of light weight, good flexibility, low cost, environmental protection and the like, and is a hotspot of the research in the field of novel energy sources at present. The hole transport layer is a functional material between the anode and the photoactive layer, and can effectively collect and transport holes and inhibit the recombination of the holes and electrons. Therefore, the selection of a proper hole transport material plays a crucial role in optimizing the photoelectric conversion efficiency and the device performance of the perovskite solar cell.
Currently, for perovskite solar cells with a p-i-n structure, the most commonly used hole transport layer material is PEDOT: PSS; but the cost is high, the thermal stability is poor, and the anode is corroded by polystyrene sulfonic acid (PSS) with strong acidity, so that the stability of the perovskite solar cell is reduced. Thus, a series of transition metal oxides (e.g., NiO)X、MoOX、VOX、CuOXAnd WOXEtc.) are used as hole transport layer materials to improve the stability of the perovskite solar cell while reducing the cost of the perovskite solar cell. Tungsten oxide (WO) in comparison to several other materialsX) Has the advantages of good chemical stability, adjustable W/O stoichiometry, adjustable energy level structure, high carrier mobility, low price and the like. However, WOXThe work function of the material is about 4.6-4.8 eV, and the material is not matched with the valence band energy level (5.3-5.4 eV) of perovskite, so that the material is not beneficial to the collection and transmission of photogenerated holes, and is not an ideal hole transmission material. Thus, for WOXThe modification or modification of the nano material to prepare the hole transport layer material suitable for the perovskite solar cell has important scientific significance and economic value.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a tungsten oxide nanorod coated with poly (3, 4-ethylenedioxythiophene).
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a tungsten oxide nanorod coated with poly (3, 4-ethylenedioxythiophene) comprises the steps of dispersing tungsten oxide nanowires prepared through a hydrothermal reaction in a solvent, adding EDOT to react to obtain a blue solution, removing PEDOT and the tungsten oxide nanowires through sedimentation, and drying.
Optimally, the tungsten oxide nanowire is prepared by dissolving a tungsten salt precursor in a first solvent to carry out hydrothermal reaction; the tungsten salt precursor is tungsten hexachloride; the first solvent is a mixture composed of one or more of ethanol, methanol, ethylene glycol and isopropanol, and the temperature of the hydrothermal reaction is 150-200 ℃.
Optimally, the solvent is water, and the dispersion concentration of the tungsten oxide nanowires is less than or equal to 50 mg/mL.
Optimally, the length of the tungsten oxide nanowire is 100-500 nm, and the width of the tungsten oxide nanowire is 5-50 nm.
Further, the ratio of the tungsten oxide nanowires to the EDOT is 10-50 mg: 5 to 25 μ L.
Optimally, the EDOT is added and then the mixture reacts for 20-50 days under the conditions of room temperature and continuous stirring to obtain a blue solution, and the stirring speed is 500-700 r/min.
The invention also aims to provide a tungsten oxide nanorod coated with poly (3, 4-ethylenedioxythiophene), which is prepared by the method.
The invention also aims to provide an application of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod, wherein the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod is dispersed in a solvent to form a dispersion liquid, and then the dispersion liquid is spin-coated on a substrate and is heated and annealed to form a hole transport layer; or mixed with PEDOT: PSS to form a hole transport layer.
Preferably, the substrate is an indium tin oxide or fluorine-doped tin oxide glass substrate.
Optimally, the doping concentration of the poly 3, 4-ethylenedioxythiophene coated tungsten oxide nanorod in PEDOT PSS is 0.5-5 mg/mL
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the preparation method of the tungsten oxide nanorod coated with the poly-3, 4-ethylenedioxythiophene has simple process steps and mild conditions, and can obtain the uniform and neutral tungsten oxide nanorod coated with the poly-3, 4-ethylenedioxythiophene; the tungsten oxide nanorod has a higher Fermi level or work function, and can effectively reduce the corrosion of the PSS to the anode substrate, so that the efficiency and the service life of the perovskite solar cell are improved; and the energy level of the perovskite solar cell is closer to that of the perovskite material, and the perovskite solar cell can be used as a hole transport layer of the perovskite solar cell, so that photoproduction holes can be effectively extracted and transported, and the energy conversion efficiency of the perovskite solar cell is further improved.
Drawings
FIG. 1 is a picture of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorods prepared in example 2: (a) WOXNanowires, (b) WOXScanning Electron Microscopy (SEM) of @ PEDOT nanorods;
FIG. 2 is a picture of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorods prepared in example 2: (a) WOXTransmission electron micrograph (SEM) of @ PEDOT nanorod, (b) elemental scanning profile;
FIG. 3 shows PEDOT, PSS and WOXNanowire, WOXUltraviolet Electron Spectroscopy (UPS) plot of @ PEDOT nanorods (example 2);
FIG. 4 shows WO of the present inventionXThe structure schematic diagram of the perovskite solar cell with the @ PEDOT nanorod as the hole transport layer; wherein 1 is cathode (Ag), 2 is cathode buffer layer (BCP), and 3 is electron transport layer (PC)61BM), 4 is a perovskite layer (CH)3NH3IxPbCl3-X) And 5 is a hole transport layer (WO)X、WOX@ PEDOT, PEDOT: PSS or PEDOT: PSS-WOX@ PEDOT), 6 is the anode (ITO conductive glass);
FIG. 5 is a current density-voltage (J-V) plot of perovskite solar cells made in various embodiments of the present invention;
fig. 6 is a graph of the decay of the photoelectric conversion efficiency of perovskite solar cells based on different hole transport layers according to the invention.
Detailed Description
The preparation method of the tungsten oxide nanorod coated with the poly (3, 4-ethylenedioxythiophene) comprises the steps of dispersing tungsten oxide nanowires prepared through a hydrothermal reaction in a solvent, adding EDOT (namely 3, 4-ethylenedioxythiophene) to react to obtain a blue solution, removing the PEDOT (namely the poly (3, 4-ethylenedioxythiophene)) and the tungsten oxide nanowires through sedimentation, and drying. The method has simple process steps and mild conditions, and can obtain uniform and neutral tungsten oxide nanorods coated by poly (3, 4-ethylenedioxythiophene).
The tungsten oxide nanowire is prepared by dissolving a tungsten salt precursor in a first solvent and carrying out hydrothermal reaction; the tungsten salt precursor is tungsten hexachloride; the first solvent is a conventional solvent capable of dissolving the tungsten salt precursor, such as a mixture of one or more selected from ethanol, methanol, ethylene glycol and isopropanol), and the temperature of the hydrothermal reaction is preferably 150-200 ℃. The solvent is a conventional solvent capable of dissolving EDOT and having good dispersibility for tungsten oxide nanowires, such as water; the dispersion concentration of the tungsten oxide nanowires is generally 50mg/mL or less, and preferably 10mg/m or more, because the dispersion is affected when the dispersion concentration of the tungsten oxide nanowires is too high. The length of the prepared tungsten oxide nanowire is preferably 100-500 nm, and the width of the tungsten oxide nanowire is preferably 5-50 nm. The ratio of the tungsten oxide nanowires to the EDOT needs to be controlled within a proper range, and is usually 10-50 mg: 5-25 μ L, preferably 35 mg: 8-24 μ L. And adding the EDOT, and reacting for 20-50 days at room temperature under the condition of continuous stirring to obtain a blue solution (usually dark blue), wherein the stirring speed is 500-700 r/min.
The prepared poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod has a higher Fermi level or work function, and can effectively reduce the corrosion of the PSS to the anode substrate, thereby improving the efficiency and the service life of the perovskite solar cell; and the energy level of the perovskite material is closer to that of the perovskite material, so that the perovskite material can be used as a hole transport layer of a perovskite solar cell. The concrete application is as follows: dispersing the tungsten oxide nanorods coated by the poly (3, 4-ethylenedioxythiophene) in a solvent (the same as the solvent) to form a dispersion, spin-coating the dispersion on a substrate, and heating and annealing to form a hole transport layer; or mixed with PEDOT: PSS to form a hole transport layer. The substrate is indium tin oxide or fluorine-doped tin oxide glass substrate. The doping concentration of the poly 3, 4-ethylenedioxythiophene coated tungsten oxide nanorod in PEDOT PSS is 0.5-5 mg/mL.
The present invention will be further illustrated with reference to the following examples.
Example 1
This example provides a tungsten oxide nanorod coated with poly-3, 4-ethylenedioxythiophene (WO for short)X@ PEDOT nano rod) and a preparation method thereof, and the preparation method specifically comprises the following steps:
(a) preparation of WOXNanowires (ref: Journal of Materials Chemistry A,2013,1, 6125-: mixing WCl6Dissolving in ethanol to prepare a solution with the concentration of 12.5mg/mL (stirring for 15 minutes until the solution is completely dissolved); transferring the solution into a hydrothermal reaction kettle, and reacting for 24 hours at 180 ℃ to generate WOXCooling the nanowires to normal temperature, centrifugally cleaning the nanowires for 3 times by using deionized water and ethanol respectively, and then drying the nanowires in a vacuum oven at 45 ℃ overnight for later use (as shown in figure 1 (a));
(b) preparation of WOX@ PEDOT nanorods: taking 35mg of WOXDispersing the nanowires in 1mL of deionized water, dropwise adding 8 mu L of EDOT, and fully stirring at normal temperature for 30 days (the rotating speed is 500-800 rpm) until the solution becomes dark blue; then standing for 3-7 days to remove settled PEDOT and WOXNano-wire to obtain uniform deep blue water solution, freeze drying to obtain WOX@ PEDOT nanorod, about 28 mg.
Example 2
This example provides a tungsten oxide nanorod coated with poly-3, 4-ethylenedioxythiophene (WO for short)X@ PEDOT nanorod) and a preparation method thereof, which are substantially identical to those of example 1, except that: in step (b), EDOT was added dropwise at 16. mu.L.
Example 3
This example provides a tungsten oxide nanorod coated with poly-3, 4-ethylenedioxythiophene (WO for short)X@ PEDOT nanorod) and a preparation method thereof, which are substantially identical to those of example 1, except that: in step (b), 24. mu.L of EDOT was added dropwise.
Example 4
This example provides a tungsten oxide nanorod coated with poly-3, 4-ethylenedioxythiophene (WO for short)X@ PEDOT nanorod) and a preparation method thereof, which are substantially identical to those of example 1, except that: in step (a), 10mg of WO is takenXThe nanowires were dispersed in 1mL of deionized water.
Example 5
This example provides a tungsten oxide nanorod coated with poly-3, 4-ethylenedioxythiophene (WO for short)X@ PEDOT nanorod) and a preparation method thereof, which are substantially identical to those of example 1, except that: in step (a), 50mg of WO is takenXThe nanowires were dispersed in 1mL of deionized water.
Comparative examples 1 to 3 it can be found that the amount of WO is 35mg/1mLXThe nanowire aqueous solution has the advantages that the preferred addition amount of EDOT is 16 mu L, and the addition amount of EDOT is too small WOXThe yield of the @ PEDOT nanorods was slightly lower, while the yield did not increase significantly with the addition of EDOT in an amount of more than 16. mu.L. In addition, comparing example 1, example 4 and example 5, it can be found that WOXLower concentration of nanowires WOXLower yield of @ PEDOT nanorods, WOXHigher concentration of nanowires WOXThe yield of the @ PEDOT nanorod is high. Thus, under the condition of a certain amount of EDOT added, WOXYield of @ PEDOT nanorods and WOXThe concentration of the nanowires is relevant. Similar WO can be obtained from five examplesX@ PEDOT nanorods, morphology characterized by SEM (as shown in FIG. 1 (b)), WOXThe length of the nanowire is about 200 nm and 300nm, and the width of the nanowire is about 5-20 nm; the product obtained after the reaction is obviously shortened, and a coating layer is obviously visible on the surface; TEM characterization (FIG. 2(a)) shows, WOXThe @ PEDOT nanorod has an obvious core-shell structure and the size of WO is about 5 x 20nmXThe nanorods are externally coated with a polymer layer, WOXThe lattice spacing of the nanorods is about
Corresponds to WO2.72[010 ] of]A face with its long axis direction perpendicular to [010 ]]And (5) kneading. The characterization results showed that the polymerization of EDOT was not only in WOXThe nanostructure surface occurs and can be followed [010 ]]Surface generation to intercept WOx nanowiresBreaking into WOX@ PEDOT nanorods. TEM element distribution scanning test (FIG. 2(b)) shows that not only W and O elements but also C and S elements exist, and further proves that PEDOT exists in WOXThe surface of the nano-rod exists. XPS analysis results show WOXW is the W element on the surface of the @ PEDOT nano rod5+The oxidation state exists and therefore a large number of oxygen vacancies exist. In WOXNanowire surface W6+/W5+Ratio of about 4.2, W5+The content of (a) is relatively low. These results show that EDOT polymerizes the W at the surface of WOx nanostructures to yield PEDOT while simultaneously polymerizing W6+Reduction to W5+Thereby generating a large number of oxygen vacancies. Since the existence of a large number of oxygen holes on the surface of the metal oxide can change the electrical property of the metal oxide, the valence electron structure of the metal oxide is further characterized by ultraviolet light electron spectroscopy (UPS), the obtained secondary electron cut-off edge is shown in figure 3, and WO can be obtained through calculationXThe work function of the @ PEDOT nanorod is about-5.2 eV, which is higher than that of the WOXThe work function (-4.8eV) of PSS is slightly higher than that (-5.1eV) of PEDOT, the work function is more matched with the lowest unoccupied orbital (LUMO) energy level (-5.3-5.4 eV) of the perovskite material, and the collection and transmission of photogenerated holes in the perovskite layer are facilitated (the test adopts the WO in the example 2)XNanowires and WOX@ PEDOT nanorods).
Example 6
This example provides an application of poly 3, 4-ethylenedioxythiophene coated tungsten oxide nanorods (i.e., preparation based on WO)XThe hole transport layer and the perovskite solar cell of @ PEDOT nanorod) specifically are:
preparing WO with the concentration of 10mg/mLX@ PEDOT nanorod aqueous solution (using WO prepared in example 2)X@ PEDOT nanorod), and ultrasonically treating for 20 minutes to uniformly disperse the PEDOT nanorod and filter the PEDOT nanorod for later use; spin-coating WO on a cleaned ITO conductive glass substrateX@ PEDOT nanorod solution, coating conditions: spin-coating at 2000 rpm for 40s, and annealing at 150 deg.C for 5 min; the spin coating was repeated once and annealed at 150 ℃ for 10 minutes in air to obtain a hole transport layer of moderate thickness (about 20 nm).
Subsequently in WOXITO substrate modified by @ PEDOT hole transport layerPerovskite (CH) with a thickness of about 300nm is spin-coated3NH3PbI3-xClx) Photosensitive layer (using CH)3NH2I(100mg)，PbCl2(50mg)，PbI2(50mg) in DMF (500. mu.L) was spin coated at 4000rpm for 40 s; under the condition of nitrogen, heating and annealing the perovskite layer, wherein the annealing temperature is 80 ℃, and the annealing time is 2 hours; then spin-coating an electron transport layer on the perovskite layer, and adopting PC with the concentration of 20mg/mL61BM chlorobenzene solution is spin-coated at the rotating speed of 2000 rpm for 40 seconds; placing the electron transport layer in vacuum for 30 minutes, spin-coating a cathode buffer layer on the surface, and adopting an isopropanol solution with the concentration of 0.5mg/mL BCP, wherein the spin-coating speed is 4000rpm, and the rotation time is 30 seconds; finally, an Ag electrode with a thickness of about 100nm is evaporated in a vacuum chamber (the specific structure is shown in FIG. 4).
Under the irradiation of light intensity of AM1.5, the open-circuit voltage of the perovskite solar cell is 1.00V, and the short-circuit current is 17.25 mA-cm-2The fill factor was 76.78% and the photoelectric conversion efficiency was 13.24% (see table 1), and the J-V characteristic curve is shown in fig. 5.
Example 7
This example provides the application of poly 3, 4-ethylenedioxythiophene coated tungsten oxide nanorods, which is substantially the same as that in example 4, except that: the resulting hole transport layer was about 10nm thick and slightly thinner than in example 4.
Under the irradiation of light intensity of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.939V, and the short-circuit current is 17.876 mA-cm-2The fill factor was 56.01%, the photoelectric conversion efficiency was 9.4% (see table 1), and the J-V characteristic curve is shown in fig. 5.
Example 8
This example provides the application of poly 3, 4-ethylenedioxythiophene coated tungsten oxide nanorods, which is substantially the same as that in example 4, except that: the resulting hole transport layer was approximately 40nm thick, slightly thicker than in example 4.
Under the irradiation of the light intensity of AM1.5, the open-circuit voltage of the perovskite solar cell was 0.891V, and the short-circuit current was 18V.08mA·cm-2The fill factor was 56.13%, the photoelectric conversion efficiency was 9.04% (see table 1), and the J-V characteristic curve is shown in fig. 5.
Comparing example 4, example 5 and example 6, it can be seen that under the conditions of example 4 (i.e. spin coating WO with a concentration of 10 mg/mL)XThe @ PEDOT nanorod solution is twice) prepared, the hole transport layer is moderate in thickness, and the perovskite solar cell prepared on the basis has the highest photoelectric conversion efficiency.
Example 9
The embodiment provides an application of a tungsten oxide nanorod coated with poly-3, 4-ethylenedioxythiophene, which specifically comprises the following steps:
preparing WO with the concentration of 1mg/mLXMixing the @ PEDOT nanorod aqueous solution with the PEDOT: PSS solution according to the volume ratio of 1:1, performing ultrasonic treatment for 20 minutes to uniformly disperse the solution, and filtering the solution for later use; spin-coating WO on a cleaned ITO conductive glass substrateX@ PEDOT: PEDOT: PSS solution, coating conditions: spin coating at 2000 rpm for 40 seconds, annealing at 150 deg.C for 5 minutes in air, repeating the above process, co-spin coating twice, and finally annealing at 150 deg.C for 10 minutes in air.
Subsequently in WOXCoating a layer of perovskite (CH) with the thickness of about 300nm on an ITO substrate modified by a @ PEDOT hole transport layer3NH3PbI3-xClx) Photosensitive layer (using CH)3NH2I(100mg)，PbCl2(50mg)，PbI2(50mg) in DMF (500. mu.L) was spin coated at 4000rpm for 40 s; under the condition of nitrogen, the perovskite layer is heated and annealed, the annealing temperature is 80 ℃, and the annealing time is 2 hours. Then spin-coating an electron transport layer on the perovskite layer, and adopting PC with the concentration of 20mg/mL61BM chlorobenzene solution, spin-coating rotating speed 2000 rpm, spin time 40 seconds. And (3) placing the electron transport layer in vacuum for 30 minutes, spin-coating a cathode buffer layer on the surface, and adopting an isopropanol solution with the concentration of 0.5mg/mL BCP, wherein the spin-coating speed is 4000rpm, and the spin time is 30 seconds. And finally, evaporating an Ag electrode with the thickness of about 100nm in a vacuum cavity.
Under the irradiation of the light intensity of AM1.5, the perovskite solar cell is openedThe voltage was 0.987V and the short-circuit current was 20.93mA cm-2The fill factor was 71.31% and the photoelectric conversion efficiency was 14.73% (see table 1), and the J-V characteristic curve is shown in fig. 5.
Example 10
This example provides the application of poly 3, 4-ethylenedioxythiophene coated tungsten oxide nanorods, which is substantially identical to that of example 7, except that: preparing WO with the concentration of 5mg/mLXAnd mixing the @ PEDOT nanorod aqueous solution with the PEDOT/PSS solution according to the volume ratio of 1: 1.
Under the irradiation of light intensity of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.927V, and the short-circuit current is 18.04 mA-cm-2The fill factor was 76.13%, the photoelectric conversion efficiency was 12.74% (see table 1), and the J-V characteristic curve is shown in fig. 5.
Comparative example 1
This comparative example provides the use of a tungsten oxide nanorod, which is essentially identical to that of example 6, except that: using only WOXThe nanowires make the hole transport layer.
Under the irradiation of light intensity of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.508V, and the short-circuit current is 8.56 mA-cm-2The fill factor was 33.61%, the photoelectric conversion efficiency was 1.46% (see table 1), and the J-V characteristic curve is shown in fig. 5.
Comparative example 2
This comparative example provides the use of PEDOT: PSS as a hole transport layer, which is essentially identical to that of example 9, except that: PSS film is coated only on the cleaned ITO conductive glass substrate to obtain a hole transport layer.
Under the irradiation of light intensity of AM1.5, the open-circuit voltage of the perovskite solar cell is 0.949V, and the short-circuit current is 19.88 mA-cm-2The fill factor was 70.27%, the photoelectric conversion efficiency was 13.26% (see table 1), and the J-V characteristic curve is shown in fig. 5.
By comparing examples 6 and 9 with comparative examples 1 and 22, WO can be seenXThe @ PEDOT nanorod serving as a hole transport material has a hole transport property far superior to that of WOXNanowires, and commercial PEDOT: PSThe S hole transport material is comparable. By using WOXThe @ PEDOT nanorod doped PEDOT/PSS hole transport layer can further improve the hole transport efficiency, so that the photoelectric conversion efficiency of the perovskite solar cell is improved. The performance parameters of the perovskite solar cell prepared in each of the above examples are shown in table 1.
TABLE 1 PERFORMANCE PARAMETERS OF PEROVASE SOLAR CELLS PREPARED IN EXAMPLES 6-10 AND COMPARATIVE EXAMPLES 1-2
Experimental example 1
This example provides stability testing of perovskite devices of the different hole transport layers described above, specifically: perovskite solar cells prepared by example 6, example 9 and comparative example 2 were stored in a glove box (N)2Atmosphere, room temperature), the stability was tested separately. As shown in fig. 6, which is a curve of the change (decay) of PCE of three perovskite solar cells with storage time, it can be seen from fig. 6 that the perovskite solar cell prepared in example 6 has the highest stability, and the PCE still maintains 95% of the initial value after 35 days. The perovskite solar cells prepared in example 7 and comparative example 1 had PCE decayed by 15% and 23% after 35 days, respectively, with only 85% and 77% of the initial values. This is because PEDOT: PSS has strong acidity and causes a certain degree of corrosion to the ITO electrode, and thus the stability of the perovskite solar cell based on PEDOT: PSS is the worst. WO prepared in example 6XThe @ PEDOT hole transport layer is neutral, and corrosion of the ITO electrode is avoided, so that the material is based on WOXThe perovskite battery of @ PEDOT does not substantially decay under storage conditions. Hole transport layer of PEDOT PSS in example 9 due to WOXThe doping of the @ PEDOT nanorod slightly reduces the acidity, slows down the corrosion to the ITO electrode, and therefore, compared with the perovskite solar cell of the comparative example 2, the stability of the perovskite solar cell is slightly improved.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of a tungsten oxide nanorod coated with poly (3, 4-ethylenedioxythiophene) is characterized by comprising the following steps: dispersing tungsten oxide nanowires prepared by hydrothermal reaction in a solvent, adding EDOT to react to obtain a blue solution, and then removing PEDOT and tungsten oxide nanowires by settling and drying; the ratio of the tungsten oxide nanowires to the EDOT is 10-50 mg: 5-25 mu L of the tungsten oxide nano-wire, wherein the solvent is water, and the dispersion concentration of the tungsten oxide nano-wire is less than or equal to 50 mg/mL.
2. The preparation method of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod according to claim 1, wherein the preparation method comprises the following steps: the tungsten oxide nanowire is prepared by dissolving a tungsten salt precursor in a first solvent and carrying out hydrothermal reaction; the tungsten salt precursor is tungsten hexachloride; the first solvent is a mixture composed of one or more of ethanol, methanol, ethylene glycol and isopropanol, and the temperature of the hydrothermal reaction is 150-200 ℃.
3. The preparation method of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod according to claim 1, wherein the preparation method comprises the following steps: the tungsten oxide nanowires are 100-500 nm in length and 5-50 nm in width.
4. The preparation method of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod according to claim 1, wherein the preparation method comprises the following steps: and adding the EDOT, and reacting for 20-50 days at room temperature under the condition of continuous stirring to obtain a blue solution, wherein the stirring speed is 500-700 r/min.
5. The tungsten oxide nanorod coated with the poly (3, 4-ethylenedioxythiophene) is characterized in that: the preparation method of the tungsten oxide nano-rod coated by the poly-3, 4-ethylenedioxythiophene in the claims 1-4.
6. The application of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod as claimed in claim 5, which is characterized in that: dispersing the tungsten oxide nanorods coated with the poly (3, 4-ethylenedioxythiophene) in a solvent to form a dispersion, spin-coating the dispersion on a substrate, and heating and annealing to form a hole transport layer; or mixed with PEDOT: PSS to form a hole transport layer.
7. The application of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod according to claim 6, wherein: the substrate is an indium tin oxide or fluorine-doped tin oxide glass substrate.
8. The application of the poly 3, 4-ethylenedioxythiophene-coated tungsten oxide nanorod according to claim 6, wherein: the doping concentration of the poly 3, 4-ethylenedioxythiophene coated tungsten oxide nanorod in PEDOT PSS is 0.5-5 mg/mL.
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| CN113045735A (en) * | 2019-12-28 | 2021-06-29 | Tcl集团股份有限公司 | Nano material and preparation method thereof, quantum dot light-emitting diode and preparation method thereof |
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