CN110577240A - Zirconium-doped brookite phase titanium dioxide nano material and application thereof in perovskite solar cell - Google Patents
Zirconium-doped brookite phase titanium dioxide nano material and application thereof in perovskite solar cell Download PDFInfo
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- CN110577240A CN110577240A CN201910965938.XA CN201910965938A CN110577240A CN 110577240 A CN110577240 A CN 110577240A CN 201910965938 A CN201910965938 A CN 201910965938A CN 110577240 A CN110577240 A CN 110577240A
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention aims to provide a zirconium-doped brookite phase titanium dioxide nano material and application thereof in a perovskite solar cell. Sequentially adding zirconium nitrate pentahydrate, titanium tetraisopropoxide and urea into oxalic acid dihydrate, violently stirring for 15 min to fully and uniformly mix all components in the solution, transferring the solution in a beaker into a high-pressure reaction kettle, placing the reaction kettle in an oven with the temperature of 170-200 ℃ for constant-temperature reaction for 8-16 h, centrifugally separating, and calcining at high temperature to prepare the zirconium-doped brookite phase titanium dioxide nanorod2Under the conditions of light intensity and AM1.5, obtainphotoelectric conversion efficiency of 16.86%.
Description
Technical Field
The invention belongs to the technical field of solar cell materials, and particularly relates to a zirconium-doped brookite phase titanium dioxide nano material and application thereof in a perovskite solar cell.
Background
at present, no relevant patent report that the zirconium-doped brookite phase titanium dioxide is used as an electron transport layer to be applied to the perovskite solar cell exists.
Perovskite Solar Cells (PSCs) are a new type of Solar Cells developed from dye-sensitized Solar Cells, and have the advantages of easy assembly, low cost, high efficiency and the like, and have attracted great attention in the world. Through the development of ten years, the photoelectric conversion efficiency of the solar cell is dramatically increased from 3.8% to 24.2% in 2009, and the solar cell becomes a next-generation photovoltaic device with application prospect after being used as a dye-sensitized solar cell. At present, titanium dioxide, tin dioxide, zinc oxide, zinc stannate, barium stannate and other metal semiconductor oxides are all used as electron transport materials of perovskite solar cells. Among them, titanium dioxide is the most widely used electron transport material because of its advantages such as appropriate forbidden bandwidth, good photoelectrochemical stability and simple preparation process. Four common crystalline phases of titanium dioxide, anatase, rutile, brookite, and B phases, have been reported as electron transport materials. Among them, reports on the use of brookite phase titanium dioxide as an electron transport material of perovskite solar cells are few, and the obtained photoelectric conversion efficiency is low. In addition, no report is found about the application of the titanium dioxide doped with the brookite phase in the perovskite solar cell.
Disclosure of Invention
the invention aims to provide a zirconium-doped brookite phase titanium dioxide nano material and application thereof in a perovskite solar cell. The invention synthesizes the zirconium-doped brookite phase titanium dioxide nanorod by a one-step hydrothermal method for the first time, and applies the zirconium-doped brookite phase titanium dioxide nanorod to the electron transmission layer of the perovskite solar cell. At 100 mW/cm2Under the conditions of light intensity of AM1.5, takeA photoelectric conversion efficiency of 16.86% was obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method for synthesizing the zirconium-doped brookite phase titanium dioxide nanorod comprises the following steps: putting 15-30mL of deionized water into a beaker with the volume of 100 mL, adding 2-4 g of oxalic acid dihydrate, and stirring for about 5 min to fully dissolve the oxalic acid dihydrate. Then, 30-100 mg of zirconium nitrate pentahydrate, 0.5-1.5 mL of titanium tetraisopropoxide and 3-5g of urea are added in sequence, and the mixture is stirred vigorously for 15 min, so that all the components in the solution are mixed uniformly. Transferring the solution in the beaker into a high-pressure reaction kettle with the volume of 50 mL, and placing the reaction kettle in an oven with the temperature of 170-200 ℃ for constant-temperature reaction for 8-16 h to obtain white precipitate. The precipitate was centrifuged and washed 3 times with deionized water. Finally, the temperature is raised to 400-500 ℃ at the speed of 2 ℃/min by using a muffle furnace and is kept constant for 2-3 h to improve the crystallinity.
the application of the zirconium-doped brookite phase titanium dioxide nano material in the perovskite solar cell specifically comprises the following steps: mixing the prepared zirconium-doped brookite phase titanium dioxide nanorod with ethyl cellulose, and adding terpineol according to the proportion of 20: 2: 1, then adding 200 mL of absolute ethyl alcohol, fully stirring, and then carrying out reduced pressure rotary evaporation at 40 ℃ for 30min to obtain white viscous slurry. Diluting the obtained white slurry with absolute ethyl alcohol according to the mass ratio of 1: 15, and stirring vigorously for 24 hours to obtain uniform dispersion liquid for later use. And (3) coating the dispersion obtained by diluting on previously cleaned FTO conductive glass in a spinning way at the speed of 2000 revolutions per second, then placing the FTO conductive glass in a muffle furnace, heating to the temperature of 400-450 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2-3 h to obtain the required electron transport layer. And finally, assembling the perovskite solar cell device, and carrying out subsequent electrochemical performance characterization.
The invention has the following remarkable advantages:
According to the invention, the zirconium-doped brookite phase titanium dioxide nanorod is synthesized by a hydrothermal method for the first time and is applied to the perovskite solar cell, so that the high conversion efficiency of 16.86% is obtained. The synthesis method is simple and easy to implement, has good reproducibility, and provides a new idea for high-performance and industrial research of the perovskite solar cell.
Drawings
FIG. 1 is an XRD spectrum of a titanium dioxide nanorod in a zirconium-doped brookite phase;
FIG. 2 is a scanning electron micrograph of an electron transport layer;
FIG. 3, scanning electron micrograph of perovskite film;
FIG. 4 is a graph of the photovoltaic performance of a perovskite solar cell.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Example 1
the method for synthesizing the zirconium-doped brookite phase titanium dioxide nanorod comprises the following steps: 25 mL of deionized water was placed in a beaker having a volume of 100 mL, 3 g of oxalic acid dihydrate was added, and the mixture was stirred for about 5 min to dissolve it sufficiently. Then, 30 mg of zirconium nitrate pentahydrate, 1mL of titanium tetraisopropoxide and 4g of urea are added in sequence, and the mixture is stirred vigorously for 15 min, so that all the components in the solution are mixed uniformly. Transferring the solution in the beaker into a high-pressure reaction kettle with the volume of 50 mL, and placing the high-pressure reaction kettle in an oven with the temperature of 180 ℃ for constant-temperature reaction for 12 hours to obtain white precipitate. The precipitate was centrifuged and washed 3 times with deionized water. Finally, the temperature is raised to 400 ℃ at the speed of 2 ℃/min by using a muffle furnace and is kept constant for 2h so as to improve the crystallinity of the material.
Application example 1
The application of the zirconium-doped brookite phase titanium dioxide nanomaterial prepared in the embodiment 1 in a perovskite solar cell specifically comprises the following steps: mixing the prepared zirconium-doped brookite phase titanium dioxide nanorod with ethyl cellulose, and adding terpineol according to the proportion of 20: 2: 1, then adding 200 mL of absolute ethyl alcohol, fully stirring, and then carrying out reduced pressure rotary evaporation at 40 ℃ for 30min to obtain white viscous slurry. Diluting the obtained white slurry with absolute ethyl alcohol according to the mass ratio of 1: 15, and stirring vigorously for 24 hours to obtain uniform dispersion liquid for later use. And (3) coating the dispersion obtained by diluting on previously cleaned FTO conductive glass in a spinning mode at the speed of 2000 revolutions per second, then placing the FTO conductive glass in a muffle furnace, heating to 400 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2 hours to obtain the required electron transport layer. And finally, assembling the perovskite solar cell device, and carrying out subsequent electrochemical performance characterization.
FIG. 1 is XRD spectrum of zirconium doped brookite phase titanium dioxide nanorod, diffraction peaks in the spectrum before and after doping can be assigned to brookite phase titanium dioxide, and JCDPS card number is 29-1360. Furthermore, the shift phenomenon of the diffraction peaks, demonstrates that zirconium is successfully doped into brookite phase titania.
FIG. 2 is a scanning electron microscope image of the electron transport layer, which shows that the zirconium doped brookite phase titanium dioxide nanorods are distributed more uniformly on the surface of the FTO, the length range is 100-200 nm, and the width is about 50 nm.
FIG. 3 is a scanning electron microscope image of the perovskite film, which shows that the perovskite has good crystallinity, the crystal size range is between 500-800 nm, and the small particles are lead diiodide which is not completely reacted.
Fig. 4 is a graph of the photovoltaic performance of a perovskite solar cell. Short-circuit current J when undoped brookite phase titanium dioxide is used as an electron transport layerscIs 20.50 mA/cm2open circuit voltage Voc At 1.03V, the corresponding photoelectric conversion efficiency was 14.78%. Short-circuit current J when using zirconium-doped brookite phase titanium dioxide as electron transport layerscAnd an open circuit voltage VocAre all improved and are respectively 22.02 mA/cm2And 1.09V, the corresponding photoelectric conversion efficiency is also improved to 16.86 percent.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A preparation method of a zirconium-doped brookite phase titanium dioxide nano material is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) Putting 15-30mL of deionized water into a beaker with the volume of 100 mL, adding 2-4 g of oxalic acid dihydrate, and stirring for 5 min to fully dissolve the oxalic acid dihydrate;
(2) Then, sequentially adding 30-100 mg of zirconium nitrate pentahydrate, 0.5-1.5 mL of titanium tetraisopropoxide and 3-5g of urea, and violently stirring for 15 min to fully and uniformly mix all the components in the solution;
(3) Transferring the solution in the beaker into a high-pressure reaction kettle with the volume of 50 mL, and placing the reaction kettle in a drying oven for constant-temperature reaction to obtain white precipitate; centrifuging the precipitate, and washing with deionized water for 3 times;
(4) And finally, heating to 400-.
2. The method for preparing the titanium dioxide nano material of the zirconium doped plate titanic phase according to the claim 1, which is characterized in that: the constant temperature reaction in the step (3) is as follows: reacting at constant temperature of 170 and 200 ℃ in an oven for 8-16 h.
3. The method for preparing the titanium dioxide nano material of the zirconium doped plate titanic phase according to the claim 1, which is characterized in that: and (4) the temperature rise rate of the muffle furnace in the step (4) is 2 ℃/min.
4. Use of the zirconium doped perovskite phase titania nanomaterial prepared by the method of claim 1 in a perovskite solar cell, wherein: the method specifically comprises the following steps: uniformly mixing the prepared zirconium-doped brookite-phase titanium dioxide nanorod with ethyl cellulose and terpineol, then adding 200 mL of absolute ethyl alcohol, fully stirring, and performing reduced pressure rotary evaporation at 40 ℃ for 30min to obtain white viscous slurry; diluting the obtained white slurry with absolute ethyl alcohol according to the mass ratio of 1: 15, and after stirring vigorously for 24 hours, obtaining uniform dispersion liquid for later use; coating the diluted dispersion liquid on previously cleaned FTO conductive glass in a spinning mode at the speed of 2000 revolutions per second, and then placing the FTO conductive glass in a muffle furnace for calcination to obtain a required electron transport layer; and finally, assembling the perovskite solar cell device, and carrying out subsequent electrochemical performance characterization.
5. Use according to claim 4, characterized in that: mixing the prepared zirconium-doped brookite phase titanium dioxide nanorod with ethyl cellulose, and adding terpineol according to the proportion of 20: 2: 1, in a mass ratio of 1.
6. use according to claim 4, characterized in that: the calcination is specifically as follows: heating to 400-450 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2-3 h.
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Citations (5)
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JP2007246301A (en) * | 2006-03-13 | 2007-09-27 | Matsumoto Fine Chemical Co Ltd | Method for producing brookite-type titanium dioxide |
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Patent Citations (5)
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JP2007246301A (en) * | 2006-03-13 | 2007-09-27 | Matsumoto Fine Chemical Co Ltd | Method for producing brookite-type titanium dioxide |
CN102332356A (en) * | 2010-06-25 | 2012-01-25 | 索尼公司 | DSSC and manufacturing approach thereof |
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