CN105576126A - A kind of preparation method of perovskite solar cell based on H-TiO2 nanopowder - Google Patents

Abstract

The invention discloses a preparation method of a perovskite solar battery based on H-TiO2 nanometer powder, and relates to a preparation method of a perovskite solar battery based on H-TiO2 nanometer powder, for solving the problems of battery performance degradation caused by severe interface compounding due to application of an H-TiO2 material as an electronic layer material of a conventional perovskite solar battery, low energy utilization of a near-infrared zone by the perovskite solar battery prepared in the prior arts and low battery efficiency. The method comprises the following steps: 1, preparing H-TiO2; 2, preparing an H-TiO2 photoanode slurry; 3, preparing a compact layer solution; 4, preparing perovskite layer solution; 5, preparing a cavity transmission layer solution; 6, cleaning a substrate; and 7, preparing the perovskite solar battery. The method provided by the invention is applied to preparation of a perovskite solar battery.

Description

A kind of preparation method of perovskite solar cell based on H-TiO2 nanopowder

technical field

The invention relates to a method for preparing a perovskite solar cell based on H- _TiO2 nanometer powder.

Background technique

The organic-inorganic hybrid perovskite (referred to as perovskite) solar cells that have emerged in recent years have attracted widespread attention from academia and industry due to their high photoelectric energy conversion efficiency and simple preparation process, and have broad development prospects. . Among them, planar heterojunction perovskite solar cells have become an important direction of current research because of their simple structure and many advantages such as low-temperature preparation. Perovskite solar cells have little energy utilization in the near-infrared region, which makes the absorption spectrum of the cell not match the solar spectrum, which limits the improvement of cell efficiency.

Hydrogenated titanium dioxide can utilize visible and near-infrared light, and has a narrow band gap and a high donor density, which makes it possible to be suitable for perovskite solar cells. Hydrogenated titanium dioxide is prepared by treating titanium dioxide with high-pressure heating. This simple and efficient method has wide applicability. Using this prepared hydrogenated titanium dioxide in perovskite solar cells has obtained higher photoelectric conversion efficiency and short-circuit current density. However, the preparation process of hydrogenated titanium dioxide always requires moderate hydrogenation and reduction. Over-hydrogenated titanium dioxide has poor conductivity, electrons are easy to recombine, and the photocurrent will decrease sharply, which will significantly reduce the photoelectric conversion efficiency of the battery.

Contents of the invention

The present invention aims to solve the problem that the hydrogenated titanium dioxide material is used as the electronic layer material of the perovskite solar cell due to the serious interface recombination of the battery performance, and the perovskite solar cell prepared by the prior art has less energy utilization in the near-infrared light region and low battery efficiency. problem, and provides a method for the preparation of perovskite solar cells based on H- _TiO2 nanopowders.

A kind of preparation method based on H- _TiO Nano powder perovskite solar cell is specifically carried out according to the following steps:

1. Place the titanium dioxide nanopowder in the quartz boat, place the quartz boat containing the titanium dioxide nanopowder in the tube furnace, continuously feed the mixed gas of nitrogen and hydrogen, and then increase the reaction temperature at a heating rate of 1°C/min. Raise the temperature from room temperature to 300°C to 600°C, keep it warm at 300°C to 600°C for 3h to 8h, then transfer it to a vacuum drying oven and let it stand for 1h to 5h, then cool to room temperature to obtain H-TiO ₂ powder; Titanium dioxide nanopowder is prepared by sol hydrothermal method; the ratio of hydrogen to nitrogen in the mixed gas of nitrogen and hydrogen is 1:9; the flow rate of the mixed gas of nitrogen and hydrogen is 100sccm～400sccm;

2. Mix H- _TiO2 powder, ethyl cellulose, terpineol and ethanol, and stir evenly to obtain a slurry; the mass ratio of H- _TiO2 powder to ethyl cellulose is 1:(0.1～0.5 ); the mass ratio of the H- _TiO2 powder to terpineol is 1:(2～7); the mass ratio of the H- _TiO2 powder to ethanol is 1:(20～40);

3. Preparation of dense layer solution: Mix hydrochloric acid with a concentration of 2mol/L and isopropanol I to obtain mixed liquid A; mix titanium isopropoxide with isopropanol II to obtain mixed liquid B; Add the mixed solution A dropwise to the mixed solution B under the conditions until the mixed solution is clarified to obtain a dense layer solution; the volume ratio of the hydrochloric acid with a concentration of 2mol/L to isopropanol I is 1:(100～500); The volume ratio of titanium propoxide to isopropanol II is 1:(10-35); the volume ratio of mixed solution A to mixed solution B is 1:(0.8-1.2);

4. Preparation of perovskite layer solution: Dissolve lead iodide in DMF, then magnetically stir for 10h to 14h at a temperature of 50°C to 80°C to obtain perovskite layer solution A; dissolve methylammonium iodide in In DMF, the perovskite layer solution B is obtained; the concentration of the perovskite layer solution A is 400mg/mL～500mg/mL; the concentration of the perovskite layer solution B is 4mg/mL～10mg/mL;

5. Preparation of hole transport layer solution: Dissolve lithium salt in acetonitrile and stir for 10min to 20min to obtain lithium salt solution; mix chlorobenzene, Spiro-OMeTAD, tributyl phosphate and lithium salt solution, and stir at room temperature for 10min ～20min, obtain hole transport layer solution; The concentration of described lithium salt solution is 500mg/mL～600mg/mL; The mass ratio of the volume of described chlorobenzene and Spiro-OMeTAD is 1mL:(50～80) mg; The volume ratio of chlorobenzene and tributyl phosphate is 1:(0.02～0.04); the volume ratio of described chlorobenzene and lithium salt solution is 1:(0.01～0.02);

6. Clean the substrate: Clean the FTO conductive glass ultrasonically for 3 to 5 times with deionized water, then ultrasonically clean with isopropanol for 3 to 5 times, then ultrasonically clean with acetone for 3 to 5 times, and finally treat with ultraviolet and ozone for 10 minutes. 20min to obtain a clean transparent conductive glass substrate;

7. Use a clean transparent conductive glass substrate as the base material, and spin it at a speed of 2000rpm to 5000rpm for 30s to 60s by spin coating, and use the dense layer solution obtained in step 3 to spin coat a layer with a thickness of 80nm to 80nm on the base material. After the dense layer of 120nm titanium dioxide, anneal at a temperature of 500°C for 30min to 60min; After spin-coating a porous titanium dioxide layer with a thickness of 280nm to 320nm on the dense layer of titanium dioxide, anneal at a temperature of 500°C for 30min to 60min; then use spin coating at a speed of 4000rpm to 8000rpm for 5s to 20s , using the perovskite layer solution A obtained in step 4 to spin-coat a layer of perovskite layer A on a porous titanium dioxide layer with a thickness of 280nm to 320nm, heat on a hot stage at a temperature of 100°C for 15min to 20min, and naturally cool to room temperature; Then spin coating at a speed of 3000rpm to 6000rpm for 5s to 20s, use the perovskite layer solution B obtained in step 4 to spin coat a layer of perovskite layer B on the perovskite layer A, and heat it at a temperature of 100°C Heating on the stage for 15min-20min, cooling down to room temperature naturally to obtain polycrystalline methylamine lead iodine film; Spin-coat a hole transport layer on the methylamine lead iodide polycrystalline film, heat it on a hot stage at 100°C for 15min to 20min, and cool it down to room temperature naturally; Evaporating the gold electrode layer completes the preparation of the perovskite solar cell based on the H- _TiO2 nanopowder.

Beneficial effects of the present invention:

The present invention prepares the perovskite solar cell based on H- _TiO nanopowder, compared with the traditional perovskite solar cell, this perovskite solar cell has the following advantages:

The TiO ₂ nanopowder is mixed with hydrogen and nitrogen to form H-TiO ₂ nanopowder. By appropriately introducing the concentration of oxygen vacancies on the surface of the nanomaterial, the donor density of the nanopowder is increased and the band gap of the powder is reduced. ; At the same time, this nano-powder prolongs the life of photogenerated electrons, which is beneficial to the improvement of battery performance. The perovskite solar cell with H- _TiO2 nanopowder enhances the utilization of incident light and improves the solar light capture efficiency of the cell. The perovskite solar cell with H- _TiO2 nanometer powder can inhibit the recombination reaction of photogenerated carriers, prolong the life of carriers in the cell, reduce dark current, and help improve cell efficiency. This perovskite solar cell with H- _TiO2 nanopowder can prolong the recombination time of electrons, accelerate the transmission of electrons, and improve the photoelectric conversion efficiency of the cell. Based on the above characteristics, the cell efficiency of this photoanode perovskite solar cell based on H- _TiO2 nanopowder spheres is increased from 10.8% to 13.2%, and the photocurrent is increased by 22.0%.

Description of drawings

Fig. 1 is the H- _TiO that embodiment one step one obtains The scanning electron micrograph of powder;

Fig. 2 is the titanium dioxide nano-powder described in embodiment two and the H- _TiO of embodiment one step one The ultraviolet-visible absorption spectrogram of the powder that obtains, wherein 1 is the titanium dioxide nano-powder described in embodiment two, and 2 is embodiment The H- _TiO powder that one step one obtains;

Fig. 3 is the Mott-Schottky curve of the titanium dioxide nanopowder described in embodiment two and the H- _TiO2 powder that embodiment one step one obtains, and wherein 1 is the titanium dioxide nanopowder described in embodiment two, and 2 is The H-TiO that embodiment 1 step ₁ obtains powder;

Fig. 4 is the photoanode cell prepared with the _TiO2 dye-sensitized solar cell photoanode obtained in embodiment two and the perovskite solar cell based on H- _TiO2 nanopowder obtained in embodiment one under simulated 1.5G sunlight The short-circuit current and open-circuit voltage curves, wherein 1 is the photoanode cell prepared by the _TiO dye-sensitized solar cell photoanode that is obtained in embodiment two, and 2 is the perovskite based on H- _TiO nano-powder obtained in embodiment one mining solar cells;

Figure 5 is the AC impedance of the photoanode cell prepared from the _TiO2 dye-sensitized solar cell photoanode obtained in Example 2 and the perovskite solar cell based on H- _TiO2 nanometer powder obtained in Example 1 under light conditions Spectrogram, wherein 1 is the TiO obtained in embodiment _two The photoanode cell prepared by the dye-sensitized solar cell photoanode, and ₂ is the H-TiO obtained in embodiment one Based on the perovskite solar cell of nanopowder;

Fig. 6 is with the TiO obtained in embodiment _two The photoanode cell prepared by the dye-sensitized solar cell photoanode and the perovskite solar cell based on H- _TiO obtained in embodiment one; The open circuit voltage decay curve, Wherein 1 is obtained with embodiment two _TiO The photoanode cell prepared by the dye-sensitized solar cell photoanode, ₂ is the H-TiO obtained in embodiment one Based on the perovskite solar cell of nanopowder;

Fig. 7 is obtained with the _TiO2 dye-sensitized solar cell photoanode prepared by embodiment two and the open circuit voltage decay curve of the perovskite solar cell based on H- _TiO2 nanopowder that embodiment one obtains, wherein 1 is the TiO that obtains with embodiment _two The photoanode cell that dye-sensitized solar cell photoanode prepares, 2 is the perovskite solar cell electronic life curve based on H- _TiO that the embodiment one obtains nanopowder;

Fig. 8 is the photoanode cell prepared with the _TiO dye-sensitized solar cell photoanode obtained in embodiment two and the perovskite solar cell based on H- _TiO nano powder obtained in embodiment one under simulated 1.5G sunlight The photoelectric conversion efficiency, wherein 1 is obtained with embodiment two TiO ₂ The photoanode cell prepared by dye-sensitized solar cell photoanode, 2 is the perovskite solar cell based on H- _TiO nanometer powder obtained in embodiment 1 ;

Fig. 9 is with the TiO that obtains in embodiment ₂ dye-sensitized solar cell photoanode prepares the photoanode cell and embodiment 1 obtains based on H-TiO ₂ The ultraviolet-visible absorption spectrum of the perovskite solar cell of nanopowder, Wherein 1 is obtained with embodiment two _TiO The photoanode cell prepared by the dye-sensitized solar cell photoanode, ₂ is the H-TiO obtained in embodiment one Based on the perovskite solar cell of nanopowder;

FIG. 10 is a cross-sectional view of a perovskite solar cell based on H-TiO ₂ nanopowder obtained in Example 1.

detailed description

Specific embodiment one: a kind of H- _TiO of the present embodiment is based on The preparation method of the perovskite solar cell of nanopowder is specifically carried out according to the following steps:

1. Place the titanium dioxide nanopowder in the quartz boat, place the quartz boat containing the titanium dioxide nanopowder in the tube furnace, continuously feed the mixed gas of nitrogen and hydrogen, and then increase the reaction temperature at a heating rate of 1°C/min. Raise the temperature from room temperature to 300°C to 600°C, keep it warm at 300°C to 600°C for 3h to 8h, then transfer it to a vacuum drying oven and let it stand for 1h to 5h, then cool to room temperature to obtain H-TiO ₂ powder; Titanium dioxide nanopowder is prepared by sol hydrothermal method; the ratio of hydrogen to nitrogen in the mixed gas of nitrogen and hydrogen is 1:9; the flow rate of the mixed gas of nitrogen and hydrogen is 100sccm～400sccm;

2. Mix H- _TiO2 powder, ethyl cellulose, terpineol and ethanol, and stir evenly to obtain a slurry; the mass ratio of H- _TiO2 powder to ethyl cellulose is 1:(0.1～0.5 ); the mass ratio of the H- _TiO2 powder to terpineol is 1:(2～7); the mass ratio of the H- _TiO2 powder to ethanol is 1:(20～40);

3. Preparation of dense layer solution: Mix hydrochloric acid with a concentration of 2mol/L and isopropanol I to obtain mixed liquid A; mix titanium isopropoxide with isopropanol II to obtain mixed liquid B; Add the mixed solution A dropwise to the mixed solution B under the conditions until the mixed solution is clarified to obtain a dense layer solution; the volume ratio of the hydrochloric acid with a concentration of 2mol/L to isopropanol I is 1:(100～500); The volume ratio of titanium propoxide to isopropanol II is 1:(10-35); the volume ratio of mixed solution A to mixed solution B is 1:(0.8-1.2);

4. Preparation of perovskite layer solution: Dissolve lead iodide in DMF, then magnetically stir for 10h to 14h at a temperature of 50°C to 80°C to obtain perovskite layer solution A; dissolve methylammonium iodide in In DMF, the perovskite layer solution B is obtained; the concentration of the perovskite layer solution A is 400mg/mL～500mg/mL; the concentration of the perovskite layer solution B is 4mg/mL～10mg/mL;

5. Preparation of hole transport layer solution: Dissolve lithium salt in acetonitrile and stir for 10min to 20min to obtain lithium salt solution; mix chlorobenzene, Spiro-OMeTAD, tributyl phosphate and lithium salt solution, and stir at room temperature for 10min ～20min, obtain hole transport layer solution; The concentration of described lithium salt solution is 500mg/mL～600mg/mL; The mass ratio of the volume of described chlorobenzene and Spiro-OMeTAD is 1mL:(50～80) mg; The volume ratio of chlorobenzene and tributyl phosphate is 1:(0.02～0.04); the volume ratio of described chlorobenzene and lithium salt solution is 1:(0.01～0.02);

6. Cleaning the substrate: Clean the FTO conductive glass with deionized water ultrasonically for 3 to 5 times, then with acetone for 3 to 5 times, then with isopropanol for 3 to 5 times, and finally with ultraviolet ozone for 10 minutes. 20min to obtain a clean transparent conductive glass substrate;

7. Use a clean transparent conductive glass substrate as the base material, and spin it at a speed of 2000rpm to 5000rpm for 30s to 60s by spin coating, and use the dense layer solution obtained in step 3 to spin coat a layer with a thickness of 80nm to 80nm on the base material. After the dense layer of 120nm titanium dioxide, anneal at a temperature of 500°C for 30min to 60min; After spin-coating a porous titanium dioxide layer with a thickness of 280nm to 320nm on the dense layer of titanium dioxide, anneal at a temperature of 500°C for 30min to 60min; then use spin coating at a speed of 4000rpm to 8000rpm for 5s to 20s , using the perovskite layer solution A obtained in step 4 to spin-coat a layer of perovskite layer A on a porous titanium dioxide layer with a thickness of 280nm to 320nm, heat on a hot stage at a temperature of 100°C for 15min to 20min, and naturally cool to room temperature; Then spin coating at a speed of 3000rpm to 6000rpm for 5s to 20s, use the perovskite layer solution B obtained in step 4 to spin coat a layer of perovskite layer B on the perovskite layer A, and heat it at a temperature of 100°C Heating on the stage for 15min-20min, cooling down to room temperature naturally to obtain polycrystalline methylamine lead iodine film; Spin-coat a hole transport layer on the methylamine lead iodide polycrystalline film, heat it on a hot stage at 100°C for 15min to 20min, and cool it down to room temperature naturally; Evaporating the gold electrode layer completes the preparation of the perovskite solar cell based on the H- _TiO2 nanopowder.

The sheet resistance of the FTO conductive glass described in this embodiment is 15 ohms/square.

Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is: in step 1, keep warm at 300° C. for 5 hours. Other steps and parameters are the same as those in the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that in Step 1, keep the temperature at 500° C. for 4 hours. Other steps and parameters are the same as those in Embodiment 1 or 2.

Embodiment 4: This embodiment is different from Embodiment 1 to Embodiment 3 in that: in step 1, the temperature is 90° C. for 20 minutes for heating and dissolving. Other steps and parameters are the same as those in the first to third specific embodiments.

Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 4 in that the mass ratio of H-TiO ₂ powder to ethyl cellulose in step 2 is 1:0.3. Other steps and parameters are the same as in one of the specific embodiments 1 to 4.

Embodiment 6: The difference between this embodiment and one of Embodiments 1 to 5 is that the mass ratio of H-TiO ₂ powder and terpineol described in step 2 is 1:5. Other steps and parameters are the same as one of the specific embodiments 1 to 5.

Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that the mass ratio of H-TiO ₂ powder to ethanol in step 2 is 1:30. Other steps and parameters are the same as one of the specific embodiments 1 to 6.

Embodiment 8: The difference between this embodiment and Embodiment 1 to 7 is that the volume ratio of hydrochloric acid and isopropanol I with a concentration of 2 mol/L as described in step 3 is 1:200; titanium isopropoxide and The volume ratio of isopropanol II is 1:30; the volume ratio of mixture A and mixture B is 1:1. Other steps and parameters are the same as one of the specific embodiments 1 to 7.

Specific embodiment nine: the difference between this embodiment and one of specific embodiments one to eight is: the concentration of the perovskite layer solution A described in step 4 is 400 mg/mL～500 mg/mL; the concentration of the perovskite layer solution B It is 4mg/mL～10mg/mL. Other steps and parameters are the same as one of the specific embodiments 1 to 8.

Specific embodiment ten: the difference between this embodiment and specific embodiment one to nine is: the mass ratio of the volume of chlorobenzene described in step 5 and Spiro-OMeTAD is 1mL:60mg; Described chlorobenzene and tributyl phosphate The volume ratio of the chlorobenzene and the lithium salt solution is 1:0.015. Other steps and parameters are the same as one of the specific implementation modes 1 to 9.

Verify the beneficial effects of the present invention through the following examples:

Embodiment one: a kind of H- _TiO of the present embodiment is based on The preparation method of the perovskite solar cell of nanopowder is specifically carried out according to the following steps:

1. Place the titanium dioxide nanopowder in the quartz boat, place the quartz boat containing the titanium dioxide nanopowder in the tube furnace, continuously feed the mixed gas of nitrogen and hydrogen, and then increase the reaction temperature at a heating rate of 1°C/min. Raise the temperature from room temperature to 300°C, keep it warm at 300°C for 5h, then transfer it to a vacuum drying oven and let it stand for 1h, then cool to room temperature to obtain H- _TiO2 powder; the titanium dioxide nanopowder is prepared by sol hydrothermal method Formed; the hydrogen-nitrogen ratio in the mixed gas of nitrogen and hydrogen is 1:9; the flow velocity of the mixed gas of nitrogen and hydrogen is 300 sccm;

2. Mix H- _TiO2 powder, ethyl cellulose, terpineol and ethanol, and stir to obtain a slurry; the mass ratio of H- _TiO2 powder to ethyl cellulose is 1:0.27; H- _TiO The mass ratio of powder and terpineol is 1:4.68; the H- _TiO The mass ratio of powder and ethanol is 1:2.98;

3. Prepare the dense layer solution: mix 10 μL ~ 20 μL of hydrochloric acid with a concentration of 2 mol/L and 2 mL ~ 5 mL of isopropanol I to obtain a mixed solution A; mix 150 μL ~ 200 μL of titanium isopropoxide with 2 mL ~ 5 mL of isopropanol II, Obtain the mixed solution B; add the mixed solution A dropwise to the mixed solution B under the condition that the stirring speed is 100rpm until the mixed solution is clarified to obtain a dense layer solution; the volume ratio of the mixed solution A to the mixed solution B is 1:1;

4. Preparation of perovskite layer solution: Dissolve lead iodide in DMF, then magnetically stir for 12 hours at a temperature of 50°C to 80°C to obtain perovskite layer solution A; dissolve methylammonium iodide in DMF , to obtain a perovskite layer solution B; the concentration of the perovskite layer solution A is 400mg/mL～500mg/mL; the concentration of the perovskite layer solution B is 4mg/mL～10mg/mL;

5. Preparation of hole transport layer solution: Dissolve lithium salt in acetonitrile, stir for 10min-20min to obtain lithium salt solution; mix 1mL chlorobenzene, 50mg-80mgSpiro-OMeTAD, 20μL-40μL tributyl phosphate and 10μL-20μL lithium The salt solution was mixed, and stirred at room temperature for 10 minutes to obtain a hole transport layer solution;

6. Clean the substrate: Clean the FTO conductive glass ultrasonically for 3 to 5 times with deionized water, then ultrasonically clean with isopropanol for 3 to 5 times, then ultrasonically clean with acetone for 3 to 5 times, and finally treat with ultraviolet and ozone for 10 minutes. 20min to obtain a clean transparent conductive glass substrate;

7. Use a clean transparent conductive glass substrate as the base material, and rotate it at a speed of 2000rpm to 5000rpm for 30s to 60s by spin coating, and use the dense layer solution obtained in step 3 to spin coat a layer of 100nm thick layer on the base material. After the dense layer of titanium dioxide, anneal at a temperature of 500°C for 30min to 60min; then use spin coating at a speed of 4000rpm to 8000rpm for 30s to 60s, and use the slurry obtained in step 2 to coat the dense layer of titanium dioxide with a thickness of 100nm After spin-coating a layer of porous titanium dioxide layer with a thickness of 300nm on the surface, anneal at a temperature of 500°C for 30min to 60min; Perovskite layer solution A spin-coats a layer of perovskite layer A on a porous titanium dioxide layer with a thickness of 300nm, heats on a hot stage at a temperature of 100°C for 15min to 20min, and naturally cools to room temperature; then spin-coats at 3000rpm Rotate at a speed of ~6000rpm for 5s~20s, use the perovskite layer solution B obtained in step 4 to spin coat a layer of perovskite layer B on the perovskite layer A, and heat it on a hot stage at a temperature of 100°C for 15min~20min, naturally Cool to room temperature to obtain a methylamine lead iodide polycrystalline film; then use spin coating at a speed of 3000rpm to 6000rpm for 5s to 20s, use the hole transport layer solution obtained in step 5 to coat the methylamine lead iodide polycrystalline film Spin-coat a layer of hole transport layer on top, heat on a hot stage at 100°C for 15min to 20min, and cool down to room temperature naturally; Preparation of H- _TiO2 Nanopowders for Perovskite Solar Cells.

The titanium dioxide nanopowder described in this embodiment is prepared by a sol hydrothermal method, and the specific operation steps are as follows:

Add 0.3mL～0.6mL HNO ₃ and 0.1g～3gF127 into 50mL～100mL deionized water, mix and stir evenly to obtain a mixed solution, and add 0.02M～0.05M tetratitanate at a rate of 60 drops/min while stirring Add butyl ester dropwise to the mixed solution; after the dropwise addition, heat the mixed solution in a water bath at a temperature of 80°C to 100°C for 4h to 8h to obtain a sol-like mixture; transfer the sol-like mixture to a sealed water in a hot kettle, and then reacted in an oven at a temperature of 160°C to 200°C for 12h to 30h. After the reaction, the product was first washed with deionized water for 3 to 5 times, then washed with absolute ethanol for 3 to 5 times, and cooled naturally to room temperature, and then centrifuge the product at a centrifugal speed of 3000rpm to 15000rpm to obtain a solid. The solid is first washed with deionized water for 2 to 5 times, and then washed with absolute ethanol for 2 to 5 times, and then placed in a vacuum at 100 ° C. Drying in an oven for 1h to 5h, and finally putting in a muffle furnace, calcining at a temperature of 300°C to 600°C for 0.5h to 6h, cooling to room temperature to obtain titanium dioxide nano powder.

Embodiment two: a kind of _TiO of the present embodiment The preparation method of dye-sensitized solar cell photoanode is specifically carried out according to the following steps:

Mix titanium dioxide nanopowder, ethyl cellulose, terpineol and ethanol, stir evenly to obtain a slurry, use a 250-mesh screen to screen-print the slurry, the effective area of the screen is 16cm ² , and print in the vertical direction Six times to obtain a six-layer TiO ₂ film, and then heat the six-layer TiO ₂ film from room temperature to 500°C at a heating rate of 1°C/min, and keep it at 500°C for 0.5h to obtain TiO ₂ dye-sensitized solar cell photoanode; the mass ratio of the titanium dioxide nano-powder and ethyl cellulose is 1:0.27; the mass ratio of the titanium dioxide nano-powder and terpineol is 1:4.68; the titanium dioxide nano-powder and The mass ratio of ethanol is 1:2.98.

The titanium dioxide nanopowder described in this embodiment is prepared by a sol hydrothermal method, and the specific operation steps are as follows:

Add 0.3mL～0.6mL HNO ₃ and 0.1g～3gF127 into 50mL～100mL deionized water, mix and stir evenly to obtain a mixed solution, and add 0.02M～0.05M tetratitanate at a rate of 60 drops/min while stirring Add butyl ester dropwise to the mixed solution; after the dropwise addition, heat the mixed solution in a water bath at a temperature of 80°C to 100°C for 4h to 8h to obtain a sol-like mixture; transfer the sol-like mixture to a sealed water in a hot kettle, and then reacted in an oven at a temperature of 160°C to 200°C for 12h to 30h. After the reaction, the product was first washed with deionized water for 3 to 5 times, then washed with absolute ethanol for 3 to 5 times, and cooled naturally to room temperature, and then centrifuge the product at a centrifugal speed of 3000rpm to 15000rpm to obtain a solid. The solid is first washed with deionized water for 2 to 5 times, and then washed with absolute ethanol for 2 to 5 times, and then placed in a vacuum at 100 ° C. Drying in an oven for 1h to 5h, and finally putting in a muffle furnace, calcining at a temperature of 300°C to 600°C for 0.5h to 6h, cooling to room temperature to obtain titanium dioxide nano powder.

Fig. 1 is the scanning electron micrograph of the H-TiO ₂ powder obtained in step 1 of Example 1; it can be seen from the figure that the prepared H-TiO ₂ powder is nano-spheres and a small amount of V-shaped crystals.

Fig. 2 is the titanium dioxide nano-powder described in embodiment two and the H- _TiO of embodiment one step one The ultraviolet-visible absorption spectrogram of the powder that obtains, wherein 1 is the titanium dioxide nano-powder described in embodiment two, and 2 is embodiment The H-TiO ₂ powder obtained in one step one; it can be seen from the figure that the H-TiO ₂ powder has a strong absorption in the visible region.

Fig. 3 is the Mott-Schottky curve of the titanium dioxide nanopowder described in embodiment two and the H- _TiO2 powder that embodiment one step one obtains, and wherein 1 is the titanium dioxide nanopowder described in embodiment two, and 2 is The H-TiO ₂ powder obtained in Step 1 of Example 1; it can be seen from the figure that the samples are all n-type semiconductors, and the hydrogenation treatment has no effect on the type of semiconductor. The slope of the H- _TiO2 nanoparticles is smaller than that of the blank _TiO2 sample, indicating that the H- _TiO2 has a higher donor density.

Fig. 4 is the photoanode cell prepared with the _TiO2 dye-sensitized solar cell photoanode obtained in embodiment two and the perovskite solar cell based on H- _TiO2 nanopowder obtained in embodiment one under simulated 1.5G sunlight The short-circuit current and open-circuit voltage curves, wherein 1 is the photoanode cell prepared by the _TiO dye-sensitized solar cell photoanode that is obtained in embodiment two, and 2 is the perovskite based on H- _TiO nano-powder obtained in embodiment one Mine solar cell; It can be seen from the figure that the perovskite solar cell based on H- _TiO2 nano powder obtained in embodiment one can increase short-circuit current and open-circuit voltage, thereby improving the photoelectric conversion efficiency of the cell.

Figure 5 is the AC impedance of the photoanode cell prepared from the _TiO2 dye-sensitized solar cell photoanode obtained in Example 2 and the perovskite solar cell based on H- _TiO2 nanometer powder obtained in Example 1 under light conditions Spectrogram, wherein 1 is the TiO obtained in embodiment _two The photoanode cell prepared by the dye-sensitized solar cell photoanode, ₂ is the H-TiO obtained in embodiment one Based on the perovskite solar cell of nanopowder; From It can be seen from the figure that the perovskite solar cell based on H- _TiO2 nanopowder obtained in Example 1 can inhibit the recombination reaction of photogenerated carriers, which is beneficial to improve the performance of the cell.

Fig. 6 is with the TiO obtained in embodiment _two The photoanode cell prepared by the photoanode of the dye-sensitized solar cell and the open circuit voltage decay curve based on the H- _TiO nanopowder that the embodiment one obtains, wherein 1 is the TiO obtained in embodiment _two The photoanode cell prepared by the dye-sensitized solar cell photoanode, 2 is the perovskite solar cell based on H- _TiO nano powder obtained in embodiment one; As can be seen from the figure It can be seen that the lifetime of carriers in the perovskite solar cell based on H- _TiO2 nanopowder obtained in Example 1 is increased.

Fig. 7 is obtained with the _TiO2 dye-sensitized solar cell photoanode prepared by embodiment two and the open circuit voltage decay curve of the perovskite solar cell based on H- _TiO2 nanopowder that embodiment one obtains, wherein 1 is the TiO that obtains with embodiment _two The photoanode cell that dye-sensitized solar cell photoanode prepares, and 2 is the perovskite solar cell electronic lifetime curve based on H- _TiO that the embodiment one obtains nanopowder; From Fig. It can be seen that the lifetime of carriers in the perovskite solar cell based on H- _TiO2 nano powder obtained in Example 1 is longer than that of the photoanode cell prepared by the _TiO2 dye-sensitized solar cell photoanode obtained in Example 2 .

Fig. 8 is the photoanode cell prepared with the _TiO dye-sensitized solar cell photoanode obtained in embodiment two and the perovskite solar cell based on H- _TiO nano powder obtained in embodiment one under simulated 1.5G sunlight The photoelectric conversion efficiency, wherein 1 is obtained with embodiment two TiO ₂ The photoanode cell prepared by dye-sensitized solar cell photoanode, 2 is the perovskite solar cell based on H- _TiO nanometer powder obtained in embodiment 1 ; It can be seen from the figure that the H-TiO ₂ photoanode cell has a high photoelectric conversion efficiency.

Fig. 9 is with the TiO that obtains in embodiment ₂ dye-sensitized solar cell photoanode prepares the photoanode cell and embodiment 1 obtains based on H-TiO ₂ The ultraviolet-visible absorption spectrum of the perovskite solar cell of nanopowder, Wherein 1 is the TiO that obtains with embodiment _two The photoanode cell that dye-sensitized solar cell photoanode prepares, and 2 is the perovskite solar cell based on H- _TiO that embodiment one obtains Nanopowder; Can be seen from the figure It can be seen that the perovskite solar cell based on H- _TiO2 nanopowder obtained in Example 1 has strong absorption in the visible region.

Fig. 10 is a cross-sectional view of the perovskite solar cell based on H-TiO ₂ nanopowder obtained in Example 1, and the layering of the cell can be clearly seen.

Claims (10)

1. one kind based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder specifically carries out according to the following steps:

One, titanic oxide nano powder is positioned in quartz boat, the quartz boat filling titanic oxide nano powder is placed in tube furnace, continue the mist passing into nitrogen and hydrogen, then with the heating rate of 1 DEG C/min by reaction temperature from room temperature to 300 DEG C ~ 600 DEG C, after 300 DEG C ~ 600 DEG C insulation 3h ~ 8h, transfer to after leaving standstill 1h ~ 5h in vacuum drying chamber, be cooled to room temperature, obtain H-TiO ₂powder; Described titanic oxide nano powder adopts sol gel synthesis to be prepared from; In the mist of described nitrogen and hydrogen, H-N ratio is 1:9; The flow velocity of the mist of described nitrogen and hydrogen is 100sccm ~ 400sccm;

Two, by H-TiO ₂powder, ethyl cellulose, terpinol and ethanol mix, and stir and obtain slurry; Described H-TiO ₂the mass ratio of powder and ethyl cellulose is 1:(0.1 ~ 0.5); Described H-TiO ₂the mass ratio of powder and terpinol is 1:(2 ~ 7); Described H-TiO ₂the mass ratio of powder and ethanol is 1:(20 ~ 40);

Three, compacted zone solution is prepared: be that the hydrochloric acid of 2mol/L mixes with isopropyl alcohol I by concentration, obtain mixed liquid A; Isopropyl titanate is mixed with isopropyl alcohol II, obtains mixed liquid B; Low whipping speed is dropwise be added drop-wise to by mixed liquid A under the condition of 80rpm ~ 120rpm in mixed liquid B to clarify to mixed liquor, obtains compacted zone solution; Described concentration is the hydrochloric acid of 2mol/L and the volume ratio of isopropyl alcohol I is 1:(100 ~ 500); The volume ratio of isopropyl titanate and isopropyl alcohol II is 1:(10 ~ 35); The volume ratio of mixed liquid A and mixed liquid B is 1:(0.8 ~ 1.2);

Four, prepare calcium titanium ore bed solution: be dissolved in by lead iodide in DMF, the condition lower magnetic force being then 50 DEG C ~ 80 DEG C in temperature stirs 10h ~ 14h, obtains calcium titanium ore bed solution A; Methylpyridinium iodide amine is dissolved in DMF, obtains calcium titanium ore bed solution B; The concentration of described calcium titanium ore bed solution A is 400mg/mL ~ 500mg/mL; The concentration of described calcium titanium ore bed solution B is 4mg/mL ~ 10mg/mL;

Five, prepare hole transmission layer solution: be dissolved in by lithium salts in acetonitrile, stir 10min ~ 20min, obtain lithium salt solution; Chlorobenzene, Spiro-OMeTAD, tributyl phosphate and lithium salt solution are mixed, stirs 10min ~ 20min at normal temperatures, obtain hole transmission layer solution; The concentration of described lithium salt solution is 500mg/mL ~ 600mg/mL; The volume of described chlorobenzene and the mass ratio of Spiro-OMeTAD are 1mL:(50 ~ 80) mg; The volume ratio of described chlorobenzene and tributyl phosphate is 1:(0.02 ~ 0.04); The volume ratio of described chlorobenzene and lithium salt solution is 1:(0.01 ~ 0.02);

Six, substrate is cleaned: FTO electro-conductive glass is first adopted deionized water ultrasonic cleaning 3 ~ 5 times, adopt acetone ultrasonic cleaning again 3 ~ 5 times, then adopt isopropyl alcohol ultrasonic cleaning 3 ~ 5 times, finally adopt UV ozone process 10min ~ 20min, obtain clean transparent conducting glass substrate;

Seven, with the transparent conducting glass substrate of cleaning for basis material, the mode of spin coating is adopted to rotate 30s ~ 60s with the rotating speed of 2000rpm ~ 5000rpm, the compacted zone solution spin coating a layer thickness on basis material adopting step 3 to obtain is after the titanium dioxide dense layer of 80nm ~ 120nm, is the 30min ~ 60min that anneals under the condition of 500 DEG C in temperature; Then the mode of spin coating is adopted to rotate 30s ~ 60s with the rotating speed of 4000rpm ~ 8000rpm, adopt the slurry that obtains of step 2 at thickness be 80nm ~ 120nm titanium dioxide dense layer on spin coating a layer thickness be again after the porous silica titanium layer of 280nm ~ 320nm, be the 30min ~ 60min that anneals under the condition of 500 DEG C in temperature; Then the mode of spin coating is adopted to rotate 5s ~ 20s with the rotating speed of 4000rpm ~ 8000rpm, adopt the calcium titanium ore bed solution A that obtains of step 4 at thickness be 280nm ~ 320nm porous silica titanium layer on again spin coating one deck calcium titanium ore bed A the thermal station of 100 DEG C heats 15min ~ 20min, naturally cool to room temperature; Then the mode of spin coating is adopted to rotate 5s ~ 20s with the rotating speed of 3000rpm ~ 6000rpm, adopt the calcium titanium ore bed solution B that obtains of step 4 spin coating one deck calcium titanium ore bed B again on calcium titanium ore bed A, be that the thermal station of 100 DEG C heats 15min ~ 20min in temperature, naturally cool to room temperature, obtain methylamine leaded iodine polycrystalline film; Then the mode of spin coating is adopted to rotate 5s ~ 20s with the rotating speed of 3000rpm ~ 6000rpm, adopt the hole transmission layer solution that obtains of step 5 spin coating one deck hole transmission layer again in methylamine leaded iodine polycrystalline film, be that the thermal station of 100 DEG C heats 15min ~ 20min in temperature, naturally cool to room temperature; Then adopt the mode of evaporation gold evaporation electrode layer on hole transmission layer, namely complete based on H-TiO ₂the preparation of the perovskite solar cell of nano-powder.

2. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that described in step one at 300 DEG C of insulation 5h.

3. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that described in step one at 500 DEG C of insulation 4h.

4. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, to is characterized in that in step one heating for dissolving 20min under temperature is the condition of 90 DEG C.

5. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that H-TiO described in step 2 ₂the mass ratio of powder and ethyl cellulose is 1:0.3.

6. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that H-TiO described in step 2 ₂the mass ratio of powder and terpinol is 1:5.

7. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that H-TiO described in step 2 ₂the mass ratio of powder and ethanol is 1:30.

8. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that concentration described in step 3 be the hydrochloric acid of 2mol/L and the volume ratio of isopropyl alcohol I is 1:200; The volume ratio of isopropyl titanate and isopropyl alcohol II is 1:30; The volume ratio of mixed liquid A and mixed liquid B is 1:1.

9. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that the concentration of the solution A of calcium titanium ore bed described in step 4 is 400mg/mL ~ 500mg/mL; The concentration of described calcium titanium ore bed solution B is 4mg/mL ~ 10mg/mL.

10. one according to claim 1 is based on H-TiO ₂the preparation method of the perovskite solar cell of nano-powder, is characterized in that the volume of chlorobenzene described in step 5 and the mass ratio of Spiro-OMeTAD are 1mL:60mg; The volume ratio of described chlorobenzene and tributyl phosphate is 1:0.03; The volume ratio of described chlorobenzene and lithium salt solution is 1:0.015.