CN111509063A - Preparation method and application of niobium-doped titanium dioxide nano material - Google Patents

Preparation method and application of niobium-doped titanium dioxide nano material Download PDF

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CN111509063A
CN111509063A CN202010331788.XA CN202010331788A CN111509063A CN 111509063 A CN111509063 A CN 111509063A CN 202010331788 A CN202010331788 A CN 202010331788A CN 111509063 A CN111509063 A CN 111509063A
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陈加藏
程昌
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The application relates to the field of new energy, in particular to preparation and application of niobium-doped nano titanium dioxide in perovskite batteries (PSCs). The specific preparation method of the niobium-doped nano titanium dioxide material comprises the following steps: firstly, putting a certain amount of niobium pentachloride pentahydrate, tetraisopropyl titanate and glacial acetic acid into a polytetrafluoroethylene reaction kettle, filtering, washing and drying at 220 ℃ for 12h to obtain unsintered niobium doped titanium dioxide; then, ball-milling the mesoporous titanium dioxide precursor solution and terpineol, adding ethyl cellulose, thermally stirring, and diluting with absolute ethyl alcohol to obtain a mesoporous titanium dioxide precursor solution; and finally, uniformly coating the titanium dioxide on the dense layer in a spin coating manner, and calcining the titanium dioxide in the air for a plurality of hours to obtain the mesoporous layer consisting of the titanium dioxide material with the niobium enriched inside. Compared with the common titanium dioxide not doped with niobium, the mesoscopic PSCs prepared by taking the material as the mesoporous layer have the advantages that the photoelectric conversion efficiency of the mesoscopic PSCs is improved, and meanwhile, the thermal stability and the ultraviolet stability of the mesoscopic PSCs are obviously improved.

Description

Preparation method and application of niobium-doped titanium dioxide nano material
Technical Field
The invention relates to the field of new energy, in particular to a niobium-doped titanium dioxide nano material, a synthesis method and application of the niobium-doped titanium dioxide nano material as a mesoporous layer in Perovskite Solar Cells (PSCs for short).
Background
With the increasing demand for energy from human beings, the application of traditional fossil fuels is also more extensive. However, the use of non-renewable fossil fuels in large quantities also poses a number of problems, such as energy crisis, environmental pollution, etc. Among many new energy sources, solar energy is widely concerned due to its green, environmental protection, large storage capacity, and no geographical restriction.
Perovskite solar cells have been a research hotspot since being discovered as a brand new solar energy utilization mode. Through the continuous efforts of a plurality of researchers, the cell efficiency of the perovskite is improved to 25.2% from the initial 2.3%, and the performance of the perovskite can be comparable to that of a crystalline silicon solar cell obtained under the laboratory condition. Compared with the crystalline silicon solar cell, the novel PSCs have the advantages of simple manufacturing process, lower cost and higher theoretical photoelectric conversion efficiency.
PSCs have a variety of structures, the two most typical of which are mesoscopic and planar. The invention mainly researches mesoscopic PSCs, and the structure mainly comprises a conductive glass substrate, a charge transport layer, a mesoporous layer, a perovskite layer, a hole transport layer and a counter electrode. At present, TiO is adopted by most mesoscopic PSCs2As a mesoporous layer. TiO compared with other semiconductor materials2Has the advantages of high forbidden band width, good photocatalytic activity and photoelectric property, no toxicity and low cost. However, when the mesoporous material is used as a mesoporous layer, the thermal stability and the ultraviolet stability of the perovskite battery are poor, and the service life and the service performance of the perovskite battery are influenced.
Disclosure of Invention
To overcome the single TiO2The invention provides a niobium-doped titanium dioxide nano material, a preparation method and application thereof as a mesoporous layer in a mesoscopic perovskite solar cell, and solves the problem that the thermal stability and the ultraviolet stability of the perovskite solar cell are poor when the material is used as the mesoporous layer.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing niobium-doped titanium dioxide nano material comprises the following steps:
adding weighed tetrabutyl titanate and niobium chloride pentahydrate into a beaker according to a certain proportion, uniformly mixing and stirring to obtain a solution A, then adding glacial acetic acid into the solution A, and stirring for 15-20min to obtain a solution B; then transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction at 220 ℃ for 12 hours, and cooling to room temperature to obtain a niobium-doped titanium dioxide colloid substance; and finally, centrifuging, washing and drying the colloidal substance to obtain the niobium-doped titanium dioxide nano material.
Preferably, the ratio of tetrabutyl titanate, niobium chloride pentahydrate and glacial acetic acid is 10m L: 0.0529-0.2117 g:3.4224m L.
Preferably, the washing is carried out by absolute ethyl alcohol, the drying temperature is 80 ℃, and the drying time is 12 h.
In addition, the invention also claims the niobium-doped titanium dioxide nano material prepared by the method and the application of the niobium-doped titanium dioxide nano material in preparing a mesoporous layer of a mesoscopic perovskite solar cell, wherein the preparation method of the mesoporous layer of the mesoscopic perovskite solar cell comprises the following steps:
weighing the prepared niobium-doped titanium dioxide nano material, grinding the material into powder, adding terpineol and ethanol, then adding ethyl cellulose under heating and stirring, uniformly stirring, and carrying out ball milling at room temperature to obtain a white colloid substance; then, diluting the obtained white colloidal substance with ethanol to obtain a mesoporous layer precursor solution; and (3) dripping the prepared mesoporous layer precursor solution onto the prepared compact layer titanium dioxide, performing spin coating after the compact layer titanium dioxide flows and is fully paved, and roasting in the air to obtain the mesoporous layer of the mesoscopic perovskite solar cell consisting of the niobium-doped titanium dioxide nano material.
Preferably, the dense layer titanium dioxide is prepared as follows: the precursor solution of the titanium dioxide of the dense layer is prepared by mixing absolute ethyl alcohol, hydrochloric acid and diisopropyl di (acetylacetonate) titanate, and the precursor solution of the titanium dioxide of the dense layer is attached to the FTO glass by adopting a thermal spraying technology, so that the titanium dioxide of the dense layer is obtained.
Preferably, the mass ratio of the niobium-doped titanium dioxide nano material to terpineol to ethyl cellulose is 1:2:4, the adding amount of ethanol before heating and stirring is 3ml for each gram of niobium-doped titanium dioxide nano material, the heating temperature under stirring is 60 ℃, the diluting amount of ethanol is 8.5ml for each gram of white colloid material, the spin-coating speed is 5000rmp, the spin-coating time is 30s, and the spin-coating acceleration is 3000 rmp/s.
Preferably, the roasting temperature is 450-550 ℃, and the roasting time is 10-40 min.
Preferably, the thickness of the meso-porous layer of the meso-perovskite solar cell, which is composed of the niobium-doped titanium dioxide nano material, is 150-200 nm.
Preferably, the FTO glass uses 30-45 μ L mesoporous layer precursor solution per square centimeter.
After the meso-porous layer of the meso-perovskite solar cell consisting of the niobium-containing doped titanium dioxide nano material is prepared by the method, a final meso-perovskite solar cell product can be obtained only by preparing a perovskite layer, preparing a hole transport layer and preparing a counter electrode, wherein the preparation of the perovskite layer, the preparation of the hole transport layer and the preparation of the counter electrode are as follows:
preparation of perovskite layer: the perovskite precursor is prepared by mixing methyl ammonium bromide, formamidine hydroiodide, lead bromide, lead iodide, N-N dimethylformamide and dimethyl sulfoxide; spin-coating the prepared perovskite precursor into a mesoscopic perovskite solar cell semi-finished product taking the niobium-doped titanium dioxide nano material as a mesoporous layer, and heating at 100 ℃ for 30min to obtain a perovskite layer;
preparation of hole transport layer: the hole transport layer precursor solution is prepared from 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD), anhydrous chlorobenzene, 4-tert-butylpyridine, a lithium bistrifluoromethanesulfonylimide solution and a cobalt-based bistrifluoromethanesulfonylimide salt solution, and the prepared hole transport layer precursor solution is spin-coated on the prepared perovskite layer;
preparing a counter electrode: and (3) putting the mesoscopic perovskite solar cell semi-finished product with the hole transport layer prepared into a mask plate, and evaporating a layer of metal counter electrode under the vacuum degree by adopting a vacuum coating method to complete the preparation of PSCs.
The mesoscopic perovskite solar cell prepared by the invention has a structural schematic diagram shown in figure 1, and is sequentially provided with an FTO glass substrate (1) from bottom to top; a dense layer titanium dioxide (2); a mesoporous layer (3); a perovskite layer (4); a hole transport layer (5); a counter electrode (6).
The technical scheme provided by the invention has the following obvious beneficial effects:
(1) according to the invention, the niobium-doped titanium dioxide nano material is calcined, and niobium is enriched in the titanium dioxide, so that the doping effect of niobium is ensured.
(2) According to the invention, the titanium dioxide material is doped with niobium, so that the niobium-doped mesoporous layer and the perovskite layer are better matched. Among PSCs, perovskite and anatase TiO2The lattice mismatch therebetween becomes severe with increasing temperature because perovskites have a higher coefficient of thermal expansion than TiO2By a factor of about 3, the strain generated internally in the doped niobium material of the present application may act on the surface and may enlarge the lattice spacing of the undoped region, may effectively mitigate the lattice mismatch, and may reduce the lattice strain generated between anatase and perovskite.
(3) Compared with PSCs prepared by taking titanium dioxide materials without niobium as mesoporous layers, PSCs prepared by taking niobium-doped titanium dioxide nano materials as mesoporous layers have obviously slow photoelectric conversion efficiency reduction rate along with the prolonging of heating time; with the extension of the ultraviolet irradiation time, the photoelectric conversion efficiency is reduced to a certain degree and then tends to be stabilized at a higher value. The PSCs prepared by taking the niobium-doped titanium dioxide nano material as the mesoporous layer have better thermal stability and ultraviolet stability, and show that the PSCs prepared by the niobium-doped titanium dioxide nano material can endure harsher use environment, have wider use occasions and have better applicability; meanwhile, from the viewpoint of photoelectric conversion efficiency, the maximum PSCs manufactured by using the niobium-doped titanium dioxide nano material as the mesoporous layer can reach 21.07%, while the photoelectric conversion efficiency of the PSCs manufactured by using the non-niobium-doped titanium dioxide material as the mesoporous layer is only 20.3%, so that the photoelectric conversion efficiency is improved to a certain extent, and the utilization efficiency of solar energy resources can be improved. In a word, the invention provides a synthesis method of a complete niobium-doped titanium dioxide nano material and application of the complete niobium-doped titanium dioxide nano material in a mesoscopic perovskite solar cell, the whole process is simple, the prepared PSCs have good thermal stability and ultraviolet stability, the service performance of the PSCs is improved, the PSCs have wide market prospect, better utilization of solar resources is facilitated, the use ratio of the solar resources is improved, fossil energy consumption can be reduced to a certain extent, and the invention has double meanings of good economic benefit and high environmental protection benefit.
Drawings
FIG. 1 is a schematic structural diagram of mesoscopic PSCs assembled according to the present invention.
FIG. 2 is a comparison of XPS before and after calcination of the niobium doped titanium dioxide nanomaterial of the present invention. It can be analyzed from the figure that the doped Nb is mainly enriched on the surface before calcination, and the Nb is enriched in the titanium dioxide after high-temperature heat treatment at 500 ℃.
FIG. 3 is a graph showing the photoelectric conversion efficiency of PSCs fabricated by using titanium dioxide with different Nb/Ti molar doping ratios as mesoporous layers and PSCs fabricated by using titanium dioxide material without niobium doping as mesoporous layers in the present invention. As can be seen from the figure, PSCs prepared by using titanium dioxide doped with 1% Nb as a mesoporous layer have the highest photoelectric conversion efficiency.
FIG. 4 is a graph showing the thermal stability of PSCs fabricated using titanium dioxide doped with 1% Nb as a mesoporous layer in accordance with the present invention compared to PSCs fabricated using titanium dioxide undoped with Nb as a mesoporous layer. Compared with PSCs prepared by taking titanium dioxide which is not doped with Nb as a mesoporous layer, PSCs prepared by taking titanium dioxide which is doped with Nb as a mesoporous layer have higher thermal stability.
Fig. 5 is a graph comparing the uv stability of PSCs fabricated with titanium dioxide doped with 1% Nb as a mesoporous layer and PSCs fabricated with titanium dioxide undoped with Nb as a mesoporous layer according to the present invention. Compared with PSCs prepared by taking titanium dioxide not doped with Nb as a mesoporous layer, PSCs prepared by taking titanium dioxide doped with 1% of Nb as a mesoporous layer have higher ultraviolet stability.
FIG. 6 is a graph showing the comparison of photoelectric conversion efficiency of the PSCs prepared by calcining the mesoporous layer of 1% Nb-doped titanium dioxide at 500 ℃ for different time periods. As can be seen from the figure, the effect is best when the calcination is carried out for 30 min.
FIG. 7 is a graph showing the comparison of photoelectric conversion efficiency of PSCs prepared by calcining 1% Nb-doped titanium dioxide as mesoporous layer at different temperatures for 30 min. As can be seen from the figure, the effect is best at a calcination temperature of 500 ℃.
Wherein the reference numerals are as follows:
the preparation method comprises the following steps of 1-FTO glass substrate, 2-dense layer titanium dioxide, 3-mesoporous layer, 4-perovskite layer, 5-hole transport layer and 6-counter electrode.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
Examples include Nb doped TiO2Preparation of material, Nb doped TiO2The material is applied to three parts of a preparation process of mesoscopic PSCs and performance evaluation of the PSCs, wherein the performance evaluation of the PSCs comprises photoelectric conversion efficiency determination, thermal stability determination and ultraviolet stability determination.
(1) 1% Nb doped TiO2The preparation process of the material is as follows:
10.04ml of TBT solution are weighed into a beaker, and 0.1058g of weighed NbCl are added5·5H2Mixing and stirring O for 10min, adding 3.26ml of glacial acetic acid, stirring for 20min, transferring the obtained mixed solution into a reaction kettle with the volume of 50ml of polytetrafluoroethylene lining stainless steel, performing hydrothermal treatment at 220 ℃ for 12h to obtain Nb-doped TiO2Cooling to room temperature after the reaction. Collecting the product by centrifugation, centrifuging and cleaning with anhydrous ethanol for multiple times, and drying the obtained product in a vacuum drying oven at 80 deg.C for 12 hr to obtain solid white substance, i.e. 1% Nb-doped TiO2。
(2) 1% Nb doped TiO2The preparation process of the mesoscopic PSCs with the mesoporous layer as the material is as follows:
(a) preparing a precursor solution of the titanium dioxide of the dense layer by directly mixing absolute ethyl alcohol, 2 mol/L hydrochloric acid and diisopropyl di (acetylacetonate) titanate (wherein the absolute ethyl alcohol: the hydrochloric acid: the diisopropyl di (acetylacetonate) titanate is 9m L: 0.7m L: 1.3m L), spraying the precursor of the titanium dioxide of the dense layer on an FTO substrate by using a thermal spraying method to obtain the titanium dioxide of the dense layer, wherein the spraying temperature is 450 ℃, and the spraying time is 30 min;
(b) preparing mesoporous layer titanium dioxide: weighing prepared Nb-doped TiO21g of the precursor is ground into powder in a mortar, 2g of terpineol and 3m of L ethanol are added into the powder, the powder is heated and stirred at the temperature of 60 ℃, 4g of ethyl cellulose is added, the mixture is ball-milled for 3 hours by a ball mill at room temperature to obtain a white colloidal substance, then 1g of the white colloidal substance is weighed, 8.5ml of ethanol is added for dilution to obtain a mesoporous layer titanium dioxide precursor solution, finally, the rotating speed of a spin coater is set to be 5000 rpm, the time is set to be 30s, the acceleration is 3500rmp/s, 63 mu L of the mesoporous layer titanium dioxide precursor solution is taken and dripped onto a dense layer titanium dioxide, the dense layer titanium dioxide precursor solution flows and is paved with an FTO (1.45cm x 1.45cm) substrate, the spin coater is started, after the spin coater is finished, the FTO loaded with the dense layer and the mesoporous layer precursor is calcined for 30min at the temperature of 500 ℃ in a muffle furnace, and the mesoscopic PSCs TiO doped with 1% Nb is obtained2A mesoporous layer. Calcined doped 1% Nb TiO2The material, Nb, is concentrated inside and exists on the surface in a small amount.
(c) Firstly, mixing methyl ammonium bromide, formamidine hydroiodide, lead bromide, lead iodide, N-N dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution (wherein the methyl ammonium bromide is 22.65mg, the formamidine hydroiodide is 187.96mg, the lead bromide is 74.3mg and the lead iodide is 528.99mg, the mixture is dissolved in a mixed solution of 20m L dimethyl sulfoxide and 80m L N-N dimethylformamide), then, using chlorobenzene as an anti-solvent, and spin-coating the prepared perovskite precursor on the titanium dioxide of the mesoporous layer prepared in the step (b), wherein the spin-coating step is two steps, the first step has the rotating speed of 2000rmp and the time of 10s and the acceleration of 2000rmp/s, the second step has the rotating speed of 6000rmp and the time of 30s and the acceleration of 2000rmp/s, and the spin-coating is finished at 100 ℃ for 30min, and the processes are carried out in a glove box;
(d) preparing a hole transport layer precursor solution from Spiro-OMeTAD, anhydrous chlorobenzene, 4-tert-butylpyridine, lithium bistrifluoromethanesulfonylimide solution and cobalt-based bistrifluoromethanesulfonylimide salt solution (wherein Spiro-OMeTAD is 72.3mg, anhydrous chlorobenzene is 1m L, 4-tert-butylpyridine is 28.8 mu L, lithium bistrifluoromethanesulfonylimide solution is 17.5 mu L and cobalt-based bistrifluoromethanesulfonylimide salt solution is 29 mu L), spin-coating the prepared hole transport layer purple black precursor solution on the perovskite layer prepared in the step (c), wherein the spin-coating speed is 3000r/min, the spin-coating time is 30s and the spin-coating acceleration is 2000 rmp/s;
(e) and (d) preparing a counter electrode, namely putting the mesoscopic perovskite solar cell semi-finished product after the hole transmission layer is prepared in the step (d) into a mask plate, and evaporating a layer of metal counter electrode under the vacuum degree of 6.0 × 10-4Pa by adopting a vacuum coating method to complete the preparation of PSCs.
(3) The procedure for evaluating the performance of PSCs is as follows:
first, a solar simulator (100 mW/cm) was used2AM 1.5G) was irradiated with PSCs, and the photoelectric conversion efficiency thereof was measured using a J-V characteristic curve measured by an electrochemical workstation, as shown in fig. 3. PSCs with titanium dioxide doped with 1% Nb as a mesoporous layer have the corresponding photovoltaic parameters as follows: voc 1.172V, Jsc 23.91mA/cm2，FF＝0.752，PCE＝21.07％。
Secondly, Nb doped TiO2PSCs made of mesoporous layer material and TiO made of undoped Nb2The results of comparing the thermal stability and the uv stability of PSCs made with mesoporous layers are shown in fig. 4 and 5, respectively. The thermal stability test was conducted by placing PSCs made of two materials in a glove box, heating at 80 ℃, and performing an efficiency test every two hours. As can be seen from fig. 4, doping with 1% Nb can improve the thermal stability of PSCs. The UV stability test was carried out by placing PSCs made of the two materials under an ultraviolet lamp having a wavelength of 375nm (equivalent to 60 suns)) Next, the UV lamp irradiation was performed under the same conditions for 250 min. As can be seen from fig. 5, the 1% Nb doping can improve the uv stability of PSCs.
Example 2
Examples include Nb doped TiO2Preparation of material, Nb doped TiO2The material is applied to three parts of a preparation process of mesoscopic PSCs and performance evaluation of the PSCs, wherein the performance evaluation of the PSCs comprises photoelectric conversion efficiency determination, thermal stability determination and ultraviolet stability determination.
(1) 0.5% Nb-doped TiO2The preparation process of the material is as follows:
10.04ml of TBT solution are weighed into a beaker, and 0.0529g of weighed NbCl are added5·5H2Mixing and stirring O for 10min, adding 3.26ml of glacial acetic acid, stirring for 20min, transferring the obtained mixed solution into a reaction kettle with the volume of 50ml of polytetrafluoroethylene-lined stainless steel, and performing hydrothermal treatment at 220 ℃ for 12h to obtain Nb-doped TiO2Cooling to room temperature after the reaction. Collecting the product by centrifugation, centrifuging and cleaning with anhydrous ethanol for multiple times, and drying the obtained product in a vacuum drying oven at 80 deg.C for 12 hr to obtain solid white substance, i.e. 0.5% Nb-doped TiO2。
(2) 0.5% Nb-doped TiO2The preparation process of the mesoscopic PSCs with the mesoporous layer as the material is as follows:
(a) preparing a precursor solution of the titanium dioxide of the dense layer by directly mixing absolute ethyl alcohol, 2 mol/L hydrochloric acid and diisopropyl di (acetylacetonate) titanate (wherein the absolute ethyl alcohol: the hydrochloric acid: the diisopropyl di (acetylacetonate) titanate is 9m L: 0.7m L: 1.3m L), spraying the precursor of the titanium dioxide of the dense layer on an FTO substrate by using a thermal spraying method to obtain the titanium dioxide of the dense layer, wherein the spraying temperature is 450 ℃, and the spraying time is 30 min;
(b) preparing mesoporous layer titanium dioxide: weighing the prepared 0.5 percent Nb-doped TiO21g, ground to a powder in a mortar, transferred to a beaker and added with 2g of terpineol and 3m of L ethanol, heated at 60 ℃ with stirring added with 4g of ethylcellulose and ball milled 3 with a ball mill at room temperatureAnd finally, setting the rotation speed of a spin coater to be 5000rmp, the time to be 30s and the acceleration to be 3500rmp/s when the parameters of the spin coater are set, dripping the mesoporous layer titanium dioxide precursor solution prepared by 90 mu L on the compact layer titanium dioxide, starting the spin coater after the FTO (1.50cm x 1.50cm) substrate is fully paved by flowing, and calcining the FTO loaded with the compact layer and the mesoporous layer precursor for 30min at 500 ℃ in a muffle furnace to obtain the mesoscopic PSCs mesoporous layer titanium dioxide doped with 0.5 percent of Nb.
(c) Firstly, mixing methyl ammonium bromide, formamidine hydroiodide, lead bromide, lead iodide, N-N dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution (wherein the methyl ammonium bromide is 22.65mg, the formamidine hydroiodide is 187.96mg, the lead bromide is 74.3mg and the lead iodide is 528.99mg, the mixture is dissolved in a mixed solution of 20m L dimethyl sulfoxide and 80m L N-N dimethylformamide), then, using chlorobenzene as an anti-solvent, and spin-coating the prepared perovskite precursor on the titanium dioxide of the mesoporous layer prepared in the step (b), wherein the spin-coating step is divided into two steps, the first step is 2000rmp at a rotating speed of 2000rmp for 10s at an acceleration of 200rmp/s, the second step is 6000rmp at a rotating speed of 30s at an acceleration of 2000rmp/s, the spin-coating is finished at 100 ℃ for 30min, and the processes are carried out in a glove box;
(d) preparing a hole transport layer precursor solution from Spiro-OMeTAD, anhydrous chlorobenzene, 4-tert-butylpyridine, lithium bistrifluoromethanesulfonylimide solution and cobalt-based bistrifluoromethanesulfonylimide salt solution (wherein Spiro-OMeTAD is 72.3mg, anhydrous chlorobenzene is 1m L, 4-tert-butylpyridine is 28.8 mu L, lithium bistrifluoromethanesulfonylimide solution is 17.5 mu L and cobalt-based bistrifluoromethanesulfonylimide salt solution is 29 mu L), spin-coating the prepared hole transport layer purple black precursor solution on the perovskite layer prepared in the step (c), wherein the spin-coating speed is 3000r/min, the spin-coating time is 30s and the spin-coating acceleration is 2000 rmp/s;
(e) and (d) preparing a counter electrode, namely putting the mesoscopic perovskite solar cell semi-finished product after the hole transmission layer is prepared in the step (d) into a mask plate, and evaporating a layer of metal counter electrode under the vacuum degree of 6.0 × 10-4Pa by adopting a vacuum coating method to complete the preparation of PSCs.
(3) The procedure for evaluating the performance of PSCs is as follows:
first, a solar simulator (100 mW/cm) was used2AM 1.5G) was irradiated with PSCs, and the photoelectric conversion efficiency thereof was measured using the J-V characteristic curve measured by the electrochemical workstation, as shown in fig. 3. The corresponding photovoltaic parameters are as follows: voc 1.118V, Jsc 23.87mA/cm2，FF＝0.722，PCE＝19.26％。
Second, Nb doped TiO2PSCs made of mesoporous layer material and TiO made of undoped Nb2The thermal stability and the ultraviolet stability of PSCs made of the material serving as the mesoporous layer are compared. The thermal stability test was conducted by placing PSCs made of two materials in a glove box, heating at 80 ℃, and performing an efficiency test every two hours. The UV stability test was carried out by placing PSCs made of the two materials under an ultraviolet lamp having a wavelength of 375nm (equivalent to 60 suns) and irradiating the PSCs under the same conditions for 250 min.
The measurement result shows that the thermal stability and the ultraviolet stability of the PSCs can be improved by doping 0.5% of Nb compared with the PSCs without doping Nb.
Example 3
Examples include Nb doped TiO2Preparation of material, Nb doped TiO2The material is applied to three parts of a preparation process of mesoscopic PSCs and performance evaluation of the PSCs, wherein the performance evaluation of the PSCs comprises photoelectric conversion efficiency determination, thermal stability determination and ultraviolet stability determination.
(1) 2% Nb doped TiO2The preparation process of the material is as follows:
10.04ml of TBT solution are weighed into a beaker, and 0.2117g of weighed NbCl are added5·5H2Mixing and stirring O for 10min, adding 3.26ml glacial acetic acid, stirring for 20min, transferring the obtained mixed solution into a reaction kettle with a volume of 50ml and a polytetrafluoroethylene lining stainless steel, and heating to 220 deg.CPerforming hydrothermal treatment for 12h to obtain Nb-doped TiO2Cooling to room temperature after the reaction. Collecting the product by centrifugation, centrifuging and cleaning with anhydrous ethanol for multiple times, and drying the obtained product in a vacuum drying oven at 80 deg.C for 12 hr to obtain solid white substance, i.e. 2% Nb-doped TiO2。
(2) 2% Nb doped TiO2The preparation process of the mesoscopic PSCs with the mesoporous layer as the material is as follows:
(a) preparing a precursor solution of the titanium dioxide of the dense layer by directly mixing absolute ethyl alcohol, 2 mol/L hydrochloric acid and diisopropyl di (acetylacetonate) titanate (wherein the absolute ethyl alcohol: the hydrochloric acid: the diisopropyl di (acetylacetonate) titanate is 9m L: 0.7m L: 1.3m L), spraying the precursor of the titanium dioxide of the dense layer on an FTO substrate by using a thermal spraying method to obtain the titanium dioxide of the dense layer, wherein the spraying temperature is 450 ℃, and the spraying time is 30 min;
(b) preparing mesoporous layer titanium dioxide: weighing the prepared 2% Nb-doped TiO21g of the mesoporous titanium dioxide precursor solution is ground into powder in a mortar, the powder is transferred into a beaker, 2g of terpineol and 3m L of ethanol are added, heating and stirring are carried out at the temperature of 60 ℃, 4g of ethyl cellulose is added, ball milling is carried out for 3h by a ball mill at room temperature, a white colloidal substance is obtained, 1g of the white colloidal substance is weighed, 8.5ml of ethanol is added for dilution, and a mesoporous titanium dioxide precursor solution is obtained.
(c) Firstly, mixing methyl ammonium bromide, formamidine hydroiodide, lead bromide, lead iodide, N-N dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution (wherein the methyl ammonium bromide is 22.65mg, the formamidine hydroiodide is 187.96mg, the lead bromide is 74.3mg and the lead iodide is 528.99mg, the mixture is dissolved in a mixed solution of 20m L dimethyl sulfoxide and 80m L N-N dimethylformamide), then, using chlorobenzene as an anti-solvent, and spin-coating the prepared perovskite precursor on the titanium dioxide of the mesoporous layer prepared in the step (b), wherein the spin-coating step is divided into two steps, the first step is 2000rmp at a rotating speed of 2000rmp for 10s at an acceleration of 200rmp/s, the second step is 6000rmp at a rotating speed of 30s at an acceleration of 2000rmp/s, the spin-coating is finished at 100 ℃ for 30min, and the processes are carried out in a glove box;
(d) preparing a hole transport layer precursor solution from Spiro-OMeTAD, anhydrous chlorobenzene, 4-tert-butylpyridine, lithium bistrifluoromethanesulfonylimide solution and cobalt-based bistrifluoromethanesulfonylimide salt solution (wherein Spiro-OMeTAD is 72.3mg, anhydrous chlorobenzene is 1m L, 4-tert-butylpyridine is 28.8 mu L, lithium bistrifluoromethanesulfonylimide solution is 17.5 mu L and cobalt-based bistrifluoromethanesulfonylimide salt solution is 29 mu L), spin-coating the prepared hole transport layer purple black precursor solution on the perovskite layer prepared in the step (c), wherein the spin-coating speed is 3000r/min, the spin-coating time is 30s and the spin-coating acceleration is 2000 rmp/s;
(e) and (d) preparing a counter electrode, namely putting the mesoscopic perovskite solar cell semi-finished product after the hole transmission layer is prepared in the step (d) into a mask plate, and evaporating a layer of metal counter electrode under the vacuum degree of 6.0 × 10-4Pa by adopting a vacuum coating method to complete the preparation of PSCs.
(3) The procedure for evaluating the performance of PSCs is as follows:
first, a solar simulator (100 mW/cm) was used2AM 1.5G) was irradiated with PSCs, and the photoelectric conversion efficiency thereof was measured using the J-V characteristic curve measured by the electrochemical workstation, as shown in fig. 3. The corresponding photovoltaic parameters are as follows: voc 1.122V, Jsc 23.79mA/cm2，FF＝0.721，PCE＝19.25％。
Secondly, Nb doped TiO2PSCs made of mesoporous layer material and TiO made of undoped Nb2The thermal stability and the ultraviolet stability of PSCs made of the material serving as the mesoporous layer are compared. Wherein the thermal stability test is that P is made of two materialsThe SCs were placed in a glove box and heated at a temperature of 80 ℃ and efficiency tests were performed two hours apart. The UV stability test was carried out by placing PSCs made of the two materials under an ultraviolet lamp having a wavelength of 375nm (equivalent to 60 suns) and irradiating the PSCs under the same conditions for 250 min.
The measurement results show that the 1% Nb-doped PSCs prepared under the conditions of this example have better thermal stability and uv stability than those of the non-Nb-doped PSCs.
Example 4
Examples include Nb doped TiO2Preparation of material, Nb doped TiO2The material is applied to three parts of a preparation process of mesoscopic PSCs and performance evaluation of the PSCs, wherein the performance evaluation of the PSCs comprises photoelectric conversion efficiency determination, thermal stability determination and ultraviolet stability determination.
(1) 1% Nb doped TiO2The preparation process of the material is as follows:
10.04ml of TBT solution are weighed into a beaker, and 0.1058g of weighed NbCl are added5·5H2Mixing and stirring O for 10min, adding 3.26ml of glacial acetic acid, stirring for 20min, transferring the obtained mixed solution into a reaction kettle with the volume of 50ml of polytetrafluoroethylene lining stainless steel, performing hydrothermal treatment at 220 ℃ for 12h to obtain Nb-doped TiO2Cooling to room temperature after the reaction. Collecting the product by centrifugation, centrifuging and cleaning with anhydrous ethanol for multiple times, and drying the obtained product in a vacuum drying oven at 80 deg.C for 12 hr to obtain solid white substance, i.e. 1% Nb-doped TiO2。
(2) 1% Nb doped TiO2The preparation process of the mesoscopic PSCs with the mesoporous layer as the material is as follows:
(a) preparing a precursor solution of the titanium dioxide of the dense layer by directly mixing absolute ethyl alcohol, 2 mol/L hydrochloric acid and diisopropyl di (acetylacetonate) titanate (wherein the absolute ethyl alcohol: the hydrochloric acid: the diisopropyl di (acetylacetonate) titanate is 9m L: 0.7m L: 1.3m L), spraying the precursor of the titanium dioxide of the dense layer on an FTO substrate by using a thermal spraying method to obtain the titanium dioxide of the dense layer, wherein the spraying temperature is 450 ℃, and the spraying time is 30 min;
(b) preparing mesoporous layer titanium dioxide: weighing the prepared 1 percent Nb-doped TiO21g of the mesoporous titanium dioxide precursor solution is ground into powder in a mortar, the powder is transferred into a beaker, 2g of terpineol and 3m L of ethanol are added, heating and stirring are carried out at the temperature of 60 ℃, 4g of ethyl cellulose is added, ball milling is carried out for 3h by a ball mill at room temperature, a white colloidal substance is obtained, 1g of the white colloidal substance is weighed, 8.5ml of ethanol is added for dilution, and a mesoporous titanium dioxide precursor solution is obtained.
(c) Firstly, mixing methyl ammonium bromide, formamidine hydroiodide, lead bromide, lead iodide, N-N dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution (wherein the methyl ammonium bromide is 22.65mg, the formamidine hydroiodide is 187.96mg, the lead bromide is 74.3mg and the lead iodide is 528.99mg, the mixture is dissolved in a mixed solution of 20m L dimethyl sulfoxide and 80m L N-N dimethylformamide), then, using chlorobenzene as an anti-solvent, and spin-coating the prepared perovskite precursor on the titanium dioxide of the mesoporous layer prepared in the step (b), wherein the spin-coating step is divided into two steps, the first step is 2000rmp at a rotating speed of 2000rmp for 10s at an acceleration of 200rmp/s, the second step is 6000rmp at a rotating speed of 30s at an acceleration of 2000rmp/s, the spin-coating is finished at 100 ℃ for 30min, and the processes are carried out in a glove box;
(d) preparing a hole transport layer precursor solution from Spiro-OMeTAD, anhydrous chlorobenzene, 4-tert-butylpyridine, lithium bistrifluoromethanesulfonylimide solution and cobalt-based bistrifluoromethanesulfonylimide salt solution (wherein Spiro-OMeTAD is 72.3mg, anhydrous chlorobenzene is 1m L, 4-tert-butylpyridine is 28.8 mu L, lithium bistrifluoromethanesulfonylimide solution is 17.5 mu L and cobalt-based bistrifluoromethanesulfonylimide salt solution is 29 mu L), spin-coating the prepared hole transport layer purple black precursor solution on the perovskite layer prepared in the step (c), wherein the spin-coating speed is 3000r/min, the spin-coating time is 30s and the spin-coating acceleration is 2000 rmp/s;
(e) and (d) preparing a counter electrode, namely putting the mesoscopic perovskite solar cell semi-finished product after the hole transmission layer is prepared in the step (d) into a mask plate, and evaporating a layer of metal counter electrode under the vacuum degree of 6.0 × 10-4Pa by adopting a vacuum coating method to complete the preparation of PSCs.
(3) The procedure for evaluating the performance of PSCs is as follows:
by using a solar simulator (100 mW/cm)2AM 1.5G) was irradiated with PSCs, and the photoelectric conversion efficiency thereof was measured using the J-V characteristic curve measured by the electrochemical workstation, as shown in fig. 6. The corresponding photovoltaic parameters are as follows: voc 1.079V and Jsc 22.23mA/cm2，FF＝0.676，PCE＝16.21％。
Secondly, Nb doped TiO2PSCs made of mesoporous layer material and TiO made of undoped Nb2The thermal stability and the ultraviolet stability of PSCs made of the material serving as the mesoporous layer are compared. The thermal stability test was conducted by placing PSCs made of two materials in a glove box, heating at 80 ℃, and performing an efficiency test every two hours. The UV stability test was carried out by placing PSCs made of the two materials under an ultraviolet lamp having a wavelength of 375nm (equivalent to 60 suns) and irradiating the PSCs under the same conditions for 250 min.
The measurement results show that the 1% Nb-doped PSCs prepared under the conditions of this example have better thermal stability and uv stability than those of the non-Nb-doped PSCs.
Example 5
Examples include Nb doped TiO2Preparation of material, Nb doped TiO2The material is applied to three parts of a preparation process of mesoscopic PSCs and performance evaluation of the PSCs, wherein the performance evaluation of the PSCs comprises photoelectric conversion efficiency determination, thermal stability determination and ultraviolet stability determination.
(1) 1% Nb doped TiO2Preparation of materialsThe process is as follows:
10.04ml of TBT solution are weighed into a beaker, and 0.1058g of weighed NbCl are added5·5H2Mixing and stirring O for 10min, adding 3.26ml of glacial acetic acid, stirring for 20min, transferring the obtained mixed solution into a reaction kettle with the volume of 50ml of polytetrafluoroethylene lining stainless steel, performing hydrothermal treatment at 220 ℃ for 12h to obtain Nb-doped TiO2Cooling to room temperature after the reaction. Collecting the product by centrifugation, centrifuging and cleaning with anhydrous ethanol for multiple times, and drying the obtained product in a vacuum drying oven at 80 deg.C for 12 hr to obtain solid white substance, i.e. 1% Nb-doped TiO2。
(2) 1% Nb doped TiO2The preparation process of the mesoscopic PSCs with the mesoporous layer as the material is as follows:
(a) preparing a precursor solution of the titanium dioxide of the dense layer by directly mixing absolute ethyl alcohol, 2 mol/L hydrochloric acid and diisopropyl di (acetylacetonate) titanate (wherein the absolute ethyl alcohol: the hydrochloric acid: the diisopropyl di (acetylacetonate) titanate is 9m L: 0.7m L: 1.3m L), spraying the precursor of the titanium dioxide of the dense layer on an FTO substrate by using a thermal spraying method to obtain the titanium dioxide of the dense layer, wherein the spraying temperature is 450 ℃, and the spraying time is 30 min;
(b) preparing mesoporous layer titanium dioxide: weighing the prepared 1 percent Nb-doped TiO21g of the precursor solution is ground into powder in a mortar, the powder is transferred into a beaker, 2g of terpineol and 3m L of ethanol are added, heating and stirring are carried out at the temperature of 60 ℃, 4g of ethyl cellulose is added, ball milling is carried out for 3h by a ball mill at room temperature to obtain a white colloidal substance, then 1g of the white colloidal substance is weighed, 8.5ml of ethanol is added for dilution to obtain a mesoporous layer titanium dioxide precursor solution, finally, the parameters of a spin coater are set, the rotating speed is 5000rmp, the time is 30s and the acceleration is 3500rmp/s when the spin coater is in spin coating, 80 mu L of the mesoporous layer titanium dioxide precursor solution is taken and dripped onto a dense layer titanium dioxide, the dense layer titanium dioxide precursor solution is paved with an FTO (1.50cm x 1.50cm) substrate in a flowing mode, the spin coater is started, after the spin coating is finished, the dense layer and mesoporous layer precursor loaded FTO is calcined for 40min in an air atmosphere in a muffle furnace at the temperature of 500 ℃, and theType PSCs mesoporous layer titanium dioxide.
(c) Firstly, mixing methyl ammonium bromide, formamidine hydroiodide, lead bromide, lead iodide, N-N dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution (wherein the methyl ammonium bromide is 22.65mg, the formamidine hydroiodide is 187.96mg, the lead bromide is 74.3mg and the lead iodide is 528.99mg, the mixture is dissolved in a mixed solution of 20m L dimethyl sulfoxide and 80m L N-N dimethylformamide), then, using chlorobenzene as an anti-solvent, and spin-coating the prepared perovskite precursor on the titanium dioxide of the mesoporous layer prepared in the step (b), wherein the spin-coating step is divided into two steps, the first step is 2000rmp at a rotating speed of 2000rmp for 10s at an acceleration of 200rmp/s, the second step is 6000rmp at a rotating speed of 30s at an acceleration of 2000rmp/s, the spin-coating is finished at 100 ℃ for 30min, and the processes are carried out in a glove box;
(d) preparing a hole transport layer precursor solution from Spiro-OMeTAD, anhydrous chlorobenzene, 4-tert-butylpyridine, lithium bistrifluoromethanesulfonylimide solution and cobalt-based bistrifluoromethanesulfonylimide salt solution (wherein Spiro-OMeTAD is 72.3mg, anhydrous chlorobenzene is 1m L, 4-tert-butylpyridine is 28.8 mu L, lithium bistrifluoromethanesulfonylimide solution is 17.5 mu L and cobalt-based bistrifluoromethanesulfonylimide salt solution is 29 mu L), spin-coating the prepared hole transport layer purple-black precursor solution on the perovskite layer prepared in the step (c), wherein the spin-coating rotation speed is 3000r/min, the spin-coating time is 30s and the spin-coating acceleration is 2000 rmp/s;
(e) and (d) preparing a counter electrode, namely putting the mesoscopic perovskite solar cell semi-finished product after the hole transmission layer is prepared in the step (d) into a mask plate, and evaporating a layer of metal counter electrode under the vacuum degree of 6.0 × 10-4Pa by adopting a vacuum coating method to complete the preparation of PSCs.
(3) The procedure for evaluating the performance of PSCs is as follows:
by using a solar simulator (100 mW/cm)2AM 1.5G) was irradiated with PSCs, and the photoelectric conversion efficiency thereof was measured using the J-V characteristic curve measured by the electrochemical workstation, as shown in fig. 6. The corresponding photovoltaic parameters are as follows: voc 1.162V, Jsc 23.85mA/cm2，FF＝0.751，PCE＝20.81％。
Secondly, Nb doped TiO2PSCs made of mesoporous layer material and TiO made of undoped Nb2The thermal stability and the ultraviolet stability of PSCs made of the material serving as the mesoporous layer are compared. The thermal stability test was conducted by placing PSCs made of two materials in a glove box, heating at 80 ℃, and performing an efficiency test every two hours. The UV stability test was carried out by placing PSCs made of the two materials under an ultraviolet lamp having a wavelength of 375nm (equivalent to 60 suns) and irradiating the PSCs under the same conditions for 250 min.
The measurement results show that the 1% Nb-doped PSCs prepared under the conditions of this example have better thermal stability and uv stability than those of the non-Nb-doped PSCs.
Example 6
Examples include Nb doped TiO2Preparation of material, Nb doped TiO2The material is applied to three parts of a preparation process of mesoscopic PSCs and performance evaluation of the PSCs, wherein the performance evaluation of the PSCs comprises photoelectric conversion efficiency determination, thermal stability determination and ultraviolet stability determination.
(1) 1% Nb doped TiO2The preparation process of the material is as follows:
10.04ml of TBT solution are weighed into a beaker, and 0.1058g of weighed NbCl are added5·5H2Mixing and stirring O for 10min, adding 3.26ml of glacial acetic acid, stirring for 20min, transferring the obtained mixed solution into a reaction kettle with the volume of 50ml of polytetrafluoroethylene lining stainless steel, performing hydrothermal treatment at 220 ℃ for 12h to obtain Nb-doped TiO2Cooling to room temperature after the reaction. Collecting the product by centrifugation, centrifuging and cleaning with anhydrous ethanol for multiple times, and drying the obtained product in a vacuum drying oven at 80 deg.C for 12 hr to obtain solid white substance, i.e. 1% Nb-doped TiO2。
(2) 1% Nb doped TiO2The preparation process of the mesoscopic PSCs with the mesoporous layer as the material is as follows:
(a) preparing a precursor solution of the titanium dioxide of the dense layer by directly mixing absolute ethyl alcohol, 2 mol/L hydrochloric acid and diisopropyl di (acetylacetonate) titanate (wherein the absolute ethyl alcohol: the hydrochloric acid: the diisopropyl di (acetylacetonate) titanate is 9m L: 0.7m L: 1.3m L), spraying the precursor of the titanium dioxide of the dense layer on an FTO substrate by using a thermal spraying method to obtain the titanium dioxide of the dense layer, wherein the spraying temperature is 450 ℃, and the spraying time is 30 min;
(b) preparing mesoporous layer titanium dioxide: weighing the prepared 1 percent Nb-doped TiO21g of the mesoporous titanium dioxide precursor solution is ground into powder in a mortar, the powder is transferred into a beaker, 2g of terpineol and 3m L of ethanol are added, heating and stirring are carried out at the temperature of 60 ℃, 4g of ethyl cellulose is added, ball milling is carried out for 3h by a ball mill at room temperature, a white colloidal substance is obtained, 1g of the white colloidal substance is weighed, 8.5ml of ethanol is added for dilution, and a mesoporous titanium dioxide precursor solution is obtained.
(c) Firstly, mixing methyl ammonium bromide, formamidine hydroiodide, lead bromide, lead iodide, N-N dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution (wherein the methyl ammonium bromide is 22.65mg, the formamidine hydroiodide is 187.96mg, the lead bromide is 74.3mg and the lead iodide is 528.99mg, the mixture is dissolved in a mixed solution of 20m L dimethyl sulfoxide and 80m L N-N dimethylformamide), then, using chlorobenzene as an anti-solvent, and spin-coating the prepared perovskite precursor on the titanium dioxide of the mesoporous layer prepared in the step (b), wherein the spin-coating step is divided into two steps, the first step is 2000rmp at a rotating speed of 2000rmp for 10s at an acceleration of 200rmp/s, the second step is 6000rmp at a rotating speed of 30s at an acceleration of 2000rmp/s, the spin-coating is finished at 100 ℃ for 30min, and the processes are carried out in a glove box;
(d) preparing a hole transport layer precursor solution from Spiro-OMeTAD, anhydrous chlorobenzene, 4-tert-butylpyridine, lithium bistrifluoromethanesulfonylimide solution and cobalt-based bistrifluoromethanesulfonylimide salt solution (wherein Spiro-OMeTAD is 72.3mg, anhydrous chlorobenzene is 1m L, 4-tert-butylpyridine is 28.8 mu L, lithium bistrifluoromethanesulfonylimide solution is 17.5 mu L and cobalt-based bistrifluoromethanesulfonylimide salt solution is 29 mu L), spin-coating the prepared hole transport layer purple-black precursor solution on the perovskite layer prepared in the step (c), wherein the spin-coating rotation speed is 3000r/min, the spin-coating time is 30s and the spin-coating acceleration is 2000 rmp/s;
(e) and (d) preparing a counter electrode, namely putting the mesoscopic perovskite solar cell semi-finished product after the hole transmission layer is prepared in the step (d) into a mask plate, and evaporating a layer of metal counter electrode under the vacuum degree of 6.0 × 10-4Pa by adopting a vacuum coating method to complete the preparation of PSCs.
(3) The procedure for evaluating the performance of PSCs is as follows:
by using a solar simulator (100 mW/cm)2AM 1.5G) was irradiated with PSCs, and the photoelectric conversion efficiency thereof was measured using the J-V characteristic curve measured by the electrochemical workstation, as shown in fig. 7. The corresponding photovoltaic parameters are as follows: voc 1.138V, Jsc 23.81mA/cm2，FF＝0.722，PCE＝19.56％。
Secondly, Nb doped TiO2PSCs made of mesoporous layer material and TiO made of undoped Nb2The thermal stability and the ultraviolet stability of PSCs made of the material serving as the mesoporous layer are compared. The thermal stability test was conducted by placing PSCs made of two materials in a glove box, heating at 80 ℃, and performing an efficiency test every two hours. The UV stability test was carried out by placing PSCs made of the two materials under an ultraviolet lamp having a wavelength of 375nm (equivalent to 60 suns) and irradiating the PSCs under the same conditions for 250 min.
The measurement results show that the 1% Nb-doped PSCs prepared under the conditions of this example have better thermal stability and uv stability than those of the non-Nb-doped PSCs.
Example 7
Examples include Nb doping of TiO2Preparation of material, Nb doped TiO2The material is applied to three parts of a preparation process of mesoscopic PSCs and performance evaluation of the PSCs, wherein the performance evaluation of the PSCs comprises photoelectric conversion efficiency determination, thermal stability determination and ultraviolet stability determination.
(1) 1% Nb doped TiO2The preparation process of the material is as follows:
10.04ml of TBT solution are weighed into a beaker, and 0.1058g of weighed NbCl are added5·5H2Mixing and stirring O for 10min, adding 3.26ml of glacial acetic acid, stirring for 20min, transferring the obtained mixed solution into a reaction kettle with the volume of 50ml of polytetrafluoroethylene lining stainless steel, performing hydrothermal treatment at 220 ℃ for 12h to obtain Nb-doped TiO2Cooling to room temperature after the reaction. Collecting the product by centrifugation, centrifuging and cleaning with anhydrous ethanol for multiple times, and drying the obtained product in a vacuum drying oven at 80 deg.C for 12 hr to obtain solid white substance, i.e. 1% Nb-doped TiO2。
(2) 1% Nb doped TiO2The preparation process of the mesoscopic PSCs with the mesoporous layer as the material is as follows:
(a) preparing a precursor solution of the titanium dioxide of the dense layer by directly mixing absolute ethyl alcohol, 2 mol/L hydrochloric acid and diisopropyl di (acetylacetonate) titanate (wherein the absolute ethyl alcohol: the hydrochloric acid: the diisopropyl di (acetylacetonate) titanate is 9m L: 0.7m L: 1.3m L), spraying the precursor of the titanium dioxide of the dense layer on an FTO substrate by using a thermal spraying method to obtain the titanium dioxide of the dense layer, wherein the spraying temperature is 450 ℃, and the spraying time is 30 min;
(b) preparing mesoporous layer titanium dioxide: weighing the prepared 1 percent Nb-doped TiO21g of the raw materials are ground into powder in a mortar, the powder is transferred into a beaker, 2g of terpineol and 3m of L ethanol are added into the beaker, the mixture is heated and stirred at the temperature of 60 ℃, 4g of ethyl cellulose is added into the mixture, the mixture is ball-milled for 3 hours by a ball mill at room temperature to obtain a white colloidal substance, then 1g of the white colloidal substance is weighed and is diluted by 8.5ml of ethanol to obtain a mesoporous-layer titanium dioxide precursor solution, finally, the rotating speed of a spin coater is set to be 5000rmp, the time is set to be 30s, the acceleration is set to be 3500rmp/s, 101 is takenAnd (3) dripping the mesoporous layer titanium dioxide precursor solution prepared by mu L on the dense layer titanium dioxide, starting a spin coater after the dense layer titanium dioxide precursor solution flows and is fully paved on an FTO (1.50cm x 1.50cm) substrate, and calcining the FTO loaded with the dense layer and the mesoporous layer precursor for 30min at 550 ℃ in a muffle furnace in the air atmosphere after the spin coating is finished to obtain the mesoscopic PSCs mesoporous layer titanium dioxide doped with 1% of Nb.
(c) Firstly, mixing methyl ammonium bromide, formamidine hydroiodide, lead bromide, lead iodide, N-N dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution (wherein the methyl ammonium bromide is 22.65mg, the formamidine hydroiodide is 187.96mg, the lead bromide is 74.3mg and the lead iodide is 528.99mg, the mixture is dissolved in a mixed solution of 20m L dimethyl sulfoxide and 80m L N-N dimethylformamide), then, using chlorobenzene as an anti-solvent, and spin-coating the prepared perovskite precursor on the titanium dioxide of the mesoporous layer prepared in the step (b), wherein the spin-coating step is divided into two steps, the first step is 2000rmp at a rotating speed of 2000rmp for 10s at an acceleration of 200rmp/s, the second step is 6000rmp at a rotating speed of 30s at an acceleration of 2000rmp/s, the spin-coating is finished at 100 ℃ for 30min, and the processes are carried out in a glove box;
(d) preparing a hole transport layer precursor solution from Spiro-OMeTAD, anhydrous chlorobenzene, 4-tert-butylpyridine, lithium bistrifluoromethanesulfonylimide solution and cobalt-based bistrifluoromethanesulfonylimide salt solution (wherein Spiro-OMeTAD is 72.3mg, anhydrous chlorobenzene is 1m L, 4-tert-butylpyridine is 28.8 mu L, lithium bistrifluoromethanesulfonylimide solution is 17.5 mu L and cobalt-based bistrifluoromethanesulfonylimide salt solution is 29 mu L), spin-coating the prepared hole transport layer purple-black precursor solution on the perovskite layer prepared in the step (c), wherein the spin-coating rotation speed is 3000r/min, the spin-coating time is 30s and the spin-coating acceleration is 2000 rmp/s;
(e) and (d) preparing a counter electrode, namely putting the mesoscopic perovskite solar cell semi-finished product after the hole transmission layer is prepared in the step (d) into a mask plate, and evaporating a layer of metal counter electrode under the vacuum degree of 6.0 × 10-4Pa by adopting a vacuum coating method to complete the preparation of PSCs.
(3) The procedure for evaluating the performance of PSCs is as follows:
by using a solar simulator (100 mW/cm)2AM 1.5G) was irradiated with PSCs, and the photoelectric conversion efficiency thereof was measured using the J-V characteristic curve measured by the electrochemical workstation, as shown in fig. 7. The corresponding photovoltaic parameters are as follows: voc 1.169V, Jsc 23.85mA/cm2，FF＝0.747，PCE＝20.83％。
Secondly, Nb doped TiO2PSCs made of mesoporous layer material and TiO made of undoped Nb2The thermal stability and the ultraviolet stability of PSCs made of the material serving as the mesoporous layer are compared. The thermal stability test was conducted by placing PSCs made of two materials in a glove box, heating at 80 ℃, and performing an efficiency test every two hours. The UV stability test was carried out by placing PSCs made of the two materials under an ultraviolet lamp having a wavelength of 375nm (equivalent to 60 suns) and irradiating the PSCs under the same conditions for 250 min.
The measurement results show that the 1% Nb-doped PSCs prepared under the conditions of this example have better thermal stability and uv stability than those of the non-Nb-doped PSCs.
It should be noted that the above-described embodiments may enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way. Thus, it will be appreciated by those skilled in the art that the invention may be modified and equivalents may be substituted; all technical solutions and modifications thereof which do not depart from the spirit and technical essence of the present invention should be covered by the scope of the present patent.

Claims (10)

1. A method for synthesizing niobium-doped titanium dioxide nano material is characterized by comprising the following steps:
adding weighed tetrabutyl titanate and niobium chloride pentahydrate into a beaker according to a certain proportion, uniformly mixing and stirring to obtain a solution A, then adding glacial acetic acid into the solution A, and stirring for 15-20min to obtain a solution B; then transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction at 220 ℃ for 12 hours, and cooling to room temperature to obtain a niobium-doped titanium dioxide colloid substance; and finally, centrifuging, washing and drying the colloidal substance to obtain the niobium-doped titanium dioxide nano material.
2. The method for synthesizing the niobium-doped titanium dioxide nano material as claimed in claim 1, wherein the ratio of the tetrabutyl titanate, the niobium chloride pentahydrate and the glacial acetic acid is 10m L: 0.0529-0.2117 g:3.4224m L.
3. The method for synthesizing the niobium doped titanium dioxide nano-material as claimed in claim 1, wherein the washing is performed by absolute ethyl alcohol, and the drying is performed at 80 ℃ for 12 h.
4. A niobium doped titania nanomaterial synthesized by the method of any one of claims 1-3.
5. The application of the niobium-doped titanium dioxide nanomaterial of claim 4 in preparing a mesoporous layer of a mesoscopic perovskite solar cell is characterized in that the preparation method of the mesoporous layer comprises the following steps:
weighing the prepared niobium-doped titanium dioxide nano material, grinding the material into powder, adding terpineol and ethanol, then adding ethyl cellulose under heating and stirring, uniformly stirring, and carrying out ball milling at room temperature to obtain a white colloid substance; then, diluting the obtained white colloidal substance with ethanol to obtain a mesoporous layer precursor solution; and (3) dripping the prepared mesoporous layer precursor solution onto the prepared compact layer titanium dioxide, performing spin coating after the compact layer titanium dioxide flows and is fully paved, and roasting in the air to obtain the mesoporous layer of the mesoscopic perovskite solar cell consisting of the niobium-doped titanium dioxide nano material.
6. The application of the niobium-doped titanium dioxide nanomaterial in preparing a mesoporous layer of a mesoscopic perovskite solar cell according to claim 5, wherein the preparation method of the dense-layer titanium dioxide comprises the following steps:
the precursor solution of the titanium dioxide of the dense layer is prepared by mixing absolute ethyl alcohol, hydrochloric acid and diisopropyl di (acetylacetonate) titanate, and the precursor solution of the titanium dioxide of the dense layer is attached to the FTO glass by adopting a thermal spraying technology, so that the titanium dioxide of the dense layer is obtained.
7. The application of the niobium-doped titanium dioxide nanomaterial in preparing the mesoporous layer of the mesoscopic perovskite solar cell as claimed in claims 5-6, wherein the mass ratio of the niobium-doped titanium dioxide nanomaterial to terpineol to ethyl cellulose is 1:2:4, the addition amount of ethanol before heating and stirring is 3ml for each gram of niobium-doped titanium dioxide nanomaterial, the heating temperature under stirring is 60 ℃, the dilution amount of ethanol is 8.5ml for each gram of white colloid substance, the spin-coating rotation speed is 5000rmp, the spin-coating time is 30s, and the spin-coating acceleration is 3000 rmp/s.
8. The application of the niobium-doped titanium dioxide nanomaterial in preparing the mesoporous layer of the mesoscopic perovskite solar cell according to claims 5-7 is characterized in that the roasting temperature is 450-550 ℃, and the roasting time is 10-40 min.
9. The application of the niobium-doped titanium dioxide nanomaterial in preparing a mesoporous layer of a mesoscopic perovskite solar cell as claimed in claim 5, wherein the thickness of the mesoporous layer of the mesoscopic perovskite solar cell consisting of the niobium-doped titanium dioxide nanomaterial is 150-200 nm.
10. Use of niobium doped titania nanomaterial according to any of claims 6-9 in the preparation of mesoporous layers for mesoscopic perovskite solar cells, characterized in that the FTO glass uses 30-45 μ L mesoporous layer precursor solution per square centimeter.
CN202010331788.XA 2020-04-24 2020-04-24 Preparation method and application of niobium-doped titanium dioxide nano material Pending CN111509063A (en)

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