CN115340520B - Hole transport material of small hysteresis perovskite battery and preparation and application thereof - Google Patents
Hole transport material of small hysteresis perovskite battery and preparation and application thereof Download PDFInfo
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Abstract
The application relates to the technical field of photoelectric materials, in particular to a hole transport material of a small hysteresis perovskite battery, and preparation and application thereof. The hole transport material is a compound I, 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] is used as a central core, and the chlorine-containing diphenylamine derivative is used as a peripheral group, wherein the introduction of chlorine atoms is beneficial to reducing the highest occupied molecular orbital energy level of the material, improving the hole mobility, enhancing the interface passivation capability and improving the hydrophobicity. Chlorine atoms are introduced into the periphery of the hole transport material, so that the hole transport material has high hole mobility, good hydrophobicity and enhanced interface passivation capability; the preparation method is used for preparing the hole transport material of the high-efficiency small-hysteresis perovskite solar cell. The prepared material has lower highest occupied molecular orbit energy level, is favorable for improving the open circuit voltage of the device, has the photoelectric conversion efficiency of the device reaching more than 22 percent, and shows negligible J-V hysteresis.
Description
Technical Field
The application relates to the technical field of photoelectric materials, in particular to a hole transport material of a small hysteresis perovskite battery, and preparation and application thereof.
Background
Perovskite solar cells are considered as potential alternatives to silicon-based solar cells, whose photoelectric conversion efficiency has been improved from 3.8% to above 25% by elaborate device design, material optimization and interface engineering. The hole transport material is used as one of important components in the perovskite solar cell structure, and has the functions of transporting holes, blocking electrons and extracting holes, and protecting the perovskite absorber from being corroded by air and moisture.
Despite the great progress made in perovskite solar cells in a short period of time, commercialization of perovskite solar cells has been hindered due to their unstable characteristics. Among them, the current density-voltage (J-V) hysteresis effect is one of the main factors restricting the development thereof. During the J-V measurement of a perovskite solar cell, there is always a hysteresis between the forward and reverse scans, i.e. the forward and reverse scans cannot overlap. For the reasons for this phenomenon, it is first of all possible to hypothesize that, since perovskite belongs to ionic crystals, which are both electronically conductive and ionically conductive, the potential difference created by the migration of electrons causes the migration of ions inside to a different extent. Ion accumulation due to ion migration produces a greater degree of n-type and p-type doping, which shields the applied voltage, changing the charge collection efficiency and ultimately resulting in current hysteresis. Such J-V hysteresis is also one of the instabilities that lead to overestimation or underestimation of the actual photoelectric conversion efficiency of the perovskite solar cell, making it difficult to evaluate the actual perovskite solar cell photovoltaic parameters. Although, many efforts have been made in the prior art to minimize J-V hysteresis. However, since the solution processed perovskite thin film is polycrystalline, a large number of grain boundaries are inevitably formed, and ion redistribution is caused by the strongly increased ion migration at the grain boundaries after electric polarization, and finally a retardation of photocurrent is generated at the grain boundaries. Therefore, solvent engineering (controlling crystal grains and grain boundaries, improving crystallinity) closely related to the quality of perovskite thin films becomes an important means for inhibiting ion migration. Another possibility is that the interface band shift and charge extraction and recombination of the perovskite layers also alter the ion transport of the perovskite, and the extent of hysteresis is also dependent on the interface properties and the choice of contact material. Thus, suppression of ion migration to reduce hysteresis by introducing an interfacial layer between the perovskite layer and the hole transport layer to passivate surface defects is the most common approach, but this approach will lead to further complications in device fabrication.
Disclosure of Invention
The present application is directed to solving at least one of the technical problems of the prior art, and therefore, an aspect of the present application is to provide a hole transport material for a small-hysteresis perovskite battery.
The hole transport material is a compound I, and the chemical structural formula of the hole transport material is as follows:
another aspect of the present application is directed to a method for preparing a hole transport material for a small hysteresis perovskite battery.
The preparation method of the hole transport material comprises the following specific steps:
s1, sequentially dissolving p-methoxyaniline, 2-chloro-4-bromoanisole and sodium tert-butoxide in toluene at room temperature, stirring uniformly, heating a reaction system, adding tri-tert-butylphosphine tetrafluoroborate and tri-dibenzylideneacetone dipalladium, carrying out reflux reaction on the whole reaction system, adding deionized water to quench the reaction after the reaction is finished, cooling to room temperature, extracting by using ethyl acetate, drying and filtering an organic phase obtained after the extraction by using anhydrous magnesium sulfate to obtain a crude product, and separating and purifying the crude product to obtain an intermediate A;
s2, sequentially dissolving the intermediate A, 2, 7-dibromospiro [ fluorene-9, 9-xanthene ] and sodium tert-butoxide obtained in the S1 into toluene, uniformly stirring, heating a reaction system, adding tri-tert-butylphosphine tetrafluoroborate and tri-dibenzylideneacetone dipalladium, carrying out reflux reaction on the whole reaction system, adding deionized water to quench the reaction after the reaction is finished, cooling to room temperature, extracting by using ethyl acetate, drying an organic phase obtained after the extraction by using anhydrous magnesium sulfate, filtering to obtain a crude product, and separating and purifying the crude product to obtain the compound I.
Preferably, in the S1, the mass ratio of the methoxyaniline, the 2-chloro-4-bromoanisole, the sodium tert-butoxide, the toluene, the tri-tert-butylphosphine tetrafluoroborate and the tri-dibenzylideneacetone dipalladium is 1:1.5-2:1-1.8:12-15-0.05-0.1; the toluene is anhydrous toluene, the reaction system is heated to 80 ℃ under the nitrogen atmosphere, the whole reaction system is subjected to reflux reaction for 10 hours at 120 ℃, and the crude product is separated and purified by using a chromatographic column; the chromatographic column is used for separation and purification, and the solvent adopts a mixed solvent of petroleum ether and ethyl acetate.
Preferably, the mass ratio of the intermediate A, 2, 7-dibromospiro [ fluorene-9, 9-xanthene ], sodium tert-butoxide, toluene, tri-tert-butylphosphine tetrafluoroborate and tri-dibenzylideneacetone dipalladium in the S2 is 1-1.5:1:0.2-0.4:12-15:0.01-0.06:0.05-0.1; the toluene is anhydrous toluene, the reaction system is heated to 80 ℃ under the nitrogen atmosphere, the whole reaction system is subjected to reflux reaction for 10 hours at 120 ℃, and the crude product is separated and purified by using a chromatographic column; the chromatographic column is used for separation and purification, and the solvent adopts a mixed solvent of petroleum ether and ethyl acetate.
The synthetic route of the preparation method of the hole transport material is as follows:
it is an object of a further aspect of the present application to provide the use of a hole transport material for a small hysteresis perovskite cell.
The application of the hole transport material is to prepare a small hysteresis perovskite solar cell. The hole transport material is one of key components for improving the performance of the perovskite solar cell, can play a role in transporting hole migration and inhibiting ion migration, and omits an interface modification layer to obtain the small-hysteresis perovskite solar cell.
The preparation method of the small hysteresis perovskite solar cell comprises the following specific steps:
s1, preparing a transparent conductive substrate: firstly, cleaning dust and pollutants attached to the surface of a conductive glass substrate by using a detergent, and then sequentially ultrasonically cleaning by using ultrapure water, isopropanol and ethanol to remove organic pollutants; the cleaned conductive glass substrate is dried by nitrogen, and then is subjected to ultraviolet-ozone treatment, so that the surface of the conductive glass substrate is clean;
s2, preparing an electron transport layer: snO is prepared 2 Preparing a solution A from a colloid solution and deionized water, spin-coating the solution A on the transparent conductive substrate prepared in the step S1, and then annealing the transparent conductive substrate on a heating plate;
s3, preparing a perovskite layer: dissolving lead iodide and cesium iodide in a mixed solvent of N, N-dimethylformamide and anhydrous dimethyl sulfoxide to obtain a solution B, spin-coating the solution B on the electron transport layer prepared in the step S2, annealing in a nitrogen glove box, cooling a substrate to room temperature in the nitrogen glove box, spin-coating with a mixed organic cation solution, and annealing in air;
s4, preparing a hole transport layer: dissolving a compound I in chlorobenzene solution, sequentially adding 4-tert-butylpyridine and lithium bistrifluoromethane sulfonyl imide to obtain solution C, and spin-coating the solution C on the surface of the perovskite layer prepared in the step S3;
s5, preparing a metal electrode: silver (Ag) electrode is deposited on the surface of the hole transport layer prepared in the step S4.
Preferably, in the step S1, ultrapure water, isopropanol and ethanol are sequentially used for ultrasonic cleaning for 20min, and ultraviolet-ozone treatment is carried out for 15min; snO in S2 2 The volume ratio of the colloid solution to deionized water is 1:2 spin-coating on the transparent conductive substrate prepared in S1 at 4000rpm for 20S, and annealing treatment on a heating plate at 150℃for 30min.
Preferably, in the S3, the mass ratio of the lead iodide, cesium iodide, N-dimethylformamide to anhydrous dimethyl sulfoxide is 0.5-1:0.01-0.05:0.5-1:0.05-0.2; spin-coating the solution B on the electron transport layer at 4000rpm for 30s, and annealing in a nitrogen glove box at 70 ℃ for 1min; the organic cation solution is prepared by dissolving formamidine, methylamine chloride, methylamine bromide and methylamine iodide in isopropanol, wherein the mass ratio of the formamidine iodide, the methylamine chloride, the methylamine bromide, the methylamine iodide and the isopropanol is (10-15): 1-2:0.5-1:0.5-2:150-160; the organic cation solution is spin-coated for 30s at 2300rpm, and then annealed in air at 150 ℃ for 15min; the mass ratio of the compound I to the chlorobenzene solution in the S4 is 35-40:1, 4-tert-butylpyridine was added in an amount of 29. Mu.l per ml of chlorobenzene solution, lithium bistrifluoromethanesulfonimide was added in an amount of 17.5. Mu.l, and solution C was spin-coated at a speed of 2500-4500rpm for 30s.
Preferably, the silver (Ag) electrode in S5 is deposited by thermal evaporation deposition, and the deposition thickness is 90nm.
The application has the following beneficial effects:
the application provides a compound I, which takes 2, 7-dibromospiro [ fluorene-9, 9' -xanthene ] as a central core and chlorine-containing diphenylamine derivatives as peripheral groups, wherein the introduction of chlorine atoms is beneficial to reducing the highest occupied molecular orbital energy level of a material, improving hole mobility, enhancing interface passivation capability and improving hydrophobicity. The application introduces chlorine atoms at the periphery of the compound I, and has high hole mobility, good hydrophobicity and enhanced interface passivation capability. The compound I is used for preparing the hole transport material of the high-efficiency small-hysteresis perovskite solar cell, which not only has the function of transporting holes but also has the function of inhibiting ion migration, and the preparation process is simple, the raw materials are easy to obtain and the cost is low. The prepared material has lower highest occupied molecular orbit energy level, is beneficial to improving the open circuit voltage of the device, and the photoelectric conversion efficiency of the device can reach more than 22%. Meanwhile, good hydrophobicity is beneficial to improving the stability of the device; the enhanced interface passivation capability is beneficial for reducing the hysteresis of the device, exhibiting negligible J-V hysteresis. The hole transport material can omit an interface modification layer of a conventional perovskite solar cell, simplifies the manufacturing operation of devices, and is very suitable for industrialized mass production.
Additional aspects and advantages of the application will become apparent in the following description or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a cyclic voltammogram of compound I of the present application;
FIG. 2 is a graph showing hole transport tests of Compound I according to an embodiment of the present application;
FIG. 3 is a differential scanning calorimetric analysis of compound I of the present application;
FIG. 4 is a thermogravimetric analysis of compound I of the present application;
FIG. 5 is a graph of water contact angle measurements of perovskite according to an embodiment of the application;
FIG. 6 is a graph of water contact angle measurements for compound I of the present application;
fig. 7 is a device structure diagram of a perovskite solar cell prepared by using the compound I as a hole transport material according to the embodiment of the application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will be more clearly understood, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It should be noted that, without conflict, the embodiments of the present application and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, the present application may be practiced otherwise than as described, and therefore the scope of the present application is not limited to the specific embodiments disclosed below.
The application relates to a hole transport material of a small hysteresis perovskite battery, which is a compound I and has the following chemical structural formula:
the preparation method of the hole transport material of the small hysteresis perovskite battery comprises the following specific steps:
s1, at room temperature, p-methoxyaniline (1.5 g,12.18 mmol), 2-chloro-4-bromoanisole (2.97 g,13.4 mmol) and sodium tert-butoxide (2.33 g,24.36 mmol) are sequentially dissolved in 30ml of anhydrous toluene, stirred uniformly, the reaction system is heated to 80 ℃ under nitrogen atmosphere, tri-tert-butylphosphine tetrafluoroborate (222.29 mg,0.24 mmol) and tri-dibenzylideneacetone dipalladium (104 mg,0.36 mmol) are added, the whole reaction system is subjected to reflux reaction at 120 ℃ for 10 hours, deionized water is added to quench the reaction after the reaction is completed, the reaction is cooled to room temperature, ethyl acetate is used for extraction, an organic phase obtained after the extraction is dried and filtered by anhydrous magnesium sulfate to obtain a crude product, the crude product is separated and purified by using a chromatographic column, and a petroleum ether and ethyl acetate mixed solvent is adopted by the chromatographic column to obtain an intermediate A (2, 44g, 76% of yellow liquid. 1 H NMR(600MHz,DMSO)δ(ppm):7.69(s,1H),7.01–6.93(m,4H),6.88–6.83(m,3H),3.76(s,3H),3.70(s,3H).MALDI-TOF:m/z[M] + cacld.C 14 H 14 ClNO 2 ,263.0688；found:263.0688。
S2, intermediate A (650 mg,2.49 mmol) obtained in S1, 2, 7-dibromospiro [ fluorene-9, 9-xanthene](1 g,2.04 mmol) and sodium t-butoxide (489.6 mg,5.1 mmol) were sequentially dissolved in 20ml of anhydrous toluene, stirred uniformly, the reaction system was warmed to 80℃under nitrogen atmosphere, and then tri-t-butylphosphine tetrafluoroborate (56.16 mg,0.2 mmol) and tri-dibenzylideneacetone dipalladium (74.66 mg,0.08 mmol) were added, the whole reaction system was subjected to reflux reaction at 120℃for 10 hours, after completion of the reaction, deionized water was added to quench the reaction, cooled to room temperature, and extraction was performed using ethyl acetate, the organic phase obtained after the extraction was dried with anhydrous magnesium sulfate and filtered to obtain a crude product, the crude product was separated and purified using a column chromatography solvent using a mixed solvent of petroleum ether and ethyl acetate to obtain compound I (1.26 g, yield 72%) as a yellow powder. 1 H NMR(600MHz,DMSO)δ(ppm):7.64(d,J＝8.3Hz,2H),7.27–7.23(m,2H),7.15(dd,J＝7.8,1.2Hz,2H),6.98–6.93(m,4H),6.92–6.88(m,6H),6.83–6.79(m,6H),6.76(dd,J＝8.4,1.8Hz,2H),6.57(d,J＝2.2Hz,2H),6.49(dd,J＝7.8,1.8Hz,2H),3.77(s,6H),3.70(s,6H). 13 C NMR(101MHz,DMSO-d6)δ(ppm):156.52,154.80,151.08,150.88,147.77,141.18,139.74,132.96,129.21,127.31,125.31,124.82,124.07,123.94,121.75,121.16,117.31,116.97,115.43,113.99,56.60,55.63.MALDI-TOF:m/z[M] + cacld.C 53 H 40 C l2 N 2 O 5 ,855.2336；found:855.2336。
Determination of photophysical Properties of Compound I:
a chlorobenzene solution of Compound I was prepared and an absorption spectrum measurement was performed on the solution of Compound I using Hitachi, inc. U-3900, U.S.A. The absorption peak of compound I in the solution state was measured to be at 390nm, and the optical band gap was 2.90eV.
Determination of the electrochemical properties of compound I:
the electrochemical properties of the compounds were measured using electrochemical Cyclic Voltammetry (CV), the laboratory instrument was an AutolabPGSTAT30 electrochemical workstation in switzerland, which employs a three-electrode system. The solvent used in the test is typically chlorobenzene, the electrolyte is tetrabutylammonium perchlorate (TBAP), and the concentration is 0.1M; the test environment requires nitrogen protection. The instrument scan rate was 100mV S -1 The reference is ferrocene, and the HOMO energy level and the LUMO energy level of the material are calculated together by measuring the voltage of the first oxidation peak and the absorption edge position in the ultraviolet absorption spectrum respectively. The Highest Occupied Molecular Orbital (HOMO) levels of compound I were-5.18 eV respectively and the lowest occupied molecular orbital (LUMO) levels were-2.28 eV respectively, as measured in fig. 1.
Determination of hole mobility for Compound I:
the hole mobility of the compound was expressed as ITO/PEDOT: PSS (40 nm)/HTM (60 nm)/MoO 3 The (5 nm)/Al (80 nm) structure is a hole-only device, and the hole mobility test characterizes the hole transport ability of the compound by using a space charge limited amperometric (SCLC) test, the higher the hole mobility, the better the hole transport ability. The hole mobility of the compound I obtained by the test shown in FIG. 2 was 1.6X10 -4 cm 2 V -1 S -1 。
Determination of thermodynamic stability of compound I:
differential Scanning Calorimetry (DSC) test: DSC spectrum test is carried out by using a DSC Q2000 differential calorimeter of the American TA company under the protection of nitrogen, wherein the heating rate is 10 ℃/min, and the cooling rate is 20 ℃/min.
Thermogravimetric analysis (TGA) test: TGA spectrum test uses German relaxation-resistant 209F3 thermogravimetry, under the protection of nitrogen, the heating rate is 10 ℃/min, the flow rate of the protection gas flow nitrogen is 30ml/min, and the weight of the material is changed until the constant weight state is reached.
Compound I was tested for thermal stability by DSC and TGA, as shown in figure 3, with a compound I glass transition temperature of 113 ℃, which is advantageous for forming uniform films with long-term morphology preservation. The TGA test of compound I shown in fig. 4 shows that the thermal decomposition temperature of compound I is 383 ℃. DSC and TGA tests show that the prepared compound has good thermal stability, and is beneficial to improving the stability of devices.
Determination of hydrophobicity of Compound I:
the hydrophobicity test shown in fig. 5-6 can obtain the water contact angle of the compound, and the larger the water contact angle is, the better the hydrophobicity is, so that the direct contact of moisture and perovskite can be effectively blocked, and the stability of the device is improved.
The photovoltaic characterization of compound I is shown in the following table:
the application provides an application of a hole transport material of a small hysteresis perovskite battery to prepare the small hysteresis perovskite solar battery. The solar cell device mainly includes: transparent conductive substrate (ITO glass substrate), electron transport layer (SnO) 2 Layer), a perovskite layer, a hole transport layer, and a metal electrode. Wherein the electron transport layer (SnO 2 Layer) as electron transport layer and perovskite layer as light absorbing layer. The structure is shown in fig. 7.
The preparation method of the small hysteresis perovskite solar cell comprises the following specific steps:
s1, preparing a transparent conductive substrate: firstly, cleaning dust and pollutants attached to the surface of a conductive glass substrate by using a detergent, and then sequentially ultrasonically cleaning the conductive glass substrate by using ultrapure water, isopropanol and ethanol for 20 minutes to remove organic pollutants; the washed conductive glass substrate is dried by nitrogen, and then is treated by ultraviolet rays and ozone for 15 minutes, so that the surface of the conductive glass substrate is clean;
s2, preparing an electron transport layer: snO is prepared 2 The volume ratio of the colloid solution to deionized water is 1:2 preparing a solution A, spin-coating the transparent conductive substrate prepared in the step S1 for 20S at a rotating speed of 4000rpm, and then annealing the transparent conductive substrate on a heating plate at 150 ℃ for 30min;
s3, preparing a perovskite layer: lead iodide (691.5 mg) and cesium iodide (19.5 mg) were dissolved in a mixed solvent of N, N-dimethylformamide (0.9 ml) and anhydrous dimethyl sulfoxide (0.1 ml) to obtain a solution B, the solution B was spin-coated on the electron transport layer prepared in S2 at a rotation speed of 4000rpm for 30S, and annealed in a nitrogen glove box at 70 ℃ for 1min, after the substrate was cooled to room temperature in the nitrogen glove box, the mixed organic cation solution (formamidine (118.6 mg), methylamine chloride (18 mg), methylamine bromide (5.6 mg) and methylamine iodide (10 mg) was dissolved in isopropanol (2 ml)) and spin-coated at a rotation speed of 2300rpm for 30S, and then annealed in air at 150 ℃ for 15min;
s4, preparing a hole transport layer: compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), followed by the addition of 4-tert-butylpyridine (29. Mu.l ml) -1 ) And lithium bis (trifluoromethanesulfonyl) imide (17.5. Mu.l ml) -1 ) Obtaining a solution C, and spin-coating the solution C on the surface of the perovskite layer prepared in the step S3 for 30S at a speed of 2500-4500 rpm;
s5, preparing a metal electrode: silver (Ag) electrode is deposited on the surface of the hole transport layer prepared in the step S4 by a thermal evaporation deposition method, and the deposition thickness is 90nm.
Solar cell J-V characteristics measurement:
the photovoltaic performance test of perovskite solar cells based on compound I is to test their J-V curve under standard solar radiation. The J-V curve shown in FIG. 7 can be tested to yield a batteryIs set to four performance parameters, open circuit voltage (V OC ) Short-circuit current (J) SC ) The Filling Factor (FF) and the Photoelectric Conversion Efficiency (PCE), and the good and bad photovoltaic performance of the battery can be seen through the four performance parameters; and calibrated by standard silicon-based solar cells.
Fill factor (HI):
HI is an important index for quantifying the hysteresis of perovskite solar cells, exhibiting a difference between forward and reverse scan efficiencies. Smaller HI indicates that perovskite solar cells have less hysteresis and can more accurately evaluate real photovoltaic parameters.
Example 1:
dissolving compound I (41.84 mg) in chlorobenzene solution (1 ml), and sequentially adding 29. Mu.lml thereto -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating the perovskite surface for 30s at 2500 rpm. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 50 mV/s.
Example 2:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.lml was added in sequence -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating the perovskite surface for 30s at 3000 rpm. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 50 mV/s.
Example 3:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.l ml was added in turn -1 4-tert-butylpyrazine and 17.5. Mu.lml -1 The hole transport layer was then prepared by spin coating the perovskite surface for 30s at 3500 rpm. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 50 mV/s.
Example 4:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.lml was added in sequence -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating the perovskite surface for 30s at 4000 rpm. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 50 mV/s.
Example 5:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.lml was added in sequence -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating on the perovskite surface at 4500rpm for 30s. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 50 mV/s.
Example 6:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.lml was added in sequence -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating the perovskite surface for 30s at 2500 rpm. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 100 mV/s.
Example 7:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.lml was added in sequence -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating the perovskite surface for 30s at 3000 rpm. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 100 mV/s.
Example 8:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.lml was added in sequence -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating the perovskite surface for 30s at 3500 rpm. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 100 mV/s.
Example 9:
compound I (41) was taken.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.lml were added in turn -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating the perovskite surface for 30s at 4000 rpm. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 100 mV/s.
Example 10:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu.lml was added in sequence -1 4-tert-butylpyrazine and 17.5. Mu.l ml -1 The hole transport layer was then prepared by spin coating on the perovskite surface at 4500rpm for 30s. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scanning at a rate of 100 mV/s.
The photovoltaic parameters measured in examples 1-10 are shown in table 1 below, with the average hysteresis factor of the compound I-based device being only 0.90% and the minimum hysteresis factor being reduced to 0.07%, indicating that a small hysteresis perovskite solar cell was produced using compound I.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. A hole transport material for a small hysteresis perovskite cell, characterized by: the hole transport material is a compound I, and the chemical structural formula of the hole transport material is as follows:
。
2. the method for preparing a hole transport material for a small hysteresis perovskite battery according to claim 1, wherein: the preparation method of the hole transport material comprises the following specific steps:
s1, sequentially dissolving p-methoxyaniline, 2-chloro-4-bromoanisole and sodium tert-butoxide in toluene at room temperature, stirring uniformly, heating a reaction system, adding tri-tert-butylphosphine tetrafluoroborate and tri-dibenzylideneacetone dipalladium, carrying out reflux reaction on the whole reaction system, adding deionized water to quench the reaction after the reaction is finished, cooling to room temperature, extracting by using ethyl acetate, drying and filtering an organic phase obtained after the extraction by using anhydrous magnesium sulfate to obtain a crude product, and separating and purifying the crude product to obtain an intermediate A;
s2, sequentially dissolving the intermediate A, 2, 7-dibromospiro [ fluorene-9, 9-xanthene ] and sodium tert-butoxide obtained in the S1 into toluene, uniformly stirring, heating a reaction system, adding tri-tert-butylphosphine tetrafluoroborate and tri-dibenzylideneacetone dipalladium, carrying out reflux reaction on the whole reaction system, adding deionized water to quench the reaction after the reaction is finished, cooling to room temperature, extracting by using ethyl acetate, drying an organic phase obtained after the extraction by using anhydrous magnesium sulfate, filtering to obtain a crude product, and separating and purifying the crude product to obtain the compound I.
3. The method for preparing a hole transport material for a small hysteresis perovskite battery according to claim 2, wherein: the mass ratio of the intermediate A, 2, 7-dibromospiro [ fluorene-9, 9-xanthene ], sodium tert-butoxide, toluene, tri-tert-butylphosphine tetrafluoroborate and tri-dibenzylideneacetone dipalladium in the S2 is 1-1.5:1:0.2-0.4:12-15:0.01-0.06:0.05-0.1; the toluene is anhydrous toluene, the reaction system is heated to 80 ℃ under the nitrogen atmosphere, the whole reaction system is subjected to reflux reaction at 120 ℃ for 10h, and the crude product is separated and purified by using a chromatographic column; the chromatographic column is used for separation and purification, and the solvent adopts a mixed solvent of petroleum ether and ethyl acetate.
4. The method for preparing a hole transport material for a small hysteresis perovskite battery according to claim 2, wherein: the synthetic route of the preparation method of the hole transport material is as follows:
。
5. the use of a hole transport material for a small hysteresis perovskite cell according to claim 1, wherein: the application of the hole transport material is to prepare a small hysteresis perovskite solar cell.
6. The use of a hole transport material for a small hysteresis perovskite cell according to claim 5, wherein: the preparation method of the small hysteresis perovskite solar cell comprises the following specific steps:
s1, preparing a transparent conductive substrate: firstly, cleaning dust and pollutants attached to the surface of a conductive glass substrate by using a detergent, and then sequentially ultrasonically cleaning by using ultrapure water, isopropanol and ethanol; blowing the cleaned conductive glass substrate with nitrogen, and then carrying out ultraviolet-ozone treatment on the cleaned conductive glass substrate;
s2, preparing an electron transport layer: snO is prepared 2 Preparing a solution A from a colloid solution and deionized water, spin-coating the solution A on the transparent conductive substrate prepared in the step S1, and then annealing the transparent conductive substrate on a heating plate;
s3, preparing a perovskite layer: dissolving lead iodide and cesium iodide in a mixed solvent of N, N-dimethylformamide and anhydrous dimethyl sulfoxide to obtain a solution B, spin-coating the solution B on the electron transport layer prepared in the step S2, annealing in a nitrogen glove box, cooling a substrate to room temperature in the nitrogen glove box, spin-coating with a mixed organic cation solution, and annealing in air;
s4, preparing a hole transport layer: dissolving a compound I in chlorobenzene solution, sequentially adding 4-tert-butylpyridine and lithium bistrifluoromethane sulfonyl imide to obtain solution C, and spin-coating the solution C on the surface of the perovskite layer prepared in the step S3;
s5, preparing a metal electrode: silver electrode is deposited on the surface of the hole transport layer prepared in the step S4.
7. The use of a hole transport material for a small hysteresis perovskite cell according to claim 6, wherein: sequentially ultrasonically cleaning the substrate in the S1 by using ultrapure water, isopropanol and ethanol for 20min, and treating the substrate by using ultraviolet rays and ozone for 15min; snO in S2 2 The volume ratio of the colloid solution to deionized water is 1:2 spin-coating 20. 20S on the transparent conductive substrate prepared in S1 at 4000rpm, and annealing treatment was performed on a heating plate at 150℃for 30min.
8. The use of a hole transport material for a small hysteresis perovskite cell according to claim 6, wherein: the silver electrode in the step S5 is deposited by a thermal evaporation deposition method, and the deposition thickness is 90nm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150144487A (en) * | 2014-06-17 | 2015-12-28 | 에스에프씨 주식회사 | Noble amine compound comprising aromatic amine group and organic light-emitting diode including the same |
| CN105622442A (en) * | 2016-02-23 | 2016-06-01 | 中节能万润股份有限公司 | Tert-butyl spirobifluorene compound and preparation method and application thereof |
| CN106977491A (en) * | 2017-01-25 | 2017-07-25 | 孙立成 | Spiro [ fluorene-9, 9-xanthene ] hole transport material and application thereof |
| CN108299407A (en) * | 2017-12-29 | 2018-07-20 | 太原理工大学 | Spiral shell [fluorenes -9,9 '-xanthene] derivative and its preparation based on the substitution of more sulphur fulvalenes and application |
| CN112707882A (en) * | 2020-12-11 | 2021-04-27 | 合肥工业大学 | Spiro [ fluorene-9, 9' -xanthene ] nuclear hole transport material and preparation method and application thereof |
| WO2022038694A1 (en) * | 2020-08-19 | 2022-02-24 | シャープ株式会社 | Display device and method for manufacturing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102249277B1 (en) * | 2013-05-15 | 2021-05-07 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
-
2022
- 2022-06-27 CN CN202210736491.0A patent/CN115340520B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150144487A (en) * | 2014-06-17 | 2015-12-28 | 에스에프씨 주식회사 | Noble amine compound comprising aromatic amine group and organic light-emitting diode including the same |
| CN105622442A (en) * | 2016-02-23 | 2016-06-01 | 中节能万润股份有限公司 | Tert-butyl spirobifluorene compound and preparation method and application thereof |
| CN106977491A (en) * | 2017-01-25 | 2017-07-25 | 孙立成 | Spiro [ fluorene-9, 9-xanthene ] hole transport material and application thereof |
| CN108299407A (en) * | 2017-12-29 | 2018-07-20 | 太原理工大学 | Spiral shell [fluorenes -9,9 '-xanthene] derivative and its preparation based on the substitution of more sulphur fulvalenes and application |
| WO2022038694A1 (en) * | 2020-08-19 | 2022-02-24 | シャープ株式会社 | Display device and method for manufacturing same |
| CN112707882A (en) * | 2020-12-11 | 2021-04-27 | 合肥工业大学 | Spiro [ fluorene-9, 9' -xanthene ] nuclear hole transport material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Kunpeng Guo, et al.. Introduction of Fluorine Into spiro[fluorene-9,90- xanthene]-Based Hole Transport Material to Obtain Sensitive-Dopant-Free, High Efficient and Stable Perovskite Solar Cells.《Sol.RRL》.2019,1800352. * |
| 邹金龙 ; 罗玉峰 ; 肖宗湖 ; 胡云 ; 饶森林 ; 刘绍欢 ; .空穴传输材料在高效钙钛矿太阳能电池中的发展演变.材料导报.2018,(第15期),2542-2554,2570. * |
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