CN115340520A - 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 invention 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 a chlorine-containing diphenylamine derivative is used as a peripheral group, wherein chlorine atoms are introduced, so that the highest molecular orbital level occupied by the material is reduced, the hole mobility is improved, the interface passivation capability is enhanced, and the hydrophobicity is improved. The invention introduces chlorine atoms at the periphery of the hole transport material, and has high hole mobility, good hydrophobicity and enhanced interface passivation capability; the preparation method is used for preparing the efficient hole transport material of the small-hysteresis perovskite solar cell. The prepared material has lower highest occupied molecular orbital energy level, is beneficial to improving the open-circuit voltage of the device, has the photoelectric conversion efficiency of over 22 percent, and shows negligible J-V hysteresis.
Description
Technical Field
The invention 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 a potential substitute for silicon-based solar cells, and the photoelectric conversion efficiency of the perovskite solar cells is improved from 3.8% to more than 25% through fine device design, material optimization and interface engineering. The hole transport material is one of important components in the perovskite solar cell structure, and not only plays a role in transporting holes, blocking electrons and extracting holes, but also plays a role in protecting a perovskite absorber from being corroded by air and moisture.
Although perovskite solar cells have made great progress in a short period of time, commercialization of perovskite solar cells is still hindered due to their unstable characteristics. Among them, the current density-voltage (J-V) hysteresis effect is one of the main factors that restrict the development thereof. During the J-V measurement of perovskite solar cells there is always a lag between the forward and reverse scans, i.e. the forward and reverse scans cannot overlap. For the reason of this phenomenon, first of all, it is possible to guess that since perovskite belongs to ionic crystal, which has both electronic conductivity and ionic conductivity, the potential difference caused by the migration of electrons causes the ions inside to migrate to different degrees. Ion accumulation due to ion migration can produce greater levels of n-type and p-type doping, which masks the applied voltage, alters the charge collection efficiency and ultimately leads to current hysteresis. The J-V hysteresis is also one of the instability which causes over-estimation or under-estimation of the practical photoelectric conversion efficiency of the perovskite solar cell, so that the evaluation of the real perovskite solar cell photovoltaic parameters is difficult. Although, the prior art has made many efforts to minimize J-V lag. However, since the solution-processed perovskite thin film is polycrystalline, a large number of grain boundaries are inevitably formed, and the strongly increased ion migration at the grain boundaries after electric polarization causes redistribution of ions, eventually resulting in retardation of photocurrent at the grain boundaries. Therefore, solvent engineering (control of crystal grains and grain boundaries, and improvement of crystallinity), which is closely related to the quality of perovskite thin films, is an important means for inhibiting ion migration. Another possibility is that interface band shifts and charge extraction and recombination of the perovskite layer also alter the ion transport of the perovskite, and the degree of hysteresis also depends on the interface properties and choice of contact material. Therefore, suppression of ion transport 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 method, but this method will lead to further complications in device fabrication.
Disclosure of Invention
The present invention has been made to solve at least one of the technical problems occurring in the prior art, and it is therefore an object of an aspect of the present invention 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 invention aims to provide 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, at room temperature, sequentially dissolving p-anisidine, 2-chloro-4-bromoanisole and sodium tert-butoxide in toluene, uniformly stirring, heating a reaction system, adding tri-tert-butylphosphine tetrafluoroborate and tris-dibenzylidene acetone dipalladium, carrying out reflux reaction on the whole reaction system, after the reaction is finished, adding deionized water for quenching reaction, cooling to room temperature, extracting with ethyl acetate, drying and filtering an organic phase obtained after extraction with 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 S1 in toluene, uniformly stirring, heating the reaction system, adding tri-tert-butylphosphine tetrafluoroborate and tris-dibenzylidene acetone dipalladium, carrying out reflux reaction on the whole reaction system, adding deionized water for quenching reaction after the reaction is finished, cooling to room temperature, extracting by using ethyl acetate, drying an organic phase obtained after 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, the mass ratio of the methoxyaniline, the 2-chloro-4-bromoanisole, the sodium tert-butoxide, the toluene, the tri-tert-butylphosphine tetrafluoroborate and the tris-dibenzylidene acetone dipalladium in the S1 is 1:1.5-2:1-1.8:12-15-0.05-0.1; the toluene is anhydrous toluene, the temperature of a reaction system is raised to 80 ℃ under the nitrogen atmosphere, the whole reaction system is subjected to reflux reaction for 10 hours at 120 ℃, and a crude product is separated and purified by using a chromatographic column; the chromatographic column is used for separation and purification, and the solvent is a mixed solvent of petroleum ether and ethyl acetate.
Preferably, the mass ratio of the intermediate A in S2, 2,7-dibromospiro [ fluorene-9,9-xanthene ], sodium tert-butoxide, toluene, tri-tert-butylphosphine tetrafluoroborate and tris-dibenzylideneacetone dipalladium is 1-1.5:1:0.2-0.4:12-15:0.01-0.06:0.05 to 0.1; the toluene is anhydrous toluene, the temperature of a reaction system is raised to 80 ℃ under the nitrogen atmosphere, the whole reaction system is subjected to reflux reaction for 10 hours at 120 ℃, and a crude product is separated and purified by using a chromatographic column; the chromatographic column is used for separation and purification, and the solvent is a mixed solvent of petroleum ether and ethyl acetate.
The preparation method of the hole transport material has the following synthetic route:
it is an object of a further aspect of the invention to provide the use of a hole transporting material for a small hysteresis perovskite battery.
The hole transport material is applied to the preparation of the 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 carrying out ultrasonic 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 to ensure that the surface of the conductive glass substrate is clean;
s2, preparing an electron transport layer: snO 2 Preparing a solution A from the colloidal solution and deionized water, spin-coating on the transparent conductive substrate prepared in the step S1, and then annealing 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 the 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 the compound I in a chlorobenzene solution, sequentially adding 4-tert-butylpyridine and lithium bis (trifluoromethanesulfonyl) imide to obtain a 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: a silver (Ag) electrode was deposited on the surface of the hole transport layer prepared in S4.
Preferably, in the step S1, ultra-pure water, isopropanol and ethanol are sequentially used for ultrasonic cleaning for 20min, and ultraviolet-ozone treatment is carried out for 15min; what is needed isSnO in said S2 2 The volume ratio of the colloidal solution to the deionized water is 1:2, spin coating at 4000rpm for 20S on the transparent conductive substrate prepared in S1, and annealing at 150 deg.C for 30min on a hot plate.
Preferably, the mass ratio of the lead iodide, cesium iodide, N-dimethylformamide and anhydrous dimethylsulfoxide in S3 is 0.5 to 1:0.01-0.05:0.5-1:0.05-0.2; spin-coating the solution B on the electron transport layer for 30s at the rotation speed of 4000rpm, and annealing for 1min in a nitrogen glove box at 70 ℃; the organic cation solution is prepared by dissolving formamidine iodide, methylamine chloride, methylamine bromide and methylamine iodide in isopropanol, wherein the mass ratio of formamidine iodide, methylamine chloride, methylamine bromide, methylamine iodide to isopropanol is 10-15:1-2:0.5-1:0.5-2:150 to 160; the organic cation solution is coated for 30s in a rotating mode at the rotating speed of 2300rpm, and then annealing treatment is carried out for 15min in air at the temperature of 150 ℃; the mass ratio of the compound I to the chlorobenzene solution in the S4 is 35-40: 1-solution C was spin-coated at 2500-4500rpm for 30s with an addition of 29. Mu.l of 4-tert-butylpyridine and 17.5. Mu.l of lithium bistrifluoromethanesulfonimide per ml of chlorobenzene solution.
Preferably, the silver (Ag) electrode in S5 is deposited by a thermal evaporation deposition method, and the deposition thickness is 90nm.
The invention has the following beneficial effects:
the invention provides a compound I, which takes 2,7-dibromospiro [ fluorene-9,9' -xanthene ] as a central nucleus and a chlorine-containing diphenylamine derivative as a peripheral group, wherein the introduction of chlorine atoms is beneficial to reducing the highest molecular orbital level occupied by the material, improving the hole mobility, enhancing the interface passivation capability and improving the hydrophobicity. According to the invention, chlorine atoms are introduced to the periphery of the compound I, so that the compound I has high hole mobility, good hydrophobicity and enhanced interface passivation capability. The compound I is used for preparing the efficient hole transport material of the small-hysteresis perovskite solar cell, the hole transport function can be achieved, the ion transport function can be inhibited, the preparation process is simple, the raw materials are easy to obtain, and the price is low. The prepared material has lower highest occupied molecular orbital energy level, is beneficial to improving the open-circuit voltage of a device, and the photoelectric conversion efficiency of the device can reach more than 22%. Meanwhile, the good hydrophobicity is favorable for improving the stability of the device; the enhanced interfacial passivation capability advantageously reduces device hysteresis, exhibiting negligible J-V hysteresis. The hole transport material can omit the interface modification layer of the conventional perovskite solar cell, simplifies the manufacturing operation of the device and is very suitable for industrial large-scale production.
Additional aspects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a cyclic voltammogram of compound I of an example of the present invention;
FIG. 2 is a hole transport test chart of Compound I of an example of the present invention;
FIG. 3 is a differential scanning calorimetry trace of Compound I of an example of the present invention;
FIG. 4 is a thermogravimetric analysis of compound I of the example of the present invention;
FIG. 5 is a water contact angle test plot of a perovskite according to an embodiment of the present invention;
FIG. 6 is a graph showing water contact angle measurements of Compound I of an example of the present invention;
fig. 7 is a device structure diagram of a perovskite solar cell prepared by using compound I of an example of the present invention as a hole transport material.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described and, therefore, the scope of the present invention is not limited by the specific embodiments disclosed below.
The invention 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, sequentially dissolving p-anisidine (1.5g, 12.18mmol), 2-chloro-4-bromoanisole (2.97g, 13.4mmol) and sodium tert-butoxide (2.33g, 24.36mmol) in 30ml of anhydrous toluene, uniformly stirring, heating the reaction system to 80 ℃ under nitrogen atmosphere, adding tri-tert-butylphosphine tetrafluoroborate (222.29mg, 0.24mmol) and tris-dibenzylidene acetone dipalladium (104mg, 0.36mmol), carrying out reflux reaction on the whole reaction system at 120 ℃ for 10h, after the reaction is finished, adding deionized water for quenching reaction, cooling to room temperature, extracting by using ethyl acetate, drying and filtering an organic phase obtained after extraction by using anhydrous magnesium sulfate to obtain a crude product, separating and purifying the crude product by using a chromatographic column, and using a mixed solvent of petroleum ether and ethyl acetate as a chromatographic column solvent to obtain an intermediate A (2, 44g, 76%) of a 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, the intermediate A (656mg, 2.49mmol) obtained in S1, 2,7-dibromospiro [ fluorene-9,9-xanthene](1g, 2.04mmol) and sodium tert-butoxide (489.6 mg, 5.1mmol) are sequentially dissolved in 20ml of anhydrous toluene, the mixture is uniformly stirred, the reaction system is heated to 80 ℃ under the nitrogen atmosphere, tri-tert-butylphosphine tetrafluoroborate (56.16mg, 0.2mmol) and tris-dibenzylidene acetone dipalladium (74.66mg, 0.08mmol) are added, the whole reaction system is refluxed for 10 hours at 120 ℃, after the reaction is finished, deionized water is added to quench the reaction, the reaction is cooled to room temperature, and ethyl acetate is used for reactionExtraction, drying of the organic phase obtained after extraction with anhydrous magnesium sulfate and filtration gave a crude product, which was isolated and purified using a column chromatography using a mixed solvent of petroleum ether and ethyl acetate to give 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 subjected to absorption spectroscopy using Hitachi, U-3900, USA. It was found that the absorption peak of compound I in the solution state was 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 determined using electrochemical Cyclic Voltammetry (CV) with the experimental instrument autolab pgstat30 electrochemical workstation, switzerland, which employs a three-electrode system. The solvent used in the test was typically chlorobenzene, the electrolyte was tetrabutylammonium perchlorate (TBAP), the concentration was 0.1M; the test environment required nitrogen protection. The rate of instrument scan was 100mV S -1 The reference substance is ferrocene, and the HOMO energy level and the LUMO energy level of the material are jointly calculated by measuring the voltage of a first oxidation peak and the position of an absorption edge in an ultraviolet absorption spectrum respectively. The highest molecular occupied orbital (HOMO) level and the lowest occupied molecular orbital (LUMO) level of Compound I were-5.18 eV and-2.28 eV, respectively, as shown in FIG. 1.
Determination of hole mobility for compound I:
the hole mobility of the compound isWith ITO/PEDOT of PSS (40 nm)/HTM (60 nm)/MoO 3 The (5 nm)/Al (80 nm) structure is a hole-only device, and a hole mobility test represents the hole transport capability of the compound by using a space charge limited current method (SCLC), wherein the higher the hole mobility, the better the hole transport capability. The hole mobility of compound I tested as shown in FIG. 2 was 1.6X 10 -4 cm 2 V -1 S -1 。
Determination of the thermodynamic stability of compound I:
differential Scanning Calorimetry (DSC) test: the DSC spectrum test uses a DSC Q2000 differential calorimeter of TA company of America, and under the condition of nitrogen protection, the temperature rise rate is 10 ℃/min, and the temperature drop rate is 20 ℃/min.
Thermogravimetric analysis (TGA) test: the TGA spectrum test uses a German relaxation-resistant 209F3 thermogravimeter, under the condition of nitrogen protection, the temperature rise rate is 10 ℃/min, the flow rate of the protective gas flow nitrogen is 30ml/min, and the weight of the material is changed until the constant weight state is reached.
The thermal stability of compound I was tested by DSC and TGA, as shown in figure 3, which shows a glass transition temperature of 113 ℃, facilitating the formation of a uniform film with long-term morphology retention. The thermal decomposition temperature of compound I was 383 ℃ as measured by TGA of compound I shown in FIG. 4. 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 for Compound I:
the hydrophobicity tests shown in fig. 5-6 can obtain the water contact angle of the compound, and the larger the water contact angle, the better the hydrophobicity, which can effectively prevent moisture from directly contacting with perovskite, and is beneficial to improving the stability of the device.
Compound I photovoltaic characterization is shown in the following table:
the invention provides an application of a hole transport material of a small-hysteresis perovskite battery in preparation of a small-hysteresis perovskite solar energy electricityAnd (4) a pool. The solar cell device mainly includes: transparent conductive substrate (ITO glass substrate), electron transport layer (SnO) 2 Layer), perovskite layer, hole transport layer and metal electrode. Wherein the electron transport layer (SnO) 2 Layer) as an electron transport layer and a perovskite layer as a light absorbing layer. The structure of which 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 carrying out ultrasonic cleaning for 20min 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 for 15min, so that the surface of the conductive glass substrate is clean and clean;
s2, preparing an electron transport layer: snO is treated 2 The volume ratio of the colloidal solution to the deionized water is 1:2 preparing a solution A, spin-coating the transparent conductive substrate prepared in the step S1 for 20S at the rotating speed of 4000rpm, and then carrying out annealing treatment on the transparent conductive substrate on a heating plate at the temperature of 150 ℃ for 30min;
s3, preparing a perovskite layer: dissolving lead iodide (691.5 mg) and cesium iodide (19.5 mg) in a mixed solvent of N, N-dimethylformamide (0.9 ml) and anhydrous dimethyl sulfoxide (0.1 ml) to obtain solution B, spin-coating solution B on the electron transport layer prepared in S2 at 4000rpm for 30S, and annealing in a 70 ℃ nitrogen glove box for 1min, cooling the substrate to room temperature in the nitrogen glove box, then spin-coating the substrate with a mixed organic cation solution (formamidine iodide (118.6 mg), methylamine chloride (18 mg), methylamine bromide (5.6 mg) and methylamine iodide (10 mg) in isopropanol (2 ml) at 2300rpm for 30S, and then annealing in 150 ℃ air for 15min;
s4, preparing a hole transport layer: compound I (41.84 mg) was dissolved in a chlorobenzene solution (1 ml), followed by addition of 4-t-butylpyridine (29. Mu.l ml) -1 ) And lithium bis (trifluoromethanesulfonylimide) (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 the speed of 2500-4500 rpm;
s5, preparing a metal electrode: and depositing a silver (Ag) electrode on the surface of the hole transport layer prepared in the step S4 by a thermal evaporation deposition method, wherein the deposition thickness is 90nm.
Solar cell J-V characteristic measurement:
the photovoltaic performance of the perovskite solar cell based on the compound I is tested by testing the J-V curve of the perovskite solar cell under standard solar radiation. The J-V curve shown in FIG. 7 can be tested to obtain four performance parameters of the battery, 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 indicator for quantifying the hysteresis of perovskite solar cells, showing the difference between forward and reverse scan efficiencies. Smaller HI indicates that the perovskite solar cell has less hysteresis effect, and the real photovoltaic parameters can be more accurately estimated.
Example 1:
compound I (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu. Lml was added in sequence -1 4-tert-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating the perovskite surface at 2500rpm for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans 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 of the same was successively added -1 4-tert-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating the perovskite surface at 3000rpm for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans at a rate of 50 mV/s.
Example 3:
compound I (41.84 mg) was dissolved in a chlorobenzene solution (1 ml), to which 29. Mu.l ml were successively added -1 4-Tert-butylpyrazole and 17.5. Mu. Lml -1 Bis (trifluoromethanesulfonyl) amide (II)Imine) lithium, followed by spin coating at 3500rpm on the perovskite surface for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans 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-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating the perovskite surface at 4000rpm for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans 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-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating of the perovskite surface at 4500rpm for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans 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-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating the perovskite surface at 2500rpm for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans 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-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating the perovskite surface at 3000rpm for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans 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-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating the perovskite surface at 3500rpm for 30s to prepare a hole transport layer. 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 (41.84 mg) was dissolved in chlorobenzene solution (1 ml), to which 29. Mu. Lml was added in sequence -1 4-tert-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating the perovskite surface at 4000rpm for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans 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-butylpyrazole and 17.5. Mu.l ml -1 Followed by spin coating the perovskite surface at 4500rpm for 30s to prepare a hole transport layer. The prepared perovskite solar cell was subjected to forward and reverse J-V curve scans at a rate of 100 mV/s.
Photovoltaic parameters measured for examples 1-10 as shown in table 1 below, the average hysteresis factor for compound I based devices was only 0.90% and the minimum hysteresis factor was reduced to 0.07%, indicating that a small hysteresis perovskite solar cell was prepared using compound I.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it is obvious to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A hole transport material for a small hysteresis perovskite battery, characterized in that: the hole transport material is a compound I, and the chemical structural formula of the hole transport material is as follows:
2. a preparation method of a hole transport material of a small-hysteresis perovskite battery is characterized by comprising the following steps: the preparation method of the hole transport material comprises the following specific steps:
s1, at room temperature, sequentially dissolving p-anisidine, 2-chloro-4-bromoanisole and sodium tert-butoxide in toluene, uniformly stirring, heating a reaction system, adding tri-tert-butylphosphine tetrafluoroborate and tris-dibenzylidene acetone dipalladium, carrying out reflux reaction on the whole reaction system, after the reaction is finished, adding deionized water for quenching reaction, cooling to room temperature, extracting with ethyl acetate, drying and filtering an organic phase obtained after extraction with 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 S1 in toluene, uniformly stirring, heating a reaction system, adding tri-tert-butylphosphine tetrafluoroborate and tris-dibenzylidene acetone dipalladium, carrying out reflux reaction on the whole reaction system, adding deionized water to carry out quenching reaction after the reaction is finished, cooling to room temperature, extracting by using ethyl acetate, drying an organic phase obtained after 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 as claimed in claim 2, wherein: the mass ratio of methoxyaniline, 2-chloro-4-bromoanisole, sodium tert-butoxide, toluene, tri-tert-butylphosphine tetrafluoroborate and tris-dibenzylideneacetone dipalladium in the S1 is 1:1.5-2:1-1.8:12-15-0.05-0.1; the toluene is anhydrous toluene, the temperature of a reaction system is raised to 80 ℃ under the nitrogen atmosphere, the whole reaction system is subjected to reflux reaction for 10 hours at 120 ℃, and a crude product is separated and purified by using a chromatographic column; the chromatographic column is used for separation and purification, and the solvent is a mixed solvent of petroleum ether and ethyl acetate.
4. The method for preparing a hole transport material for a small hysteresis perovskite battery as claimed in claim 2, wherein: the mass ratio of the intermediate A in the S2 to the 2,7-dibromospiro [ fluorene-9,9-xanthene ], sodium tert-butoxide, toluene, tri-tert-butylphosphine tetrafluoroborate and tris-dibenzylidene acetone dipalladium is 1-1.5:1:0.2-0.4:12-15:0.01-0.06:0.05 to 0.1; the toluene is anhydrous toluene, the temperature of a reaction system is raised to 80 ℃ under the nitrogen atmosphere, the whole reaction system is subjected to reflux reaction for 10 hours at 120 ℃, and a crude product is separated and purified by using a chromatographic column; the chromatographic column is used for separation and purification, and the solvent is a mixed solvent of petroleum ether and ethyl acetate.
5. The method for preparing a hole transport material for a small hysteresis perovskite battery according to claim 2, characterized in that: the preparation method of the hole transport material has the following synthetic route:
6. the application of a hole transport material of a small-hysteresis perovskite battery is characterized in that: the hole transport material is applied to the preparation of a small-hysteresis perovskite solar cell.
7. The use of the hole transport material for a small hysteresis perovskite battery as claimed in claim 6, 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; the cleaned conductive glass substrate is dried by nitrogen, and then is subjected to ultraviolet-ozone treatment;
s2, preparing an electron transport layer: snO 2 Preparing a solution A from a colloidal solution and deionized water, spin-coating on the transparent conductive substrate prepared in the step S1, and then annealing 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 the 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 the compound I in a chlorobenzene solution, sequentially adding 4-tert-butylpyridine and lithium bis (trifluoromethanesulfonyl) imide to obtain a 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: and depositing a silver electrode on the surface of the hole transport layer prepared in S4.
8. Use of a hole transport material for a small hysteresis perovskite battery as claimed in claim 7, characterized in that: in the step S1, ultra-pure 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 colloidal solution to the deionized water is 1:2, spin coating at 4000rpm for 20S on the transparent conductive substrate prepared in S1, and annealing at 150 deg.C for 30min on a hot plate.
9. The use of the hole transport material for a small hysteresis perovskite battery as claimed in claim 7, wherein: the mass ratio of the lead iodide, the cesium iodide, the N, N-dimethylformamide and the anhydrous dimethyl sulfoxide in the S3 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 for 30s at the rotation speed of 4000rpm, and annealing for 1min in a nitrogen glove box at 70 ℃; the organic cation solution is prepared by dissolving formamidine iodide, methylamine chloride, methylamine bromide and methylamine iodide in isopropanol, wherein the mass ratio of formamidine iodide, methylamine chloride, methylamine bromide, methylamine iodide to isopropanol is 10-15:1-2:0.5-1:0.5-2:150 to 160; the organic cation solution is coated for 30s in a rotating mode at the rotating speed of 2300rpm, and then annealing treatment is carried out for 15min in air at the temperature of 150 ℃; the mass ratio of the compound I to the chlorobenzene solution in the S4 is 35-40: 1-29. Mu.L of 4-tert-butylpyridine and 17.5. Mu.l of lithium bistrifluoromethanesulfonimide per ml of chlorobenzene solution, solution C was spin-coated for 30s at 2500-4500 rpm.
10. Use of a hole transport material for a small hysteresis perovskite battery as claimed in claim 7, characterized in that: and the silver electrode in the S5 is deposited by a thermal evaporation deposition method, and the deposition thickness is 90nm.
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