CN113135925B - Aza-spiroalkene micromolecule perovskite solar cell hole transport material and preparation method thereof - Google Patents
Aza-spiroalkene micromolecule perovskite solar cell hole transport material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of perovskite solar cells, and aims to provide an azaspiroalkene micromolecule perovskite solar cell hole transport material and a preparation method thereof. The structural general formula of the azaspiroalkene micromolecule perovskite solar cell hole transport material is shown as formula (I) or (II). The product of the invention is used as a hole transport layer of the perovskite solar cell, has the characteristics of high glass transition temperature, high conductivity and high mobility, and is far superior to the existing product or the existing technical scheme in the aspect of long-term stability at 85 ℃.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to an azaspiroalkene micromolecule perovskite solar cell hole transport material, a preparation method thereof and application in photoelectric devices.
Background
In the last decade, organic-inorganic halogenated Perovskite Solar Cells (PSCs) have been demonstrated to have tunable optical band gaps, high optical absorption coefficients, long excited state lifetimes and solution processability. The highest Photoelectric Conversion Efficiency (PCE) of PSCs has been rapidly upgraded from 3.8% in 2009 to 25.17% today. The most effective n-i-p-type PSCs reported to date are obtained by applying the method to TiO2A perovskite layer and an organic Hole Transport Layer (HTL) are sequentially coated on the electron transport layer. In the prior art, the most widely used organic Hole Transport Materials (HTMs) of perovskite solar cells are D-pi-D type triarylamine organic small molecular materials represented by 2,2 ' -7,7 ' -tetra (N, N-bis (4-methoxyphenyl) amino-9, 9 ' -spirobifluorene (spiro-OMeTAD).
The strategy generally adopted for solving the problems is to construct conjugated small molecules with enhanced intermolecular interaction force and improved carrier transport performance. However, the rigid conjugated backbone of such molecules can affect their solubility, making such HTMs less prone to forming thin, high quality films. So far, there are still few literature reporting HTMs with completely new pi conjugated backbone that can achieve highly efficient, 85 ℃ thousand hours thermally stable PSCs. Therefore, it is necessary to develop HTMs having good solubility, high glass transition temperature, high mobility and high conductivity by a new strategy.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides an azaspiroene small-molecule perovskite solar cell hole transport material and a preparation method thereof. The perovskite solar cell prepared by the method has the advantages of solution processing, high glass transition temperature, high mobility and high conductivity, and the perovskite solar cell prepared by the method has high photoelectric conversion efficiency and good thermal stability.
In order to solve the technical problem, the solution of the invention is as follows:
the nitrogen heterocyclic spiroalkene micromolecule perovskite solar cell hole transport material is provided, and the structural general formula is shown as formula (I) or formula (II):
in the formula, R1、R2、R3Respectively C1-C6 alkyl.
Preferably, the azaspiroalkene small molecule perovskite solar cell hole transport material has a structural general formula as described in any one of the following formulas:
the invention further provides a preparation method of the azaspiroalkene micromolecule perovskite solar cell hole transport material, which has the following chemical reaction formula:
in the formula, R1、R2、R3Respectively C1-C6 alkyl;
the preparation process of the preparation method comprises the following steps:
(1) according to the mol ratio of 1: 5: 0.03: 0.09: 5, the mixture is mixed
1-chloronaphthalene-2-amine, palladium acetate, (oxydi-2, 1-phenylene) bis (diphenylphosphine) and sodium tert-butoxide are added together to toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; purifying by a chromatographic column to obtain a solid which is an intermediate product shown in a formula III;
(2) adding the intermediate product shown in the formula III, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and potassium carbonate into N, N-dimethylacetamide according to the mol ratio of 1: 0.15: 0.3: 9; heating to 130 ℃ under stirring under the protection of argon, and reacting for 24 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; recrystallizing and purifying to obtain a solid as an intermediate product shown in a formula IV;
(3) dissolving an intermediate product shown in a formula IV in a mixed solvent of N, N-dimethylformamide and tetrahydrofuran in a volume ratio of 1: 1; under the condition of room temperature, adding iodoalkane and sodium hydride with the mol ratio of 1: 5: 6 to the intermediate product shown in the formula IV while stirring, and reacting for 4 h; filtering the organic solvent to obtain a crude product; purifying by a chromatographic column to obtain a solid as an intermediate product shown in a formula V;
(4) taking an intermediate product shown in a formula V and N-bromosuccinimide according to a molar ratio of 1: 3, dissolving the intermediate product and the N-bromosuccinimide in dichloromethane, and reacting for 1h while stirring under the condition of ice water bath; adding a sodium sulfite saturated aqueous solution to quench the reaction, and filtering an organic solvent to obtain a solid which is an intermediate product shown in a formula VI;
(5) reacting an intermediate product of formula VI with
Palladium acetate, (oxydi-2, 1-phenylene) bis (diphenylphosphine) and sodium tert-butoxide are added together in a molar ratio of 1: 5: 0.03: 0.09: 5 to toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product A;
adding the crude product A, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and potassium carbonate into N, N-dimethylacetamide according to the molar ratio of 1: 0.15: 0.3: 9; heating to 130 ℃ under stirring under the protection of argon, and reacting for 10 hours; standing and cooling to room temperature, adding tetrahydrofuran with the same volume, adding iodoalkane and sodium hydride with the molar ratio of 1: 5: 6 to the crude product A, and reacting for 4 h; filtering the organic solvent to obtain a crude product of a final product; and purifying by a chromatographic column to obtain the azaspiroalkene micromolecule perovskite solar cell hole transport material shown in the formula I.
The invention further provides a preparation method of the azaspiroalkene micromolecule perovskite solar cell hole transport material shown in the formula (II), and the chemical reaction formula of the preparation method is as follows:
in the formula, R1、R2、R3Respectively C1-C6 alkyl;
the preparation process of the preparation method comprises the following steps:
(1) according to the mol ratio of 1: 5: 0.03: 0.09: 5, the mixture is mixed
Adding 2-chloronaphthalene-1-amine, palladium acetate, (oxydi-2, 1-phenylene) bis (diphenylphosphine) and sodium tert-butoxide into toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; purifying by a chromatographic column to obtain a solid which is an intermediate product shown in a formula VII;
(2) adding an intermediate product shown in a formula VII, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and potassium carbonate into N, N-dimethylacetamide according to a molar ratio of 1: 0.15: 0.3: 9; heating to 130 ℃ under stirring under the protection of argon, and reacting for 24 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; recrystallizing and purifying to obtain a solid which is an intermediate product shown in a formula VIII;
(3) dissolving an intermediate product shown in a formula VIII in a mixed solvent of N, N-dimethylformamide and tetrahydrofuran in a volume ratio of 1: 1; under the condition of room temperature, adding iodoalkane and sodium hydride with the mol ratio of 1: 5: 6 to the intermediate product shown in the formula VIII while stirring, and reacting for 4 h; filtering the organic solvent to obtain a crude product; purifying by a chromatographic column to obtain a solid which is an intermediate product shown in a formula IX;
(4) taking an intermediate product shown in a formula IX and N-bromosuccinimide according to a molar ratio of 1: 3, dissolving the intermediate product and the N-bromosuccinimide in dichloromethane, and reacting for 1h under the condition of ice-water bath while stirring; adding a sodium sulfite saturated aqueous solution to quench the reaction, and filtering an organic solvent to obtain a solid which is an intermediate product shown in the formula X;
(5) reacting an intermediate product of formula X with
Palladium acetate, (oxydi-2, 1-phenylene) bis (diphenylphosphine) and sodium tert-butoxide are added together in a molar ratio of 1: 5: 0.03: 0.09: 5 to toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product B;
adding the obtained crude product B, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and potassium carbonate into N, N-dimethylacetamide according to the molar ratio of 1: 0.15: 0.3: 9; heating to 130 ℃ under stirring under the protection of argon, and reacting for 10 hours; standing and cooling to room temperature, adding tetrahydrofuran with the same volume, adding iodoalkane and sodium hydride with the molar ratio of 1: 5: 6 to the crude product B, and reacting for 4 h; filtering the organic solvent to obtain a crude product of a final product; and purifying by a chromatographic column to obtain the azaspiroalkene micromolecule perovskite solar cell hole transport material shown in the formula II.
The invention also provides an application method of the azaspiroalkene micromolecule perovskite solar cell hole transport material, which is to prepare the azaspiroalkene micromolecule perovskite solar cell hole transport material into a hole transport layer to be applied to a perovskite solar cell device; the perovskite solar cell device has a multilayer structure and sequentially comprises: FTO glass substrate/dense TiO2Layer/mesoporous TiO2Layer/perovskite layer/hole transport layer/metal electrode layer.
Compared with the prior art, the invention has the beneficial effects that:
the hole transport layer made of the azaspiroalkene micromolecule perovskite solar cell hole transport material prepared by the invention is used for perovskite solar cells, the photoelectric conversion efficiency can reach 21.9-22.1%, and the retention rate of the photoelectric conversion efficiency of devices can be more than 80% by heat aging at 85 ℃ for thousands of hours.
Drawings
FIG. 1 is a DSC curve of example 1 of the present invention;
FIG. 2 is a voltage-current curve of a perovskite solar cell prepared in example 1 of the present invention before and after aging at 85 ℃ for thousands hours;
FIG. 3 is a DSC curve of example 2 of the present invention;
FIG. 4 is a voltage-current curve of a perovskite solar cell prepared in example 2 of the present invention before and after aging at 85 ℃ for thousands hours;
FIG. 5 is a voltage-current curve of a perovskite solar cell prepared in comparative example 1 of the present invention at 85 ℃ before and after 500-hour aging;
fig. 6 shows hole mobilities of examples 1 and 2 of the present invention;
FIG. 7 is the conductivity of examples 1 and 2 of the present invention;
fig. 8 is a schematic device structure diagram of a perovskite solar cell provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Synthesizing TBPC-611;
(1) will be provided with
(10g, 30mmol), 1-chloronaphthalene-2-amine (28.2g, 150mmol), palladium acetate (202mg,0.9mmol), (oxydi-2, 1-phenylene) bis (diphenylphosphine) (1.45g, 2.7mmol) and sodium tert-butoxide (14.4g, 150mmol) were added together with toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; purifying by a chromatographic column to obtain the compound 1.
(2) Adding the compound 1(12.5g, 20mmol) obtained in (1) together with palladium acetate (674mg, 3mmol), tri-tert-butylphosphine tetrafluoroborate (1.74g, 6mmol) and potassium carbonate (25.7g, 180mmol) to N, N-dimethylacetamide; heating to 130 ℃ under stirring under the protection of argon, and reacting for 24 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; and recrystallizing and purifying to obtain the compound 2.
(3) Dissolving the compound 2 obtained in the step (2) in N, N-dimethylformamide and tetrahydrofuran in a volume ratio of 1: 1, adding iodoalkane and sodium hydride with the molar ratio of 1: 5: 6 to the compound 2 under stirring at room temperature, and reacting for 4 h; filtering the organic solvent to obtain a crude product; purifying by a chromatographic column to obtain the compound 3.
(4) Dissolving the compound 3(4.48g, 6mmol) obtained in the step (3) in dichloromethane, adding N-bromosuccinimide (3.18g, 18mmol) under the condition of ice-water bath with stirring, and reacting for 1 h; adding sodium sulfite saturated aqueous solution to quench the reaction, and filtering the organic solvent to obtain a compound 4.
(5) The compound 4(6g, 6mmol) obtained in (4) was reacted with
(4.8g, 30mmol), palladium acetate (40.4mg, 0.18mmol), (oxydi-2, 1-phenylene) bis (diphenylphosphine) (290.8mg, 0.54mmol), and sodium tert-butoxide (2.9g, 30mmol) were added together to toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product 5; the resulting crude product 5, palladium acetate (202mg,0.9mmol), tri-tert-butylphosphine tetrafluoroborate (522mg,1.8mmol) and potassium carbonate (7.4g,54mmol) were added together to N, N-dimethylacetamide; heating to 130 ℃ under stirring under the protection of argon, and reacting for 10 hours; standing and cooling to room temperature, adding tetrahydrofuran with the same volume, adding iodoalkane and sodium hydride with the molar ratio of 1: 5: 6 to the crude product 5, and reacting for 4 h; filtering the organic solvent to obtain a crude product of a final product; purifying by a chromatographic column to obtain a TBPC-611 product.
Performing structural characterization on the obtained target product azaspiroalkene shown in the formula (I-1) by adopting a nuclear magnetic resonance, mass spectrometry and an element analysis method, and performing high-resolution mass spectrometry on the result: 1146.6131. elemental analysis results: c, 81.64%; h,6.85 percent and N,7.32 percent.
The nmr characterization data is as follows:
1H NMR(500MHz,THF-d8)δ10.36(d,J＝8.5,1H),10.26(dd,J＝8.4,1.2Hz,1H),10.06(d,J＝8.3Hz,0H),9.84(dd,J＝8.2,1.3Hz,1H),8.99(dd,J＝8.3,2.4Hz,3H),8.47–8.22(m,3H),8.04–7.85(m,3H),7.82–7.52(m,6H),7.37–7.19(m,3H),5.34(ddd,J＝14.4,9.6,4.8Hz,1H),5.08–4.95(m,J＝27.3,14.1,9.1,5.4Hz,2H),4.90(ddd,J＝15.0,9.9,5.9Hz,1H),4.79(ddd,J＝14.4,9.4,5.3Hz,1H),4.68–4.50(m,10H),4.23(d,J＝10.8Hz,6H),4.16(d,J＝3.2Hz,3H),1.36–1.26(m,2H),0.77–0.06ppm(m,31H)。
13C NMR(126MHz,THF-d8)δ155.91,155.83,155.77,142.45,141.87,141.36,140.03,140.03,139.77,138.74,138.38,137.96,137.81,137.75,137.55,131.26,131.15,130.78,128.67,127.31,127.28,126.06,125.42,125.30,124.83,124.75,124.69,124.29,124.08,123.69,123.67,122.56,122.35,122.27,122.24,121.69,121.66,118.16,117.58,117.25,115.94,115.08,114.87,114.66,114.23,111.36,111.35,111.29,111.27,110.28,110.19,106.37,106.18,105.44,56.95,56.67,56.56,54.23,53.95,53.75,35.51,35.26,35.10,32.18,31.92,31.77,27.92,27.59,27.41,27.10,27.01,26.98,23.19,23.05,22.91,14.14,14.00,13.96ppm。
the glass transition temperature of the azaspiroalkene represented by the formula (I-1) thus obtained was measured, and was 192 ℃ as shown in FIG. 1.
The hole mobility of the azaspiroene represented by the formula (I-1) thus prepared was measured to be 6.1X 10- 4cm2V-1s-1As shown in fig. 6.
The electric conductivity of the azaspiroene represented by the formula (I-1) thus prepared was measured, and found to be 304. mu.S cm-1As shown in fig. 7.
Example 2
Synthesizing TPTA 6H;
(1) will be provided with
(10g, 30mmol), 2-chloronaphthalen-1-amine (28.2g, 150mmol), palladium acetate (202mg,0.9mmol), (oxydi-2, 1-phenylene) bis (diphenylphosphine) (1.45g, 2.7mmol) and sodium tert-butoxide (14.4g, 150mmol) were added together with toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; purifying by a chromatographic column to obtain the compound 6.
(2) The compound 6(16.0g, 26.4mmol) obtained in (1) was added to N, N-dimethylacetamide together with palladium acetate (177mg, 0.79mmol), tri-tert-butylphosphine tetrafluoroborate (458mg, 1.6mmol), and potassium carbonate (18.2g,132.0 mmol); heating to 130 ℃ under stirring under the protection of argon, and reacting for 24 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; and recrystallizing and purifying to obtain the compound 7.
(3) Dissolving the compound 7 obtained in the step (2) in N, N-dimethylformamide and tetrahydrofuran in a volume ratio of 1: 1, adding iodoalkane and sodium hydride with the molar ratio of 1: 5: 6 to the compound 7 under stirring at room temperature, and reacting for 4 h; filtering the organic solvent to obtain a crude product; purifying by a chromatographic column to obtain the compound 8.
(4) Dissolving the compound 8(3.45g, 4.6mmol) obtained in the step (3) in dichloromethane, adding N-bromosuccinimide (2.46g, 13.8mmol) under the condition of ice-water bath with stirring, and reacting for 1 h; adding sodium sulfite saturated aqueous solution to quench the reaction, and filtering the organic solvent to obtain a compound 9.
(5) The compound 9(4.50g, 4.6mmol) obtained in (4) was reacted with
(3.6g, 22.8mmol), palladium acetate (30.8mg, 0.14mmol), (bis-2, 1-phenylene oxide) bis (diphenylphosphine) (221mg, 0.41mmol) and sodium tert-butoxide (2.2g, 22.8mmol) were added together to toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product 10; the resulting crude product 10, palladium acetate (103mg, 0.46mmol), tri-tert-butylphosphine tetrafluoroborate (265mg, 0.91mmol) and potassium carbonate (5.7g, 41.1mmol) were added together to N, N-dimethylacetamide; heating to 130 ℃ under stirring under the protection of argon, and reacting for 10 hours; standing and cooling to room temperature, adding tetrahydrofuran with the same volume, adding iodoalkane and sodium hydride with the molar ratio of 1: 5: 6 to the crude product 10, and reacting for 4 h; filtering the organic solvent to obtain a crude product of a final product; purifying with chromatographic column to obtain TPTA 6]H, the product of (A).
Performing structural characterization on the obtained target product azaspiroalkene shown in the formula (II-1) by adopting a nuclear magnetic resonance, mass spectrometry and an element analysis method, and performing high-resolution mass spectrometry on the result: 1146.6130. elemental analysis results: c, 81.61%; h, 6.83% and N, 7.38%.
The nmr characterization data is as follows:
1H NMR(400MHz,THF-d8)δ:9.08(d,J＝6.4Hz,3H),8.69(d,J＝6.5Hz,3H),8.52(d,J＝1.8Hz,3H),7.75–7.57(m,9H),7.15(dd,J＝7.1,1.9Hz,3H),5.29–5.00(m,3H),4.74–4.66(m,3H),4.58(s,9H),3.23(s,3H),1.05–0.89(m,3H),0.81–0.65(m,3H),0.66–0.47(m,6H),0.47–0.35(m,9H),0.30(t,J＝5.8Hz,9H),0.22–0.09ppm(m,3H).
13C NMR(400MHz,THF-d8)δ:155.07,144.42,137.42,135.70,133.10,125.37,125.33,125.28,124.57,124.46,124.08,123.23,117.95,116.14,115.67,110.41,110.00,106.17,57.82,55.43,53.18,35.44,32.22,27.02,22.89,14.22ppm.
the glass transition temperature of the azaspiroalkene of the formula (II-1) thus obtained was measured and found to be 195 ℃ as shown in FIG. 3.
The hole mobility of the azaspiroene represented by the formula (II-1) thus prepared was measured to be 2.9X 10- 3cm2V-1s-1As shown in fig. 6.
The electric conductivity of the azaspiroene represented by the formula (I-1) thus prepared was measured, and found to be 353. mu.S cm-1As shown in fig. 7.
Example 3
Synthesis of TBPC-161
Compared with the example 1, in the present example, the iodohexane in the step (3) is changed to iodomethane, the iodomethane in the step (5) is changed to iodomethane, and the rest of the reaction process, the reagent name and the reagent amount are consistent with those in the example 1.
The structural formula of the final product is shown as the following formula:
performing structural characterization on the obtained target product azaspiroalkene shown in the formula (I-2) by adopting a nuclear magnetic resonance, mass spectrometry and an element analysis method, and performing high-resolution mass spectrometry on the result: 1146.6126. elemental analysis results: c, 81.62%; h,6.86 percent, N,7.34 percent
1H NMR(500MHz,THF-d8)δ10.25(dd,J＝34.4,8.3Hz,2H),9.82(d,J＝8.1Hz,1H),8.86–8.78(m,3H),8.37–8.18(m,3H),8.06–7.88(m,3H),7.87–7.64(m,6H),7.31–7.22(m,3H),5.07–5.04(m,5H),4.21(dd,J＝39.7,24.3Hz,13H),3.94(s,3H),3.83(s,3H),2.20(ddt,J＝30.2,14.9,8.7Hz,7H),1.70–1.24(m,17H),0.96(td,J＝7.6,4.4Hz,9H).13C NMR(125MHz,THF-d8)155.79,155.77,155.55,144.33,143.48,143.33,142.67,142.28,142.02,137.29,137.20,137.03,136.67,136.60,130.98,130.84,130.67,130.65,130.37,130.14,128.88,127.10,127.05,125.44,125.34,124.85,124.43,124.32,124.20,123.81,122.12,122.08,121.93,121.79,121.33,121.31,116.87,116.44,115.19,115.10,114.64,114.48,113.98,113.84,111.75,111.60,111.24,110.25,110.23,105.45,104.67,56.61,56.44,56.21,47.36,47.13,42.83,42.17,42.10,32.89,32.86,32.82,31.25,31.19,30.99,30.94,30.87,30.84,27.80,27.74,23.91,23.88,14.74,14.71.ppm.
The glass transition temperature of the azaspiroalkene represented by the formula (I-2) thus obtained was measured, and found to be 155 ℃.
The hole mobility of the azaspiroene represented by the formula (I-2) thus prepared was measured, and found to be 6.3X 10- 5cm2V-1s-1。
The conductivity of the azaspiroene represented by the formula (I-2) thus prepared was measured, and found to be 185. mu.S cm-1。
Example 4
Synthesis of TBPC-116
In this example, compared with example 1, the iodohexane in step (3) was changed to methyl iodide, and the iodohexane in step (5) was changed to methyl iodide
Instead, it is changed into
The rest of the reaction process, the names of the reagents and the amounts of the reagents were the same as those in example 1.
The structural formula of the final product is shown as the following formula:
performing structural characterization on the obtained target product azaspiroalkene shown in the formula (I-2) by adopting a nuclear magnetic resonance, mass spectrometry and an element analysis method, and performing high-resolution mass spectrometry on the result: 1146.6114. elemental analysis results: c, 81.60%; h, 6.83% and N, 7.29%.
1H NMR(500MHz,THF-d8)δ10.21(dd,J＝31.2,8.3Hz,2H),9.98(d,J＝8.2Hz,0H),9.79(d,J＝8.1Hz,1H),9.03(dd,J＝13.0,8.5Hz,3H),8.29–8.16(m,3H),8.04–7.88(m,3H),7.84–7.74(m,3H),7.68(t,J＝7.8Hz,3H),7.31–7.21(m,3H),4.64–4.57(m,9H),4.56–4.21(m,7H),4.17(s,3H),3.93(s,3H),3.82(s,3H),2.02–1.96(m,7H),1.68–1.44(m,12H),1.29(s,3H),1.02ppm(dt,J＝18.1,6.6Hz,10H).
13C NMR(125MHz,THF-d8)δ155.21,155.17,155.01,144.31,143.34,143.25,142.50,142.14,141.98,138.63,137.86,137.70,137.60,137.42,137.22,130.97,130.84,130.67,130.65,130.39,128.77,126.97,126.92,125.50,125.42,124.93,124.87,124.78,124.42,124.02,123.77,122.33,121.99,121.89,121.76,121.64,116.68,116.63,116.22,115.77,115.68,115.38,114.95,114.47,113.97,113.87,111.56,111.47,110.69,109.87,109.83,105.82,105.70,104.91,42.79,42.12,42.08,36.30,35.45,35.25,35.13,33.28,33.23,33.14,33.10,30.83,30.52,30.50,28.20,27.40,27.37,27.22,24.10,24.00,23.86,14.89,14.84,14.76ppm。
The glass transition temperature of the azaspiroalkene represented by the formula (I-3) thus obtained was measured, and found to be 102 ℃.
The hole mobility of the azaspiroene represented by the formula (I-3) thus prepared was measured, and found to be 6.0X 10- 5cm2V-1s-1。
The electric conductivity of the azaspiroene represented by the formula (I-3) thus prepared was measured, and it was 168. mu.S cm-1。
Example 6 preparation of perovskite solar cell
Laser etched fluorine doped tin oxide (FTO) glass with cleaner, deionized water, acetone and ethanol in sequenceThe glass is cleaned by ultrasonic bath for 10 minutes. Thereafter, an ethanol solution of diisopropoxytitanium bis (acetylacetonate) (40mM) and acetylacetone (400mM) was deposited by spray pyrolysis on FTO glass preheated at 450 ℃ to form dense TiO2And (3) a layer. Previously prepared by dissolving anhydrous ethanol in a solvent of 1: 6 weight ratio dilution of commercially available TiO2Slurry (30NR-D) to produce TiO2And (3) slurry. Next, the TiO was spin coated at 4000rpm2Slurry for 20s to form mesoporous TiO of about 200nm2And (3) a layer. After curing in air at 100 ℃ for 10 minutes, it was sintered in a dry air stream at 450 ℃ for 30 minutes to remove all carbon components to give a mesoporous film. Spin-coating CsMAFA perovskite film by a two-step method, firstly performing the spin-coating for 10s at 2000 rpm; the next step was carried out at 6000rpm for 30 seconds. Note that 150 μ L of chlorobenzene was dropped on the substrate at a time of 15s before the end of the rotation. The deposited film was then annealed at 120 ℃ for 1 hour to produce a black perovskite phase. The perovskite precursor solution is prepared by mixing 1.3M PbI2、1.2M FAI，0.1M PbBr20.1M MABr and 0.07M CsI in a mixed solvent of DMSO and DMF (v: v, 1: 4). 40mM of formula (I-1) or formula (II-1), 20mM of BPTFSI, and 112mM of TBP were added to 1mL of chlorobenzene to prepare an HTM solution. The HTM solution was then deposited on the perovskite layer by dynamic spin coating by spinning at 4000rpm for 30 s. Finally, at 1X 10-4A gold layer of about 100nm thickness was thermally evaporated under vacuum of Pa to complete the manufacture of the cell. The perovskite solar cell has a structure as shown in FIG. 8, and the effective area of the cell is 0.258cm2。
Example 7 aging testing of perovskite solar cells
The packaged cells were stored in an 85 ℃ FD56 oven for long term thermal stability evaluation at an ambient relative humidity of 45% to 85%. And taking out the powder from the oven at certain intervals for measurement.
The illumination intensity is 100mW cm-2The voltage-current curve of the device is tested under simulated sunlight irradiation of AM1.5G, and the results are shown in FIG. 2 and FIG. 4. Fig. 2 is a voltage-current curve of the perovskite solar cell prepared in example 1 of the present invention before and after aging at 85 ℃ for thousands hours. Aging ofThe open-circuit voltage of the front cell was 1.135V and the short-circuit current density was 24.39mA cm-2The filling factor is 78.2 percent, and the photoelectric conversion efficiency is 21.6 percent; the open-circuit voltage of the battery after 85 ℃ thousands of hours of aging is 1.110V, and the short-circuit current density is 23.38mA cm-2The filling factor is 67.7%, the photoelectric conversion efficiency is 17.6%, and the photoelectric conversion efficiency retention rate of the device is 81%. FIG. 4 is a voltage-current curve of the perovskite solar cell prepared in example 2 of the present invention before and after aging at 85 ℃ for thousands hours. The open-circuit voltage of the cell before aging was 1.120V and the short-circuit current density was 24.41mA cm-2The fill factor is 77.6%, and the photoelectric conversion efficiency is 21.2%; the open-circuit voltage of the battery after 85 ℃ thousands of hours of aging is 1.105V, and the short-circuit current density is 22.81mA cm-2The filling factor is 69.2%, the photoelectric conversion efficiency is 17.5%, and the photoelectric conversion efficiency retention rate of the device is 82%.
Comparative example 1
A perovskite solar cell was prepared according to the procedure of example 6, taking commercially available spiro-OMeTAD as HTM, and the performance test was performed under the same conditions according to the procedure of example 7, and the results showed that: the open-circuit voltage of the cell before aging was 1.120V and the short-circuit current density was 24.50mA cm-2The filling factor is 76.2 percent, and the photoelectric conversion efficiency is 20.9 percent; the open-circuit voltage of the cell after aging for 500 hours at 85 ℃ is 1.030V, and the short-circuit current density is 21.30mA cm-2The filling factor is 59.8%, the photoelectric conversion efficiency is 13.1%, and the photoelectric conversion efficiency retention rate of the device is 63%.
FIG. 2 is a voltage-current curve of a perovskite solar cell prepared in example 1 of the present invention before and after aging at 85 ℃ for thousands hours; fig. 5 is a voltage-current curve of the perovskite solar cell prepared in comparative example 1 at 85 ℃ before and after 500-hour aging.
The test result shows that the product of the invention is used as a hole transport layer of the perovskite solar cell, has the characteristics of high glass transition temperature, high conductivity and high mobility, and is far superior to the existing product or the existing technical scheme in the aspect of long-term stability at 85 ℃.
The above description of the embodiments is provided to aid in understanding the methods and core concepts of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (5)
1. An azaspiroalkene micromolecule perovskite solar cell hole transport material is characterized in that the structural general formula is shown as formula (I) or (II):
in the formula, R1、R2、R3Respectively C1-C6 alkyl.
2. The azaspiroene small molecule perovskite solar cell hole transport material as claimed in claim 1, characterized in that the structural general formula is as described in any one of the following formulas:
3. the preparation method of the azaspiroene small molecule perovskite solar cell hole transport material of the formula (I) in claim 1 is characterized in that the chemical reaction formula of the preparation method is as follows:
in the formula, R1、R2、R3Respectively C1-C6 alkyl;
the preparation process of the preparation method comprises the following steps:
(1) according to the mol ratio of 1: 5: 0.03: 0.09: 5, the mixture is mixed
1-chloronaphthalene-2-amine, palladium acetate, (oxydi-2, 1-phenylene) bis (diphenylphosphine) and sodium tert-butoxide are added together to toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; purifying by a chromatographic column to obtain a solid which is an intermediate product shown in a formula III;
(2) adding the intermediate product shown in the formula III, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and potassium carbonate into N, N-dimethylacetamide according to the mol ratio of 1: 0.15: 0.3: 9; heating to 130 ℃ under stirring under the protection of argon, and reacting for 24 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; recrystallizing and purifying to obtain a solid as an intermediate product shown in a formula IV;
(3) dissolving an intermediate product shown in a formula IV in a mixed solvent of N, N-dimethylformamide and tetrahydrofuran in a volume ratio of 1: 1; at room temperature, adding R with the molar ratio of 1: 5: 6 to the intermediate product shown in the formula IV while stirring1I and sodium hydride, and reacting for 4 hours; filtering the organic solvent to obtain a crude product; purifying by a chromatographic column to obtain a solid as an intermediate product shown in a formula V;
(4) taking an intermediate product shown in a formula V and N-bromosuccinimide according to a molar ratio of 1: 3, dissolving the intermediate product and the N-bromosuccinimide in dichloromethane, and reacting for 1h while stirring under the condition of ice water bath; adding a sodium sulfite saturated aqueous solution to quench the reaction, and filtering an organic solvent to obtain a solid which is an intermediate product shown in a formula VI;
(5) reacting an intermediate product of formula VI with
Palladium acetate, (oxydi-2, 1-phenylene) bis (diphenylphosphine) and sodium tert-butoxide are added together in a molar ratio of 1: 5: 0.03: 0.09: 5 to toluene; heating to 120 deg.C under argon protection while stirringReacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product A;
adding the crude product A, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and potassium carbonate into N, N-dimethylacetamide according to the molar ratio of 1: 0.15: 0.3: 9; heating to 130 ℃ under stirring under the protection of argon, and reacting for 10 hours; standing and cooling to room temperature, adding tetrahydrofuran with the same volume, and adding R with the molar ratio of the product crude material A being 1: 5: 62I and sodium hydride, and reacting for 4 hours; filtering the organic solvent to obtain a crude product of a final product; and purifying by a chromatographic column to obtain the azaspiroalkene micromolecule perovskite solar cell hole transport material shown in the formula I.
4. The preparation method of the azaspiroene small molecule perovskite solar cell hole transport material of the formula (II) in the claim 1 is characterized in that the chemical reaction formula of the preparation method is as follows:
in the formula, R1、R2、R3Respectively C1-C6 alkyl;
the preparation process of the preparation method comprises the following steps:
(1) according to the mol ratio of 1: 5: 0.03: 0.09: 5, the mixture is mixed
Adding 2-chloronaphthalene-1-amine, palladium acetate, (oxydi-2, 1-phenylene) bis (diphenylphosphine) and sodium tert-butoxide into toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; purifying by a chromatographic column to obtain a solid which is an intermediate product shown in a formula VII;
(2) adding an intermediate product shown in a formula VII, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and potassium carbonate into N, N-dimethylacetamide according to a molar ratio of 1: 0.15: 0.3: 9; heating to 130 ℃ under stirring under the protection of argon, and reacting for 24 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product; recrystallizing and purifying to obtain a solid which is an intermediate product shown in a formula VIII;
(3) dissolving an intermediate product shown in a formula VIII in a mixed solvent of N, N-dimethylformamide and tetrahydrofuran in a volume ratio of 1: 1; at room temperature, R is added with stirring and in a molar ratio of 1: 5: 6 with the intermediate product shown in the formula VIII1I and sodium hydride, and reacting for 4 hours; filtering the organic solvent to obtain a crude product; purifying by a chromatographic column to obtain a solid which is an intermediate product shown in a formula IX;
(4) taking an intermediate product shown in a formula IX and N-bromosuccinimide according to a molar ratio of 1: 3, dissolving the intermediate product and the N-bromosuccinimide in dichloromethane, and reacting for 1h under the condition of ice-water bath while stirring; adding a sodium sulfite saturated aqueous solution to quench the reaction, and filtering an organic solvent to obtain a solid which is an intermediate product shown in the formula X;
(5) reacting an intermediate product of formula X with
Palladium acetate, (oxydi-2, 1-phenylene) bis (diphenylphosphine) and sodium tert-butoxide are added together in a molar ratio of 1: 5: 0.03: 0.09: 5 to toluene; heating to 120 ℃ under stirring under the protection of argon, and reacting for 8 hours; standing and cooling to room temperature, and filtering an organic solvent to obtain a crude product B;
adding the obtained crude product B, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and potassium carbonate into N, N-dimethylacetamide according to the molar ratio of 1: 0.15: 0.3: 9; heating to 130 ℃ under stirring under the protection of argon, and reacting for 10 hours; standing and cooling to room temperature, adding tetrahydrofuran with the same volume, and adding R with the molar ratio of the R to the crude product B of 1: 5: 62I and sodium hydride, and reacting for 4 hours; filtering the organic solvent to obtain a crude product of a final product; and purifying by a chromatographic column to obtain the azaspiroalkene micromolecule perovskite solar cell hole transport material shown in the formula II.
5. The application method of the azaspiroene small molecule perovskite solar cell hole transport material as claimed in claim 1, characterized in thatThe method is characterized in that the method is used for preparing a hole transport layer for applying to a perovskite solar cell device; the perovskite solar cell device has a multilayer structure and sequentially comprises: FTO glass substrate/dense TiO2Layer/mesoporous TiO2Layer/perovskite layer/hole transport layer/metal electrode layer.
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