A polymer hole transport material and its preparation method and application

Abstract

The present invention discloses a polymer hole transport material and a preparation method and application thereof. The structural formula of the polymer hole transport material is shown in formula (I): Formula (I); The perovskite solar cell prepared from the polymer hole transport material of the present invention has a higher open circuit voltage and significantly improves the battery energy conversion efficiency.

Description

Technical Field

[0001] The invention belongs to the technical field of high molecular polymer materials, and in particular relates to a polymer hole transport material and a preparation method and application thereof. Background Art

[0002] As traditional non-renewable energy sources such as electricity, coal, and oil are frequently in short supply, energy issues are increasingly becoming a bottleneck restricting the economic development of the international community. Seeking and developing new energy sources that promote economic prosperity has gradually become the current social research direction for energy. Solar radiation energy is the most important source of energy on the earth, and because solar energy has the characteristics of being inexhaustible, clean, stable, and pollution-free, it has become a hot topic in the research of renewable resources.

[0003] Solar cells are devices that directly convert light energy into electrical energy through the photoelectric effect or photochemical effect. Among them, perovskite solar cells show excellent photoelectric performance and have become an important resource in photovoltaic materials. However, the energy conversion efficiency of existing perovskite solar cells is generally low. The hole transport layer of perovskite solar cells plays the role of extracting and transporting holes as a hole transport layer, which plays an important role in improving the energy conversion efficiency of perovskite solar cells.

[0004] Among them, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) is a common hole transport material with high efficiency and is widely used in the preparation of perovskite solar cells. However, PTAA as a hole transport material cannot effectively improve the open circuit voltage of perovskite solar cells. Summary of the invention

[0005] In view of the deficiencies in the above-mentioned prior art, a method for preparing a polymer hole transport material and application thereof are provided. The polymer hole transport material provided by the present invention is used to prepare a perovskite solar cell having a higher open circuit voltage, which has a significant effect on improving the energy conversion efficiency of the perovskite solar cell.

[0006] The object of the present invention is to provide a polymer hole transport material, the structural formula of the polymer hole transport material is shown in formula (I):

[0007]

[0008] Formula (I)

[0009] The number average molecular weight of the polymer hole transport material is 7000-54000 g / mol, and the PDI is 1.5-2.5.

[0010] Another object of the present invention is to provide a method for preparing a polymer hole transport material, comprising the following steps:

[0011] Under the action of pyridine carboxaldehyde palladium catalyst and auxiliary agent, dibromo-substituted triphenylamine compound and triphenylamine boric acid pinacol ester compound undergo polymerization reaction to obtain polymer hole transport material;

[0012] The structure of the pyridine carboxaldehyde palladium catalyst is shown in formula (II):

[0013]

[0014] Formula (II);

[0015] The structure of the dibromo-substituted triphenylamine compound is shown in formula (III):

[0016]

[0017] Formula (III);

[0018] The structure of the triphenylamine boric acid pinacol ester compound is shown in formula (IV):

[0019]

[0020] Formula (IV).

[0021] In some embodiments of the present invention, the molar ratio of the pyridine carboxaldehyde palladium catalyst, the dibromo-substituted triphenylamine compound and the triphenylamine boric acid pinacol ester compound is 0.01-0.09:1:1.

[0022] In some embodiments of the present invention, the polymerization reaction is carried out at a temperature of 80-120° C. and for a time of 12-24 hours.

[0023] In some embodiments of the present invention, the auxiliary agent includes a quaternary ammonium salt, an inorganic base, an organic phosphine and a solvent.

[0024] In some embodiments of the present invention, the quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide and methyltrialkylammonium chloride.

[0025] In some embodiments of the present invention, the molar ratio of the dibromo-substituted triphenylamine compound to the quaternary ammonium salt is 1:0.05-0.15.

[0026] In some embodiments of the present invention, the inorganic base is selected from at least one of potassium phosphate and potassium carbonate.

[0027] In some embodiments of the present invention, the molar ratio of the dibromo-substituted triphenylamine compound to the inorganic base is 1:2-10.

[0028] In some embodiments of the present invention, the organic phosphine is selected from tri(2-furyl)phosphine.

[0029] In some embodiments of the present invention, the molar ratio of the dibromo-substituted triphenylamine compound to the organic phosphine is 1:0.01-0.2.

[0030] In some embodiments of the present invention, the solvent is a mixed solvent of toluene and water.

[0031] In some embodiments of the present invention, the volume ratio of toluene to water is 1-10:1.

[0032] In some embodiments of the present invention, after the polymerization reaction is completed, a purification step is further included.

[0033] Another object of the present invention is to provide the use of the polymer hole transport material or the polymer hole transport material prepared by the preparation method of the polymer hole transport material in the preparation of perovskite solar cells.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The polymer hole transport material provided by the present invention is used to prepare a perovskite solar cell, which has a higher open circuit voltage and significantly improves the energy conversion efficiency of the perovskite solar cell; after long-term use, the battery energy conversion efficiency is still relatively high, and it can be stored for a long time in an atmospheric environment and maintain high stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the H NMR spectrum of the polymer hole transport material P1 prepared in Example 3.

[0037] Figure 2 This is the NMR carbon spectrum of the polymer hole transport material P1 prepared in Example 3. DETAILED DESCRIPTION

[0038] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0039] All raw materials of the present invention are conventionally commercially available.

[0040] The structure of the dibromo-substituted triphenylamine compound used in all embodiments of the present invention for preparing polymer hole transport materials is as follows:

[0041] ;

[0042] The structure of the triphenylamine boric acid pinacol ester compound used in all embodiments of the present invention for preparing polymer hole transport materials is as follows:

[0043] ;

[0044] The structures of the pyridine carboxaldehyde palladium catalysts used in all the embodiments and comparative examples of the present invention for preparing polymer hole transport materials are as follows:

[0045] .

[0046] Example 1

[0047] This embodiment provides a dibromo-substituted triphenylamine compound, and the preparation method thereof comprises the following steps:

[0048] 3,4,5-trimethoxyaniline (2mmol), 4-bromoiodobenzene (4.4mmol), potassium tert-butoxide (4mmol), and di(tri-tert-butyl)palladium (0.05mmol) were added to a clean 100 mL reaction bottle in sequence, and 40 mL of toluene was added as solvent. The reaction was refluxed at 110°C for 6 h. After the reaction was completed, the mixture was cooled to room temperature, the product was filtered, the filtrate was concentrated, separated by column chromatography, and dried to obtain a dibromo-substituted triphenylamine compound.

[0049] Example 2

[0050] This embodiment provides a triphenylamine boric acid pinacol ester compound, and the preparation method thereof comprises the following steps:

[0051] A dibromo-substituted triphenylamine compound (5 mmol), biboric acid pinacol ester (12 mmol), tri(2-furyl)phosphine (0.5 mmol), Pd(dppf)Cl2 (0.4 mmol), potassium carbonate (10 mmol), and 1,4-epoxyhexadecane (40 mL) were placed in a clean 100 mL reaction bottle, heated to 100 ° C and refluxed for 12 h; after the reaction was cooled, the product was filtered, the filtrate was concentrated, separated by column chromatography, and dried to obtain a triphenylamine biboric acid pinacol ester compound.

[0052] Example 3

[0053] This embodiment provides a polymer hole transport material P1, and the preparation method thereof comprises the following steps:

[0054] A dibromo-substituted triphenylamine compound (5 mmol), a triphenylamine-type pinacol borate ester compound (5 mmol), tri(2-furyl)phosphine (0.08 mmol), potassium carbonate (10 mmol) and tetrabutylammonium bromide (0.5 mmol) were placed in a clean 150 mL reaction bottle, 30 mL of toluene and 10 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.05 mmol) was added, heated to 100 ° C and the reaction was continued for 12 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P1.

[0055] The structural formula of the polymer hole transport material P1 is as follows:

[0056]

[0057] The number average molecular weight of the polymer hole transport material P1 is 7168 g / mol, and the PDI is 1.6.

[0058] Example 4

[0059] This embodiment provides a polymer hole transport material P2, and the preparation method thereof comprises the following steps:

[0060] A dibromo-substituted triphenylamine compound (5 mmol), a triphenylamine-type pinacol borate ester compound (5 mmol), tri(2-furyl)phosphine (0.38 mmol), potassium carbonate (24 mmol) and tetrabutylammonium bromide (0.58 mmol) were placed in a clean 150 mL reaction bottle, 40 mL of toluene and 20 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.15 mmol) was added, heated to 100 ° C and the reaction was continued for 18 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P2.

[0061] The structural formula of the polymer hole transport material P2 is as follows:

[0062]

[0063] The number average molecular weight of the polymer hole transport material P2 is 20267 g / mol, and the PDI is 1.7.

[0064] Example 5

[0065] This embodiment provides a polymer hole transport material P3, and the preparation method thereof comprises the following steps:

[0066] A dibromo-substituted triphenylamine compound (5 mmol), a triphenylamine-type pinacol borate ester compound (5 mmol), tri(2-furyl)phosphine (0.72 mmol), potassium carbonate (36 mmol) and tetrabutylammonium bromide (0.54 mmol) were placed in a clean 150 mL reaction bottle, 30 mL of toluene and 20 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.07 mmol) was added, heated to 80°C and the reaction was continued for 24 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P3.

[0067] The structural formula of the polymer hole transport material P3 is as follows:

[0068]

[0069] The number average molecular weight of the polymer hole transport material P3 is 10845 g / mol, and the PDI is 1.5.

[0070] Example 6

[0071] This embodiment provides a polymer hole transport material P4, and the preparation method thereof comprises the following steps:

[0072] A dibromo-substituted triphenylamine compound (7 mmol), a triphenylamine-type pinacol borate ester compound (7 mmol), tri(2-furyl)phosphine (0.07 mmol), potassium carbonate (14 mmol) and tetrabutylammonium bromide (0.35 mmol) were placed in a clean 150 mL reaction bottle, 80 mL of toluene and 20 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.35 mmol) was added, heated to 120° C. and the reaction was continued for 16 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P4.

[0073] The structural formula of the polymer hole transport material P4 is as follows:

[0074]

[0075] The number average molecular weight of the polymer hole transport material P4 is 41978 g / mol, and the PDI is 2.5.

[0076] Example 7

[0077] This embodiment provides a polymer hole transport material P5, and the preparation method thereof comprises the following steps:

[0078] A dibromo-substituted triphenylamine compound (5 mmol), a triphenylamine-type boric acid pinacol ester compound (5 mmol), tri(2-furyl)phosphine (0.25 mmol), potassium carbonate (28 mmol) and tetrabutylammonium bromide (0.34 mmol) were placed in a clean 150 mL reaction bottle, 50 mL of toluene and 10 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.25 mmol) was added, heated to 110° C. and the reaction was continued for 16 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P5.

[0079] The polymer hole transport material P5 has the following structure:

[0080]

[0081] The number average molecular weight of the polymer hole transport material P5 is 27431 g / mol, and the PDI is 2.1.

[0082] Example 8

[0083] This embodiment provides a polymer hole transport material P6, and the preparation method thereof comprises the following steps:

[0084] A dibromo-substituted triphenylamine compound (5 mmol), a triphenylamine-type boric acid pinacol ester compound (5 mmol), tri(2-furyl)phosphine (0.28 mmol), potassium carbonate (32 mmol) and tetrabutylammonium bromide (0.52 mmol) were placed in a clean 150 mL reaction bottle, 50 mL of toluene and 20 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.45 mmol) was added, heated to 100 ° C and the reaction was continued for 12 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P6.

[0085] The polymer hole transport material P6 has the following structure:

[0086]

[0087] The number average molecular weight of the polymer hole transport material P6 is 54000 g / mol, and the PDI is 1.7.

[0088] Example 9

[0089] This embodiment provides a polymer hole transport material P7, and the preparation method thereof comprises the following steps:

[0090] A dibromo-substituted triphenylamine compound (5 mmol), a triphenylamine-type boric acid pinacol ester compound (5 mmol), tri(2-furyl)phosphine (0.4 mmol), potassium carbonate (20 mmol) and tetrabutylammonium bromide (0.44 mmol) were placed in a clean 150 mL reaction bottle, 60 mL of toluene and 20 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.45 mmol) was added, heated to 80°C and the reaction was continued for 20 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P7.

[0091] The polymer hole transport material P7 has the following structure:

[0092]

[0093] The number average molecular weight of the polymer hole transport material P7 is 36632 g / mol, and the PDI is 2.0.

[0094] Example 10

[0095] This embodiment provides a polymer hole transport material P8, and the preparation method thereof comprises the following steps:

[0096] A dibromo-substituted triphenylamine compound (6 mmol), a triphenylamine-type boric acid pinacol ester compound (6 mmol), tri(2-furyl)phosphine (0.18 mmol), potassium carbonate (25 mmol) and tetrabutylammonium bromide (0.31 mmol) were placed in a clean 150 mL reaction bottle, 40 mL of toluene and 10 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.45 mmol) was added, heated to 100 ° C and the reaction was continued for 18 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P8.

[0097] The polymer hole transport material P8 has the following structure:

[0098]

[0099] The number average molecular weight of the polymer hole transport material P8 is 47682 g / mol, and the PDI is 1.8.

[0100] Comparative Example 1

[0101] This comparative example provides a polymer hole transport material P9, the preparation method of which comprises the following steps:

[0102] S1. Add 3,4,5-trimethylaniline (2mmol), 4-bromoiodobenzene (4.4mmol), potassium tert-butoxide (4mmol), and di(tri-tert-butyl)palladium (0.05mmol) into a clean 100 mL reaction bottle in sequence, add 40mL of toluene as solvent, reflux at 110°C for 6 h, cool to room temperature after the reaction, filter the product, concentrate the filtrate, separate by column chromatography, and dry to obtain compound A;

[0103] S2. Compound A (5 mmol), bipyraclostrobin (12 mmol), tri(2-furyl)phosphine (0.5 mmol), Pd(dppf)Cl2 (0.4 mmol), potassium carbonate (10 mmol), and 1,4-epoxyhexadecane (40 ml) were placed in a clean 100 mL reaction bottle, heated to 100 °C and refluxed for 12 h; after the reaction was cooled, the product was filtered, the filtrate was concentrated, separated by column chromatography, and dried to obtain compound B;

[0104] S3. Compound A (5 mmol), compound B (5 mmol), tri(2-furyl)phosphine (0.08 mmol), potassium carbonate (15 mmol) and tetrabutylammonium bromide (0.5 mmol) were placed in a clean 150 mL reaction bottle, 30 mL of toluene and 10 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.05 mmol) was added, and the mixture was heated to 100°C and the reaction was continued for 12 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the product was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P9;

[0105] The structural formula of the polymer hole transport material P9 is as follows:

[0106]

[0107] The number average molecular weight of the polymer hole transport material P9 is 13578 g / mol, and the PDI is 1.7.

[0108] Comparative Example 2

[0109] This comparative example provides a polymer hole transport material P10, and the preparation method thereof comprises the following steps:

[0110] S1. Add 3,4-dimethoxyaniline (2mmol), 4-bromoiodobenzene (4.4mmol), potassium tert-butoxide (4mmol), and di(tri-tert-butyl)palladium (0.05mmol) into a clean 100 mL reaction bottle in sequence, add 40mL of toluene as solvent, reflux at 110°C for 6 h, cool to room temperature after the reaction, filter the product, concentrate the filtrate, separate by column chromatography, and dry to obtain compound C;

[0111] S2. Compound C (5 mmol), bipyraclostrobin (12 mmol), tri(2-furyl)phosphine (0.5 mmol), Pd(dppf)Cl2 (0.4 mmol), potassium carbonate (10 mmol), and 1,4-epoxyhexadecane (40 mL) were placed in a clean 100 mL reaction bottle, heated to 100 °C and refluxed for 12 h; after the reaction was cooled, the product was filtered, the filtrate was concentrated, separated by column chromatography, and dried to obtain compound D;

[0112] S3. Compound C (5 mmol), compound D (5 mmol), tri(2-furyl)phosphine (0.08 mmol), potassium carbonate (10 mmol) and tetrabutylammonium bromide (0.5 mmol) were placed in a clean 150 mL reaction bottle, 30 mL of toluene and 10 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.05 mmol) was added, and the mixture was heated to 100°C and the reaction was continued for 12 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the product was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a polymer hole transport material P10;

[0113] The structural formula of the polymer hole transport material P10 is as follows:

[0114]

[0115] The number average molecular weight of the polymer hole transport material P10 is 11317 g / mol, and the PDI is 1.9.

[0116] Embodiment 11

[0117] This embodiment provides a pin-type perovskite solar cell, the specific cell structure is ITO / polymer hole transport material / perovskite active layer / PCBM / BCP / Ag, and the specific implementation steps are as follows:

[0118] (1) Cleaning of the transparent substrate layer: First, take out the ITO transparent conductive glass, tear off the plastic protective film on the surface, and first use detergent to gently wipe the surface oil and dirt, and then ultrasonically clean it in a 0.2wt% detergent aqueous solution, deionized water, and isopropanol for 15 minutes respectively. Finally, use nitrogen to blow dry the isopropanol on the ITO surface and put it in a box for later use.

[0119] (2) Deposition of hole transport layer: The polymer hole transport material of Example 3 was prepared into a 2.5 mg / mL precursor solution, the solvent was chlorobenzene, the cleaned ITO was first placed in an ultraviolet ozone cleaner for surface hydrophilic treatment, and then the precursor solution was sucked out with a pipette to evenly cover the ITO surface, and then coated on the ITO glass by scraping.

[0120] (3) Preparation of perovskite active layer: The FAPbI3 system perovskite precursor solution was aspirated with a pipette and evenly covered on the surface of the wetting layer. The perovskite active layer was formed by a combination of scraping and flash evaporation, and then annealed at 100°C on a hot stage for 30-60 min.

[0121] (5) Deposition of electron transport layer: 20 mg of PCBM was weighed and added with 1 mL of chlorobenzene to prepare a precursor solution of the electron transport layer, and the precursor solution of the electron transport layer was deposited on the surface of the perovskite active layer by blade coating.

[0122] (6) Deposition of hole blocking layer: 8 mg of BCP was weighed and 16 mL of isopropanol was added to prepare a precursor solution. The prepared precursor solution was then aspirated with a pipette and evenly covered on the surface of the hole blocking layer, and then deposited on the surface of the electron transport layer by scraping.

[0123] (7) Deposition of metal electrode layer: A 100 nm thick Ag film was thermally evaporated under high vacuum at an evaporation rate of 0.3 Å / s for 20 nm and then deposited on the surface of the hole blocking layer at 1 Å / s to a thickness of 100 nm.

[0124] Examples 12 to 18 and Comparative Examples 3 to 4

[0125] The present invention provides a pin-type perovskite solar cell, which is different from Example 11 in that the "polymer hole transport material of Example 3" mentioned in point (2) of Example 11 is replaced by "polymer hole transport materials of Examples 4 to 10 and Comparative Examples 1 to 2", respectively, to obtain pin-type perovskite solar cells of Examples 12 to 18 and Comparative Examples 3 to 4, respectively.

[0126] The performance of the pin-type perovskite solar cells of Examples 11 to 18 and Comparative Examples 3 to 4 was tested. The test method is as follows. The results are shown in Table 1.

[0127] (1) JV characteristic curve: The JV characteristic curve of the device was measured using a Keithley 2440 light source under a simulated AM1.5G spectrum.

[0128] The light intensity was calibrated using a solar simulator (Newport, 91160) from NREL using a standard silicon solar cell device. The effective measurement area was 0.07 cm 2 , under reverse and forward bias scans, the scan rate was 100mV / s and the bias range was from -0.2V to 1.2V.

[0129] Table 1. Performance of perovskite solar cells of Examples 11-18 and Comparative Examples 3-4.

[0130] sample Voc(V) <![CDATA[Jsc(mA / cm 2 )]]> FF(%) PCE(%) Embodiment 11 1.08 24.21 82.65 21.61 Example 12 1.1 24.91 81.74 22.40 Example 13 1.07 24.36 82.54 21.51 Embodiment 14 1.12 24.08 82.59 22.27 Embodiment 15 1.08 24.57 82.62 21.92 Example 16 1.06 23.96 82.34 20.91 Embodiment 17 1.05 24.01 80.13 20.20 Embodiment 18 1.08 24.23 82.68 21.64 Comparative Example 3 0.91 21.04 78.35 15.00 Comparative Example 4 0.95 24.15 76.27 17.50

[0131] As can be seen from Table 1, the polymer hole transport materials prepared in Examples 3 to 10 of the present invention are used to prepare perovskite solar cells, which can maintain a high variable open circuit voltage at a high short-circuit current density and fill factor, thereby significantly improving the energy conversion efficiency of the battery.

[0132] The unpackaged pin-type perovskite solar cells of Examples 11 to 18 and Comparative Examples 3 to 4 were stored in an atmospheric environment for 30 days and then subjected to performance tests. The results are shown in Table 2.

[0133] Table 2. Performance of perovskite solar cells of Examples 11-18 and Comparative Examples 3-4.

[0134] sample PCE(%) Embodiment 11 19.02 Example 12 20.37 Example 13 19.13 Embodiment 14 20.73 Embodiment 15 19.31 Example 16 18.94 Embodiment 17 19.22 Embodiment 18 19.69 Comparative Example 3 11.17 Comparative Example 4 14.21

[0135] It can be seen from Table 1 and Table 2 that the polymer hole transport materials prepared in Examples 3 to 10 of the present invention are used to prepare perovskite solar cells, which can maintain a relatively high variable open circuit voltage, thereby effectively improving the energy conversion efficiency of the battery, and can enable the perovskite solar cell to maintain a relatively high energy conversion efficiency during long-term use, so that the unpackaged perovskite solar cell can also maintain a relatively high stability in the atmospheric environment for a long time.

[0136] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that after reading the specification of this application, the technicians can still modify or replace the specific implementation mode of the present invention with equivalents, but these modifications or changes do not deviate from the scope of protection of the pending claims of the present application.

Claims

1. A polymer hole transport material, characterized in that: The structural formula of the polymer hole transport material is shown in formula (I): Formula (I) The number average molecular weight of the polymer hole transport material is 7000-54000 g / mol, and the PDI is 1.5-2.

5.

2. The method for preparing the polymer hole transport material according to claim 1, characterized in that: The steps include: Under the action of pyridine carboxaldehyde palladium catalyst and auxiliary agent, dibromo-substituted triphenylamine compound and triphenylamine boric acid pinacol ester compound undergo polymerization reaction to obtain polymer hole transport material; The structure of the pyridine carboxaldehyde palladium catalyst is shown in formula (II): Formula (II); The structure of the dibromo-substituted triphenylamine compound is shown in formula (III): Formula (III); The structure of the triphenylamine boric acid pinacol ester compound is shown in formula (IV): Formula (IV).

3. The method for preparing a polymer hole transport material according to claim 2, characterized in that: The molar ratio of the pyridine formaldehyde palladium catalyst, the dibromo-substituted triphenylamine compound and the triphenylamine boric acid pinacol ester compound is 0.01-0.09:1:

1.

4. The method for preparing a polymer hole transport material according to claim 2, characterized in that: The polymerization reaction is carried out at a temperature of 80 to 120° C. and for a time of 12 to 24 hours.

5. The method for preparing a polymer hole transport material according to claim 2, characterized in that: The auxiliary agent includes quaternary ammonium salt, inorganic base, organic phosphine and solvent.

6. The method for preparing a polymer hole transport material according to claim 5, characterized in that: The inorganic base is selected from at least one of potassium phosphate and potassium carbonate; The quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide and methyltrialkylammonium chloride; The organic phosphine is selected from tri(2-furyl)phosphine.

7. The method for preparing a polymer hole transport material according to claim 5, characterized in that: The molar ratio of the dibromo-substituted triphenylamine compound to the quaternary ammonium salt is 1:0.05-0.15; The molar ratio of the dibromo-substituted triphenylamine compound to the inorganic base is 1:2-10.

8. The method for preparing a polymer hole transport material according to claim 5, characterized in that: The molar ratio of the dibromo-substituted triphenylamine compound to the organic phosphine is 1:0.01-0.

2.

9. The method for preparing a polymer hole transport material according to claim 8, characterized in that: The solvent is a mixed solvent of toluene and water, and the volume ratio of toluene to water is 1-10:

1.

10. Use of the polymer hole transport material according to claim 1 or the polymer hole transport material prepared by the preparation method of the polymer hole transport material according to any one of claims 2 to 8 in the preparation of perovskite solar cells.

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