A phenyl pentyl oxide copolymer and its preparation method and application

Abstract

The present invention discloses a phenyl epoxypentane copolymer and a preparation method and application thereof. The structural formula of the phenyl epoxypentane copolymer is shown in formula (I): #imgabs0# In formula (I), the ratio of x to y is 80-97:3-20; the phenyl epoxypentane copolymer of the present invention is used to prepare a perovskite solar cell, and the prepared perovskite solar cell has a high Voc value and FF value, so that a high PCE value can be obtained, which significantly improves the battery energy conversion efficiency. In addition, the perovskite solar cell prepared by the phenyl epoxypentane copolymer provided by the present invention can maintain a high battery energy conversion efficiency during long-term use, and can maintain high stability in an atmospheric environment for a long time.

Description

Technical Field

[0001] The invention belongs to the technical field of organic polymer copolymers, and in particular relates to a phenyl pentyl oxide copolymer and a preparation method and application thereof. Background Art

[0002] As a renewable energy source, solar energy is one of the important energy sources to meet the growing energy demand worldwide. Solar cells are devices that directly convert light energy into electrical energy through the photoelectric effect or photochemical reaction. They are the technical basis for the widespread application of solar photovoltaic power generation. Among them, perovskite solar cells have attracted worldwide attention and become a very promising new photovoltaic device.

[0003] In recent years, perovskite solar cells have developed rapidly, but there are still common problems such as difficulty in improving cell conversion efficiency and poor stability. Studies have shown that introducing a hole transport material into perovskite solar cells can effectively improve the output voltage, fill factor, and short-circuit current density of perovskite solar cells, thereby effectively improving the cell energy conversion efficiency.

[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, due to the strong hydrophobicity of PTAA, the perovskite precursor solution has a poor spreading effect on its surface, so the performance of perovskite solar cells prepared by the coating method is very unstable, and it is impossible to ensure a stable high open circuit voltage and fill factor, and the long-term stability is poor. Summary of the invention

[0005] In view of the deficiencies in the above-mentioned prior art, the present invention provides a phenyl epoxy pentane copolymer, by introducing an alkoxy group into the phenyl side chain of the phenyl epoxy pentane copolymer, the wettability of the copolymer is improved, the interlayer interaction is enhanced, and the phenyl epoxy pentane copolymer of the present invention is a random copolymer, so that the phenyl epoxy pentane copolymer has good solubility and crystallinity, optimizes the energy level, absorption spectrum and coplanarity of the phenyl epoxy pentane copolymer, and applies the phenyl epoxy pentane copolymer to the preparation of perovskite solar cells, so that the prepared perovskite solar cell has a higher Voc value and FF value, so that a high PCE value can be obtained, and the battery energy conversion efficiency is significantly improved. In addition, the perovskite solar cell prepared by the phenyl epoxy pentane copolymer provided by the present invention can maintain a higher battery energy conversion efficiency during long-term use, and can maintain a higher stability in an atmospheric environment for a long time.

[0006] The object of the present invention is to provide a phenyl pentyl oxide copolymer, the structural formula of the phenyl pentyl oxide copolymer is shown in formula (I):

[0007]

[0008] Formula (I)

[0009] Among them, the ratio of x to y is 80~97:3~20.

[0010] Preferably, the ratio of x to y is 80-85:15-20.

[0011] Preferably, the number average molecular weight of the phenyl pentane oxide copolymer is 10000-18000 g / mol, and the PDI is 1.5-2.5.

[0012] Another object of the present invention is to provide a method for preparing the phenyl pentyl oxide copolymer, comprising the following steps:

[0013] Under the action of palladium catalyst and auxiliary agent, the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound undergo polymerization reaction to obtain a phenyl epoxypentane copolymer;

[0014] The structural formula of the palladium catalyst is shown in formula (II):

[0015]

[0016] Formula (II)

[0017] Among them, R 1 , R 2 , R 3 are independently selected from hydrogen or methyl formate, and R 1 , R 2 , R 3 Not at the same time hydrogen;

[0018] The structural formula of the dibromo-substituted triphenylamine compound is as follows: ) as shown:

[0019]

[0020] Mode( )

[0021] The epoxypentane boric acid pinacol ester compound is shown in formula (IV):

[0022]

[0023] Formula (IV)

[0024] The triphenylamine boric acid pinacol ester compound is shown in formula (V):

[0025]

[0026] Formula (V)

[0027] Preferably, the molar ratio of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound, and the triphenylamine boric acid pinacol ester compound is 1-2:1-4:1-4.

[0028] Preferably, the total molar ratio of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound to the molar ratio of the palladium catalyst is 1:0.001-0.02;

[0029] Preferably, the polymerization reaction temperature is 80-120°C.

[0030] Preferably, the polymerization reaction time is 12 to 36 hours.

[0031] Preferably, the reaction further comprises an inorganic base, an organic phosphine, a quaternary ammonium salt and a solvent.

[0032] Preferably, the inorganic base includes at least one of potassium phosphate and potassium carbonate.

[0033] Preferably, the organic phosphine includes at least one of tri(2-furyl)phosphine and tributylphosphine.

[0034] Preferably, the quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide and methyltrialkylammonium chloride.

[0035] Preferably, the ratio of the total mole of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound to the mole of the inorganic base is 1-1.5:1-1.5.

[0036] Preferably, the ratio of the total mole of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound to the mole of the organic phosphine is 2-4:1.

[0037] Preferably, the total molar ratio of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound to the molar ratio of the quaternary ammonium salt is 1:0.01-0.2.

[0038] Preferably, the solvent is a mixture of toluene and water, and the volume ratio of toluene to water is 2~10:1~2.

[0039] Another object of the present invention is to provide the use of the phenyl oxirane copolymer or the phenyl oxirane copolymer prepared by the preparation method of the phenyl oxirane copolymer in the preparation of perovskite solar cells.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] (1) The phenyl pentane oxide copolymer provided by the present invention is used to prepare a perovskite solar cell. The prepared perovskite solar cell has a higher Voc value and FF value, thereby obtaining a high PCE value, which significantly improves the energy conversion efficiency of the cell.

[0042] (2) The perovskite solar cell prepared by the phenyl oxirane copolymer provided by the present invention can maintain a high battery energy conversion efficiency during long-term use, and can maintain a high stability in the atmospheric environment for a long time. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is the H NMR spectrum of the phenyl pentyl oxide copolymer prepared in Example 4.

[0044] Figure 2 This is the NMR carbon spectrum of the phenyl pentane oxide copolymer prepared in Example 4. DETAILED DESCRIPTION

[0045] 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.

[0046] All raw materials of the present invention can be obtained through commercial channels.

[0047] The structure of the dibromo-substituted triphenylamine compound used in all embodiments of the present invention for preparing phenyl pentylene oxide copolymers is as follows:

[0048] ;

[0049] The structure of the epoxypentane boric acid pinacol ester compound used in all embodiments of the present invention for preparing phenyl epoxypentane copolymers is as follows:

[0050] ;

[0051] The structure of the triphenylamine boric acid pinacol ester compound used in all embodiments of the present invention for preparing phenyl pentane oxide copolymers is as follows:

[0052] .

[0053] Example 1

[0054] This embodiment provides a dibromo-substituted triphenylamine compound, and the preparation method thereof comprises the following steps:

[0055] 2,4,6-aniline (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.

[0056] Example 2

[0057] This embodiment provides a triphenylamine boric acid pinacol ester compound, and the preparation method thereof comprises the following steps:

[0058] Dibromo-substituted triphenylamine compound (5 mmol), biboric acid pinacol ester (12 mmol), tri(2-furyl)phosphine (0.5 mmol), Pd(dppf)Cl 2 (0.4mmol), potassium carbonate (10mmol), and 1,4-epoxyhexadecane (40mL) were placed in a clean 100mL reaction bottle, heated to 100°C and refluxed for 12 hours; after the reaction was cooled, the product was filtered, the filtrate was concentrated, separated by column chromatography, and dried to obtain a triphenylamine boric acid pinacol ester compound.

[0059] Example 3

[0060] This embodiment provides an epoxypentane boric acid pinacol ester compound, and the preparation method thereof comprises the following steps:

[0061] 2-(3,5-dibromophenyl)-1,3-dioxolane (5 mmol), biboric acid pinacol ester (12 mmol), tri(2-furyl)phosphine (0.5 mmol), Pd(dppf)Cl 2 (0.4mmol), potassium carbonate (10mmol), and 1,4-epoxyhexadecane (40mL) were placed in a clean 100mL reaction bottle, heated to 100°C and refluxed for 12 hours; after the reaction was cooled, the product was filtered, the filtrate was concentrated, separated by column chromatography, and dried to obtain an epoxypentane boric acid pinacol ester compound.

[0062] Example 4

[0063] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0064] A dibromo-substituted triphenylamine compound (3.2 mmol), an epoxypentane boric acid pinacol ester compound (3.2 mmol), a triphenylamine type boric acid pinacol ester compound (3.2 mmol), tri(2-furyl)phosphine (2.4 mmol), potassium phosphate (9.6 mmol) and methyltrialkylammonium chloride (1.9 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; a palladium catalyst (0.09 mmol) was added, and the mixture was heated to 100° C. and reacted for 24 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 65%; the PDI of the phenyl epoxypentane copolymer was 2.5, and the number average molecular weight was 15803 g / mol;

[0065] The structure of the palladium catalyst is shown below:

[0066] ;

[0067] The structure of the phenyl pentane oxide copolymer is shown below:

[0068]

[0069] Among them, x=80mmol%, y=20mmol%.

[0070] Example 5

[0071] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0072] A dibromo-substituted triphenylamine compound (3.6 mmol), an epoxypentane boric acid pinacol ester compound (3.6 mmol), a triphenylamine type boric acid pinacol ester compound (3.6 mmol), tri(2-furyl)phosphine (5.4 mmol), potassium phosphate (11 mmol) and methyltrialkylammonium chloride (1.2 mmol) were placed in a clean 150 mL reaction bottle, 60 mL of toluene and 15 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; a palladium catalyst (0.02 mmol) was added, and the mixture was heated to 80° C. and reacted for 36 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 55%; the PDI of the phenyl epoxypentane copolymer was 2.2, and the number average molecular weight was 15613 g / mol;

[0073] The structure of the palladium catalyst is shown below:

[0074] ;

[0075] The structure of the phenyl pentane oxide copolymer is shown below:

[0076]

[0077] Among them, x=88mmol%, y=12mmol%.

[0078] Example 6

[0079] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0080] A dibromo-substituted triphenylamine compound (4 mmol), an epoxypentane boronic acid pinacol ester compound (4 mmol), a triphenylamine boronic acid pinacol ester compound (4 mmol), tri(2-furyl)phosphine (4.8 mmol), potassium phosphate (12 mmol) and methyltrialkylammonium chloride (0.96 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; a palladium catalyst (0.07 mmol) was added, and the mixture was heated to 90° C. and reacted for 30 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 53%; the PDI of the phenyl epoxypentane copolymer was 2.0, and the number average molecular weight was 10800 g / mol;

[0081] The structure of the palladium catalyst is shown below:

[0082] ;

[0083] The structure of the phenyl pentane oxide copolymer is shown below:

[0084]

[0085] Among them, x=97mmol%, y=3mmol%.

[0086] Example 7

[0087] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0088] A dibromo-substituted triphenylamine compound (5 mmol), an epoxypentane boric acid pinacol ester compound (5 mmol), a triphenylamine type boric acid pinacol ester compound (5 mmol), tri(2-furyl)phosphine (4.3 mmol), potassium phosphate (16.5 mmol) and methyltrialkylammonium chloride (0.6 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; a palladium catalyst (0.12 mmol) was added, and the mixture was heated to 100° C. and reacted for 18 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 56%; the PDI of the phenyl epoxypentane copolymer was 2.3, and the number average molecular weight was 13228 g / mol;

[0089] The structure of the palladium catalyst is shown below:

[0090] ;

[0091] The structure of the phenyl pentane oxide copolymer is shown below:

[0092]

[0093] Among them, x=89mmol%, y=11mmol%.

[0094] Example 8

[0095] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0096] A dibromo-substituted triphenylamine compound (3.6 mmol), an epoxypentane boric acid pinacol ester compound (3.6 mmol), a triphenylamine type boric acid pinacol ester compound (3.6 mmol), tri(2-furyl)phosphine (2.7 mmol), potassium phosphate (12 mmol) and methyltrialkylammonium chloride (1.6 mmol) were placed in a clean 150 mL reaction bottle, 70 mL of toluene and 20 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; a palladium catalyst (0.08 mmol) was added, and the mixture was heated to 100° C. and reacted for 20 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 59%; the PDI of the phenyl epoxypentane copolymer was 2.4, and the number average molecular weight was 17115 g / mol;

[0097] The structure of the palladium catalyst is shown below:

[0098] ;

[0099] The structure of the phenyl pentane oxide copolymer is shown below:

[0100]

[0101] Among them, x=95mmol%, y=5mmol%.

[0102] Example 9

[0103] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0104] A dibromo-substituted triphenylamine compound (5.2 mmol), an epoxypentane boronic acid pinacol ester compound (5.2 mmol), a triphenylamine boronic acid pinacol ester compound (5.2 mmol), tri(2-furyl)phosphine (4.4 mmol), potassium phosphate (16 mmol) and methyltrialkylammonium chloride (0.8 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; a palladium catalyst (0.16 mmol) was added, and the mixture was heated to 110° C. and reacted for 16 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 58%; the PDI of the phenyl epoxypentane copolymer was 2.1, and the number average molecular weight was 15853 g / mol;

[0105] The structure of the palladium catalyst is shown below:

[0106] ;

[0107] The structure of the phenyl pentane oxide copolymer is shown below:

[0108]

[0109] Among them, x=91mmol%, y=9mmol%.

[0110] Example 10

[0111] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0112] A dibromo-substituted triphenylamine compound (4.8 mmol), an epoxypentane boronic acid pinacol ester compound (4.8 mmol), a triphenylamine boronic acid pinacol ester compound (4.8 mmol), tri(2-furyl)phosphine (5.8 mmol), potassium phosphate (15 mmol) and methyltrialkylammonium chloride (1.0 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; a palladium catalyst (0.07 mmol) was added, and the mixture was heated to 120° C. and reacted for 12 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 57%; the PDI of the phenyl epoxypentane copolymer was 2.2, and the number average molecular weight was 13268 g / mol;

[0113] The structure of the palladium catalyst is shown below:

[0114] ;

[0115] The structure of the phenyl pentane oxide copolymer is shown below:

[0116]

[0117] Among them, x=85mmol%, y=15mmol%.

[0118] Embodiment 11

[0119] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0120] A dibromo-substituted triphenylamine compound (5.5 mmol), an epoxypentane boric acid pinacol ester compound (5.5 mmol), a triphenylamine type boric acid pinacol ester compound (5.5 mmol), tri(2-furyl)phosphine (4.2 mmol), potassium phosphate (18 mmol) and methyltrialkylammonium chloride (0.16 mmol) were placed in a clean 150 mL reaction bottle, 40 mL of toluene and 30 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; a palladium catalyst (0.02 mmol) was added, and the mixture was heated to 80° C. and reacted for 32 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 54%; the PDI of the phenyl epoxypentane copolymer was 2.5, and the number average molecular weight was 15917 g / mol;

[0121] The structure of the palladium catalyst is shown below:

[0122] ;

[0123] The structure of the phenyl pentane oxide copolymer is shown below:

[0124]

[0125] Among them, x=92mmol%, y=8mmol%.

[0126] Example 12

[0127] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0128] A dibromo-substituted triphenylamine compound (4.2 mmol), an epoxypentane boric acid pinacol ester compound (4.2 mmol), a triphenylamine type boric acid pinacol ester compound (4.2 mmol), tri(2-furyl)phosphine (5.0 mmol), potassium phosphate (15 mmol) and methyltrialkylammonium chloride (0.5 mmol) were placed in a clean 150 mL reaction bottle, 50 mL of toluene and 5 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; a palladium catalyst (0.04 mmol) was added, and the mixture was heated to 90° C. and reacted for 24 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 56%; the PDI of the phenyl epoxypentane copolymer was 2.3, and the number average molecular weight was 13760 g / mol;

[0129] The structure of the palladium catalyst is shown below:

[0130] ;

[0131] The structure of the phenyl pentane oxide copolymer is shown below:

[0132]

[0133] Among them, x=90mmol%, y=10mmol%.

[0134] Embodiment 13

[0135] This embodiment provides a phenyl pentane oxide copolymer, and the preparation method thereof comprises the following steps:

[0136] A dibromo-substituted triphenylamine compound (3.5 mmol), an epoxypentane boric acid pinacol ester compound (3.5 mmol), a triphenylamine type boric acid pinacol ester compound (3.5 mmol), tri(2-furyl)phosphine (7 mmol), potassium phosphate (16 mmol) and methyltrialkylammonium chloride (0.52 mmol) were placed in a clean 150 mL reaction bottle, 75 mL of toluene and 15 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; a palladium catalyst (0.2 mmol) was added, and the mixture was heated to 100° C. and reacted for 18 hours; after the reaction was cooled to room temperature, methanol was added to the product for precipitation, and the mixture was washed with water, washed with alcohol, extracted with n-hexane, and dried to obtain a phenyl epoxypentane copolymer with a yield of 57%; the PDI of the phenyl epoxypentane copolymer was 2.4, and the number average molecular weight was 16331 g / mol;

[0137] The structure of the palladium catalyst is shown below:

[0138] ;

[0139] The structure of the phenyl pentane oxide copolymer is shown below:

[0140]

[0141] Among them, x=84mmol%, y=16mmol%.

[0142] Comparative Example 1

[0143] This comparative example provides a poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], the preparation method of which comprises the following steps:

[0144] 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;

[0145] 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;

[0146] 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 carboxaldehyde 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 poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine];

[0147] The structural formula of the pyridine carboxaldehyde palladium catalyst is as follows:

[0148] ;

[0149] The structural formula of the poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] is as follows:

[0150]

[0151] The number average molecular weight of the poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] is 8345 g / mol, and the PDI is 2.5.

[0152] Embodiment 14

[0153] This embodiment provides a pin-type perovskite solar cell, the specific cell structure is ITO / phenyl pentane oxide copolymer / perovskite active layer / PCBM / BCP / Ag, and the specific implementation steps are as follows:

[0154] (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.

[0155] (2) Deposition of hole transport layer: The phenyl pentyl oxide copolymer of Example 4 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.

[0156] (3) Preparation of perovskite active layer: FAPbI 3The system perovskite precursor solution (1000 rpm / min, 3s; 5000rpm / min, 30s, 100μL chlorobenzene was added as anti-solvent at 21s) was sucked out with a pipette and evenly covered on the surface of the wetting layer. The perovskite active layer was formed by a combination of scraping + flash evaporation, and then annealed at 100°C on a hot stage for 30~60min.

[0157] (4) 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 scraping.

[0158] (5) 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.

[0159] (6) 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.

[0160] Embodiment 15

[0161] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 5" to obtain the pin-type perovskite solar cell of Embodiment 15.

[0162] Example 16

[0163] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 6", thereby obtaining the pin-type perovskite solar cell of Embodiment 16.

[0164] Embodiment 17

[0165] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 6", thereby obtaining the pin-type perovskite solar cell of Embodiment 17.

[0166] Embodiment 18

[0167] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 6", thereby obtaining the pin-type perovskite solar cell of Embodiment 18.

[0168] Embodiment 19

[0169] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 6", thereby obtaining the pin-type perovskite solar cell of Embodiment 19.

[0170] Embodiment 20

[0171] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 6", thereby obtaining the pin-type perovskite solar cell of Embodiment 20.

[0172] Embodiment 21

[0173] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 6" to obtain the pin-type perovskite solar cell of Embodiment 21.

[0174] Embodiment 22

[0175] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 6", thereby obtaining the pin-type perovskite solar cell of Embodiment 22.

[0176] Embodiment 23

[0177] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 14 in that the "phenyl oxirane copolymer of Embodiment 4" in step (2) of Embodiment 14 is replaced with "phenyl oxirane copolymer of Embodiment 6", thereby obtaining the pin-type perovskite solar cell of Embodiment 23.

[0178] Comparative Example 2

[0179] This comparative example provides a pin-type perovskite solar cell, which differs from Example 14 in that the "phenyl oxirane copolymer of Example 4" in step (2) of Example 14 is replaced with "poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] of Comparative Example 1" to obtain the pin-type perovskite solar cell of Comparative Example 2.

[0180] The performance of the pin-type perovskite solar cells of Examples 14 to 23 and Comparative Example 2 was tested. The test method is as follows, and the results are shown in Table 1.

[0181] (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.

[0182] 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.

[0183] Table 1. Performance of perovskite solar cells of Examples 14 to 23 and Comparative Example 2.

[0184] sample Voc(V) <![CDATA[Jsc(mA / cm 2 )]]> FF(%) PCE(%) Embodiment 14 0.98 23.74 82.59 19.21 Embodiment 15 1.01 24.31 82.62 20.29 Example 16 0.96 24.37 79.84 18.68 Embodiment 17 1.02 23.93 81.13 19.80 Embodiment 18 0.94 24.06 80.79 18.27 Embodiment 19 0.95 24.18 81.90 18.81 Embodiment 20 0.97 23.86 81.68 18.90 Embodiment 21 0.93 23.98 81.35 18.14 Embodiment 22 0.91 23.91 83.27 18.11 Embodiment 23 1.03 23.89 82.08 20.20 Comparative Example 2 0.81 21.46 78.31 13.61

[0185] As can be seen from Table 1, the phenyl oxirane copolymers prepared in Examples 4 to 13 of the present invention have higher Voc values ​​and FF values ​​when used to prepare perovskite solar cells, thereby obtaining a high PCE value.

[0186] The unpackaged pin-type perovskite solar cells of Examples 14 to 23 and Comparative Example 2 were stored in an atmospheric environment for 30 days and then subjected to performance testing. The results are shown in Table 2.

[0187] Table 2. Performance of perovskite solar cells of Examples 14 to 23 and Comparative Example 2.

[0188] sample PCE(%) Embodiment 14 19.02 Embodiment 15 19.39 Example 16 18.52 Embodiment 17 18.54 Embodiment 18 17.98 Embodiment 19 18.36 Embodiment 20 18.59 Embodiment 21 17.87 Embodiment 22 17.98 Embodiment 23 19.31 Comparative Example 2 11.62

[0189] The phenyl pentane oxide copolymers prepared in Examples 4 to 13 of the present invention are used to prepare perovskite solar cells, which can enable the perovskite solar cells to maintain a high energy conversion efficiency during long-term use, thereby enabling unpackaged perovskite solar cells to maintain a high stability in the atmospheric environment for a long time.

[0190] 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 phenyl pentyl oxide copolymer, characterized in that: The structural formula of the phenyl pentylene oxide copolymer is shown in formula (I): Formula (I) Among them, the ratio of x to y is 80~97:3~20.

2. The phenyl pentane oxide copolymer according to claim 1, characterized in that The ratio of x to y is 80~85:15~20.

3. The phenyl pentane oxide copolymer according to claim 1, characterized in that The number average molecular weight of the phenyl pentylene oxide copolymer is 10000-18000 g / mol, and the PDI is 1.5-2.

5.

4. The method for preparing the phenyl pentane oxide copolymer according to any one of claims 1 to 3, characterized in that: The steps include: Under the action of palladium catalyst and auxiliary agent, the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound undergo polymerization reaction to obtain a phenyl epoxypentane copolymer; The structural formula of the palladium catalyst is shown in formula (II): Formula (II) wherein R1, R2, and R3 are independently selected from hydrogen or methyl formate, and R1, R2, and R3 are not hydrogen at the same time; The structural formula of the dibromo-substituted triphenylamine compound is as follows: ) as shown: Mode( ) The epoxypentane boric acid pinacol ester compound is shown in formula (IV): Formula (IV) The triphenylamine boric acid pinacol ester compound is shown in formula (V): Formula (V).

5. The method for preparing the phenyl pentane oxide copolymer according to claim 4, characterized in that: The molar ratio of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound, and the triphenylamine boric acid pinacol ester compound is 1-2:1-4:1-4; and / or, the ratio of the total mole of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound to the mole of the palladium catalyst is 1:0.001-0.02; And / or, the polymerization reaction temperature is 80-120° C., and the time is 12-36 hours.

6. The method for preparing the phenyl pentane oxide copolymer according to claim 4, characterized in that: The reaction further includes an inorganic base, an organic phosphine, a quaternary ammonium salt and a solvent.

7. The method for preparing the phenyl pentane oxide copolymer according to claim 6, characterized in that: The inorganic base includes at least one of potassium phosphate and potassium carbonate; And / or, the organic phosphine includes at least one of tri(2-furyl)phosphine and tributylphosphine; And / or, the quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide and methyltrialkylammonium chloride.

8. The method for preparing the phenyl pentane oxide copolymer according to claim 6, characterized in that: The ratio of the total mole of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound to the mole of the inorganic base is 1-1.5:1-1.5; and / or, the ratio of the total mole of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound to the mole of the organic phosphine is 2-4:1; And / or, the ratio of the total mole of the dibromo-substituted triphenylamine compound, the epoxypentane boric acid pinacol ester compound and the triphenylamine boric acid pinacol ester compound to the mole of the quaternary ammonium salt is 1:0.01-0.

2.

9. The method for preparing the phenyl pentane oxide copolymer according to claim 6, characterized in that: The solvent is a mixture of toluene and water, and the volume ratio of toluene to water is 2-10:1-2.

10. Use of the phenyl pentyl oxide copolymer prepared by the preparation method of the phenyl pentyl oxide copolymer according to any one of claims 1 to 3 or the phenyl pentyl oxide copolymer according to any one of claims 4 to 9 in the preparation of perovskite solar cells.

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