A bis(4-phenyl)pyridinamine polymer and its preparation method and application
By using bis(4-phenyl)pyridineamine polymer as hole transport material in perovskite solar cells, the problems of low energy conversion efficiency and poor stability of perovskite solar cells are solved, and high battery energy conversion efficiency and long-term stability are achieved.
Patent Information
- Application Number
- CN202510001152.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-02
- Publication Date
- 2025-04-04
AI Technical Summary
The existing perovskite solar cells have problems of low energy conversion efficiency and poor stability, which limits their further development.
Bis(4-phenyl)pyridineamine polymer is used as hole transport material, and the trimethylbenzene unit is replaced by pyridine units to adjust wetting and promote interlayer anchoring, which is used to prepare perovskite solar cells.
The open circuit voltage, short circuit current density and filling factor of perovskite solar cells are significantly improved, thereby improving the energy conversion efficiency of the battery and maintaining high stability during long-term use and in the atmospheric environment.
Smart Images
Figure CN119751827A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of high molecular polymer materials, and in particular relates to a bis(4-phenyl)pyridinamine polymer and a preparation method and application thereof. Background Art
[0002] The extensive use of traditional non-renewable energy such as coal and oil will not only lead to the gradual depletion of available natural resources, but also cause serious damage to the natural environment. Therefore, seeking and developing green renewable new energy has become the research focus of various industries. Solar energy is the most important source of energy on the earth. It has the advantages of being inexhaustible, clean, stable, green and pollution-free. Therefore, solar energy has gradually become a dominant force 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 have a simple preparation process, low production cost, and excellent photoelectric performance, becoming an important resource in photovoltaic materials and expected to become an important clean energy source for mankind in the future. However, existing perovskite solar cells generally have problems such as low energy conversion efficiency and poor stability, which limits the further development of perovskite solar cells.
[0004] 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 and has poor long-term stability. Summary of the invention
[0005] In view of the deficiencies in the above-mentioned prior art, the present invention provides a bis(4-phenyl)pyridinamine polymer and a preparation method and application thereof. The present invention utilizes a pyridine unit to replace a trimethylbenzene unit to adjust wettability and promote interlayer anchoring, and is applied to the preparation of a perovskite solar cell. The obtained perovskite solar cell has a higher Jsc value, Voc value and FF value, thereby obtaining a higher PCE value; the perovskite solar cell can also maintain a higher cell conversion efficiency and a higher stability in an atmospheric environment after long-term use.
[0006] The object of the present invention is to provide a bis(4-phenyl)pyridinamine polymer, the structure of which is shown in formula (I):
[0007]
[0008] Formula (I);
[0009] The number average molecular weight of the bis(4-phenyl)pyridinamine polymer is 5000-18000 g / mol, and the PDI is 2-3.
[0010] Another object of the present invention is to provide a method for preparing a bis(4-phenyl)pyridinamine polymer, comprising the following steps:
[0011] Under the action of pyridine carboxaldehyde palladium catalyst and auxiliary agent, dibromo-substituted pyridine aniline compound and pyridine aniline type boric acid pinacol ester compound undergo polymerization reaction to obtain bis(4-phenyl)pyridine amine polymer;
[0012] The structure of the dibromo-substituted pyridine aniline compound is shown in formula (II):
[0013]
[0014] Formula (II);
[0015] The structure of the pyridine aniline boric acid pinacol ester compound is shown in formula (III):
[0016]
[0017] Formula (III);
[0018] The structural formula of the pyridine carboxaldehyde palladium catalyst 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 pyridine aniline compound and the aniline boric acid pinacol ester compound is 0.01-0.08:1:1-1.5.
[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 16-32 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 pyridine aniline compound to the quaternary ammonium salt is 1:0.01-0.5.
[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 pyridine aniline compound to the organic base is 1:2-8.
[0028] In some embodiments of the present invention, the organic phosphine is selected from tributylphosphine;
[0029] In some embodiments of the present invention, the molar ratio of the dibromo-substituted pyridine aniline compound to the organic phosphine is 1:0.01-0.4.
[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 a bis(4-phenyl)pyridinamine polymer or a bis(4-phenyl)pyridinamine polymer prepared by the preparation method of the bis(4-phenyl)pyridinamine polymer and use the bis(4-phenyl)pyridinamine polymer in the preparation of perovskite solar cells.
[0034] Compared with the prior art, the present invention has the following beneficial effects:
[0035] (1) The perovskite solar cell prepared by the polymer hole transport material provided by the present invention has a higher open circuit voltage, so that the prepared perovskite solar cell obtains a higher PCE value, which reflects that the perovskite solar cell prepared by the bis(4-phenyl)pyridinamine polymer provided by the present invention has a higher cell energy conversion efficiency.
[0036] (2) The perovskite solar cell prepared by the bis(4-phenyl)pyridinamine polymer provided by the present invention still maintains a high battery energy conversion efficiency after long-term use, and can be stored for a long time in the atmospheric environment and maintain high stability. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Figure 1 This is the hydrogen NMR spectrum of the bis(4-phenyl)pyridinamine polymer 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 can be purchased through commercial channels.
[0040] The structure of the dibromo-substituted pyridine aniline compound used in all embodiments of the bis(4-phenyl)pyridinamine polymer of the present invention is as follows:
[0041] ;
[0042] The structure of the pyridine aniline boric acid pinacol ester compound used in all embodiments of the present invention for preparing bis(4-phenyl)pyridinamine polymers is as follows:
[0043] ;
[0044] The structure of the pyridine carboxaldehyde palladium catalyst used in all embodiments of the present invention for preparing bis(4-phenyl)pyridinamine polymers is as follows:
[0045] .
[0046] Example 1
[0047] This embodiment provides a dibromo-substituted pyridine aniline compound, and the preparation method thereof comprises the following steps:
[0048] 3-Aminopyridine (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 dibromosubstituted pyridineaniline compound.
[0049] Example 2
[0050] This embodiment provides a pyridine aniline type boric acid pinacol ester compound, and the preparation method thereof comprises the following steps:
[0051] A dibromo-substituted pyridine aniline compound (5 mmol), diboric 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 pyridine aniline type boric acid pinacol ester compound.
[0052] Example 3
[0053] This embodiment provides a bis(4-phenyl)pyridinamine polymer, and the preparation method thereof comprises the following steps:
[0054] A dibromo-substituted pyridine aniline compound (4.6 mmol), a pyridine aniline-type pinacol borate ester compound (4.6 mmol), tributylphosphine (0.09 mmol), potassium phosphate (13.8 mmol) and tetrabutylammonium bromide (0.14 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; pyridine formaldehyde palladium catalyst (0.14 mmol) was added, heated to 100 ° 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 bis(4-phenyl)pyridinamine polymer with a yield of 65%; the PDI of the bis(4-phenyl)pyridinamine polymer was 2.5, and the number average molecular weight was 12640 g / mol.
[0055] The structural formula of the bis(4-phenyl)pyridinamine polymer is as follows:
[0056] .
[0057] Example 4
[0058] This embodiment provides a bis(4-phenyl)pyridinamine polymer, and the preparation method thereof comprises the following steps:
[0059] A dibromo-substituted pyridine aniline compound (5.3 mmol), a pyridine aniline type boric acid pinacol ester compound (5.3 mmol), tributylphosphine (0.05 mmol), potassium phosphate (10.6 mmol) and tetrabutylammonium bromide (0.42 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 (0.11 mmol) was added, heated to 100 ° 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 bis(4-phenyl)pyridinamine polymer with a yield of 61%; the PDI of the bis(4-phenyl)pyridinamine polymer was 2.1, and the number average molecular weight was 5992 g / mol.
[0060] The structural formula of the bis(4-phenyl)pyridinamine polymer is as follows:
[0061] .
[0062] Example 5
[0063] This embodiment provides a bis(4-phenyl)pyridinamine polymer, and the preparation method thereof comprises the following steps:
[0064] A dibromo-substituted pyridine aniline compound (5.5 mmol), a pyridine aniline type boric acid pinacol ester compound (5.5 mmol), tributylphosphine (0.05 mmol), potassium phosphate (22 mmol) and tetrabutylammonium bromide (0.44 mmol) were placed in a clean 150 mL reaction bottle, 30 mL of toluene and 30 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; pyridine formaldehyde palladium catalyst (0.06 mmol) was added, heated to 80 ° C and the reaction was continued for 32 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 bis(4-phenyl)pyridinamine polymer with a yield of 61%; the PDI of the bis(4-phenyl)pyridinamine polymer was 2.3, and the number average molecular weight was 17816 g / mol.
[0065] The structural formula of the bis(4-phenyl)pyridinamine polymer is as follows:
[0066] .
[0067] Example 6
[0068] This embodiment provides a bis(4-phenyl)pyridinamine polymer, and the preparation method thereof comprises the following steps:
[0069] A dibromo-substituted pyridine aniline compound (4.2 mmol), a pyridine aniline type boric acid pinacol ester compound (4.2 mmol), tributylphosphine (0.63 mmol), potassium phosphate (23 mmol) and tetrabutylammonium bromide (0.42 mmol) were placed in a clean 150 mL reaction bottle, 45 mL of toluene and 5 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 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 bis(4-phenyl)pyridinamine polymer with a yield of 60%; the PDI of the bis(4-phenyl)pyridinamine polymer was 2.8, and the number average molecular weight was 13012 g / mol.
[0070] The structural formula of the bis(4-phenyl)pyridinamine polymer is as follows:
[0071] .
[0072] Example 7
[0073] This embodiment provides a bis(4-phenyl)pyridinamine polymer, and the preparation method thereof comprises the following steps:
[0074] A dibromo-substituted pyridine aniline compound (3.8 mmol), a pyridine aniline type boric acid pinacol ester compound (3.8 mmol), tributylphosphine (0.76 mmol), potassium phosphate (11.4 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 (0.3 mmol) was added, heated to 110°C and the reaction was continued for 30 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 bis(4-phenyl)pyridinamine polymer with a yield of 60%; the PDI of the bis(4-phenyl)pyridinamine polymer was 2.0, and the number average molecular weight was 15201 g / mol.
[0075] The structural formula of the bis(4-phenyl)pyridinamine polymer is as follows:
[0076] .
[0077] Example 8
[0078] This embodiment provides a bis(4-phenyl)pyridinamine polymer, and the preparation method thereof comprises the following steps:
[0079] A dibromo-substituted pyridine aniline compound (5.2 mmol), a pyridine aniline type boric acid pinacol ester compound (5.2 mmol), tributylphosphine (0.42 mmol), potassium phosphate (20.8 mmol) and tetrabutylammonium bromide (0.05 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 (0.26 mmol) was added, heated to 90°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 bis(4-phenyl)pyridinamine polymer with a yield of 58%; the PDI of the bis(4-phenyl)pyridinamine polymer was 2.7, and the number average molecular weight was 8073 g / mol.
[0080] The structural formula of the bis(4-phenyl)pyridinamine polymer is as follows:
[0081] .
[0082] Example 9
[0083] This embodiment provides a bis(4-phenyl)pyridinamine polymer, and the preparation method thereof comprises the following steps:
[0084] A dibromo-substituted pyridine aniline compound (4.8 mmol), a pyridine aniline type boric acid pinacol ester compound (4.8 mmol), tributylphosphine (0.24 mmol), potassium phosphate (12 mmol) and tetrabutylammonium bromide (0.72 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 (0.09 mmol) was added, heated to 100°C and the reaction was continued for 22 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 bis(4-phenyl)pyridinamine polymer with a yield of 59%; the PDI of the bis(4-phenyl)pyridinamine polymer was 2.9, and the number average molecular weight was 9824 g / mol.
[0085] The structural formula of the bis(4-phenyl)pyridinamine polymer is as follows:
[0086] .
[0087] Example 10
[0088] This embodiment provides a bis(4-phenyl)pyridinamine polymer, and the preparation method thereof comprises the following steps:
[0089] A dibromo-substituted pyridine aniline compound (4.5 mmol), a pyridine aniline type boric acid pinacol ester compound (4.5 mmol), tributylphosphine (0.36 mmol), potassium phosphate (18 mmol) and tetrabutylammonium bromide (0.6 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; pyridine formaldehyde palladium catalyst (0.18 mmol) was added, heated to 90°C and the reaction was continued for 28 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 bis(4-phenyl)pyridinamine polymer with a yield of 62%; the PDI of the bis(4-phenyl)pyridinamine polymer was 2.4, and the number average molecular weight was 12290 g / mol.
[0090] The structural formula of the bis(4-phenyl)pyridinamine polymer is as follows:
[0091] .
[0092] Comparative Example 1
[0093] This comparative example provides a poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], the preparation method of which comprises the following steps:
[0094] 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;
[0095] 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;
[0096] 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];
[0097] The structural formula of the poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] is as follows:
[0098]
[0099] 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.
[0100] Embodiment 11
[0101] This embodiment provides a pin-type perovskite solar cell, the specific cell structure is ITO / bis(4-phenyl)pyridinamine polymer / perovskite active layer / PCBM / BCP / Ag, and the specific implementation steps are as follows:
[0102] (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 0.2 wt% detergent aqueous solution, deionized water, and isopropanol for 15 min respectively. Finally, use nitrogen to blow dry the isopropanol on the ITO surface and put it in a box for later use.
[0103] (2) Deposition of hole transport layer: The bis(4-phenyl)pyridinamine polymer of Example 3 was prepared into a 2.5 mg / mL precursor solution, and the solvent was a mixed solvent containing 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.
[0104] (3) Preparation of perovskite active layer: The FACsPbI3 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.
[0105] (4) Deposition of electron transport layer: Weigh 20 mg of PCBM and add 1 mL of chlorobenzene to prepare the precursor solution of the electron transport layer. The electron transport layer precursor solution is deposited on the surface of the perovskite active layer by scraping.
[0106] (5) Deposition of hole blocking layer: Weigh 8 mg of BCP and add 16 mL of isopropanol to prepare a precursor solution. Then, the prepared precursor solution is 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.
[0107] (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.
[0108] Example 12
[0109] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 11 in that the "bis(4-phenyl)pyridinamine polymer of Embodiment 3" mentioned in Embodiment 11 is replaced with "bis(4-phenyl)pyridinamine polymer of Embodiment 4" to obtain the pin-type perovskite solar cell of Embodiment 12.
[0110] Embodiment 13
[0111] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 11 in that the "bis(4-phenyl)pyridinamine polymer of Embodiment 3" mentioned in Embodiment 11 is replaced with "bis(4-phenyl)pyridinamine polymer of Embodiment 5" to obtain the pin-type perovskite solar cell of Embodiment 13.
[0112] Embodiment 14
[0113] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 11 in that the "bis(4-phenyl)pyridinamine polymer of Embodiment 3" mentioned in Embodiment 11 is replaced with "bis(4-phenyl)pyridinamine polymer of Embodiment 6" to obtain the pin-type perovskite solar cell of Embodiment 14.
[0114] Embodiment 15
[0115] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 11 in that the "bis(4-phenyl)pyridinylamine polymer of Embodiment 3" mentioned in Embodiment 11 is replaced with "bis(4-phenyl)pyridinylamine polymer of Embodiment 7" to obtain the pin-type perovskite solar cell of Embodiment 15.
[0116] Example 16
[0117] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 11 in that the "bis(4-phenyl)pyridinamine polymer of Embodiment 3" mentioned in Embodiment 11 is replaced with "bis(4-phenyl)pyridinamine polymer of Embodiment 8" to obtain the pin-type perovskite solar cell of Embodiment 16.
[0118] Embodiment 17
[0119] This embodiment provides a pin-type perovskite solar cell, which differs from Embodiment 11 in that the "bis(4-phenyl)pyridinamine polymer of Embodiment 3" mentioned in Embodiment 11 is replaced with "bis(4-phenyl)pyridinamine polymer of Embodiment 9" to obtain the pin-type perovskite solar cell of Embodiment 17.
[0120] Embodiment 18
[0121] This embodiment provides a pin-type perovskite solar cell, which differs from Example 11 in that the "bis(4-phenyl)pyridinamine polymer of Example 3" mentioned in Example 11 is replaced with "bis(4-phenyl)pyridinamine polymer of Example 10" to obtain the pin-type perovskite solar cell of Example 18.
[0122] Comparative Example 2
[0123] This comparative example provides a pin-type perovskite solar cell, which differs from Example 11 in that the "bis(4-phenyl)pyridinamine polymer of Example 3" mentioned in Example 11 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.
[0124] The performance of the pin-type perovskite solar cells of Examples 11 to 18 and Comparative Example 2 was tested. The test method is as follows, and the results are shown in Table 1.
[0125] (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.
[0126] 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.
[0127] Table 1. Performance of perovskite solar cells of Examples 11 to 18 and Comparative Example 2.
[0128] sample Voc(V) <![CDATA[Jsc(mA / cm 2 )]]> FF(%) PCE(%) Embodiment 11 0.92 24.74 83.59 19.02 Example 12 0.93 24.11 82.62 18.52 Embodiment 13 0.92 23.57 84.02 18.21 Embodiment 14 0.92 24.05 82.79 18.31 Embodiment 15 0.92 24.02 82.95 18.33 Example 16 0.93 23.86 82.68 18.14 Embodiment 17 0.92 23.58 82.35 18.05 Embodiment 18 0.91 23.84 83.27 18.19 Comparative Example 2 0.81 21.46 78.31 13.61
[0129] As can be seen from Table 1, the bis(4-phenyl)pyridinamine polymers 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.
[0130] The unpackaged pin-type perovskite solar cells of Examples 11 to 18 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.
[0131] Table 2. Performance of perovskite solar cells of Examples 11 to 18 and Comparative Example 2.
[0132] sample PCE(%) Embodiment 11 18.91 Example 12 18.14 Embodiment 13 18.03 Embodiment 14 18.22 Embodiment 15 18.16 Example 16 18.05 Embodiment 17 17.98 Embodiment 18 17.86 Comparative Example 2 11.62
[0133] As can be seen from Tables 1 and 2, the bis(4-phenyl)pyridinamine polymers obtained in Examples 3 to 10 of the present invention are used to prepare perovskite solar cells, and can maintain high Jsc values, Voc values, and FF values, thereby obtaining high PCE values, which reflects that the perovskite solar cells prepared by the bis(4-phenyl)pyridinamine polymers obtained in Examples 3 to 10 of the present invention have high battery energy conversion efficiency; the perovskite solar cells prepared by the bis(4-phenyl)pyridinamine polymers obtained in Examples 3 to 10 of the present invention can maintain high energy conversion efficiency during long-term use, and the unencapsulated perovskite solar cells can also maintain high stability in the atmospheric environment for a long time.
[0134] 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 bis(4-phenyl)pyridinamine polymer, characterized in that The structure of the bis(4-phenyl)pyridinamine polymer is shown in formula (I): Formula (I); The number average molecular weight of the bis(4-phenyl)pyridinamine polymer is 5000-18000 g / mol, and the PDI is 2-3.
2. The method for preparing the bis(4-phenyl)pyridinamine polymer according to claim 1, characterized in that: The steps include: Under the action of pyridine carboxaldehyde palladium catalyst and auxiliary agent, dibromo-substituted pyridine aniline compound and pyridine aniline type boric acid pinacol ester compound undergo polymerization reaction to obtain bis(4-phenyl)pyridine amine polymer; The structure of the dibromo-substituted pyridine aniline compound is shown in formula (II): Formula (II); The structure of the pyridine aniline boric acid pinacol ester compound is shown in formula (III): Formula (III); The structural formula of the pyridine carboxaldehyde palladium catalyst is shown in formula (IV): Formula (IV).
3. The method for preparing the bis(4-phenyl)pyridinamine polymer according to claim 2, characterized in that: The molar ratio of the pyridine carboxaldehyde palladium catalyst, the dibromo-substituted pyridine aniline compound and the aniline boric acid pinacol ester compound is 0.01-0.08:1:
1.
4. The method for preparing the bis(4-phenyl)pyridinamine polymer according to claim 2, characterized in that: The polymerization reaction temperature is 80-120° C. and the reaction time is 16-32 hours.
5. The method for preparing the bis(4-phenyl)pyridinamine polymer 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 the bis(4-phenyl)pyridinamine polymer according to claim 2, characterized in that: The quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide and methyltrialkylammonium chloride; The molar ratio of the dibromo-substituted pyridine aniline compound to the quaternary ammonium salt is 1:0.01-0.
5.
7. The method for preparing the bis(4-phenyl)pyridinamine polymer according to claim 2, characterized in that: The inorganic base is selected from at least one of potassium phosphate and potassium carbonate; The molar ratio of the dibromo-substituted pyridine aniline compound to the inorganic base is 1:2-8.
8. The method for preparing the bis(4-phenyl)pyridinamine polymer according to claim 2, characterized in that: The organic phosphine is selected from tributylphosphine; The molar ratio of the dibromo-substituted pyridine aniline compound to the organic phosphine is 1:0.01-0.
4.
9. The method for preparing the bis(4-phenyl)pyridinamine polymer according to claim 2, characterized in that: The solvent is a mixed solvent of toluene and water; The volume ratio of toluene to water is 1-10:
1.
10. Use of the bis(4-phenyl)pyridinamine polymer according to claim 1 or the bis(4-phenyl)pyridinamine polymer prepared by the preparation method of the bis(4-phenyl)pyridinamine polymer according to any one of claims 2 to 9 in the preparation of perovskite solar cells.