CN114315856B - Doping-free hole transport material containing phenazine dithiophene and preparation method and application thereof - Google Patents
Doping-free hole transport material containing phenazine dithiophene and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a phenazine bithiophene-containing doping-free hole transport material, a preparation method thereof and application thereof in a perovskite solar cell. The hole transport material takes phenazine dithiophene as a molecular core, and the electron-withdrawing property of the hole transport material can effectively reduce the HOMO energy level of hole molecules and improve the open-circuit voltage of a battery device; meanwhile, the rigid planarization molecular configuration of the material obviously enhances the pi-pi accumulation effect among molecules and improves the hole transmission performance. The invention has simple synthetic route and low cost, and the synthesized material has high photo-thermal stability. The perovskite solar cell can be applied to the perovskite solar cell, the photoelectric conversion efficiency of 19.07 percent can be obtained without doping, and the perovskite solar cell has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a phenazine bithiophene-containing doping-free hole transport material and a preparation method and application thereof.
Background
As a new generation of photovoltaic technology, perovskite solar cells have the advantages of easily modulated materials, high efficiency, simple preparation process, low cost and the like, and have attracted attention in the field of solar cells in recent years. The efficiency is improved from 3.9% (J.Am.Chen.Soc, 2009,131,6050.) to 25.6% (Nature, 2021,592,381.). The hole transport layer is used as an important component of PSCs, plays a role in collecting holes of the perovskite absorption layer and transporting the holes to a counter electrode, and can effectively inhibit the recombination of device interface electrons, thereby playing a crucial role in the efficiency and stability of the battery. Hole transport materials are largely divided into two broad classes, organic and inorganic. The selectable range of the inorganic hole transport material is narrow, and the photoelectric conversion efficiency of a corresponding device is relatively low; the organic cavity material has flexible molecular design and easy regulation of spectrum and energy level. Currently, the most widely and efficiently used hole transport material in perovskite solar cells is Spiro-OMeTAD. However, the synthesis and preparation cost of the Spiro-OMeTAD molecule is high, and the perovskite solar cell prepared by the Spiro-OMeTAD molecule needs to be doped, so that the preparation cost of the device is increased, the stability of the device is reduced, and the wide-range application of commercialization of the perovskite solar cell is limited. Therefore, the research and development of novel doping-free organic hole transport materials are effective means for further improving the efficiency and stability of the cell, and become a research hotspot in the field of the current perovskite solar cell.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a phenazine bithiophene-containing doping-free hole transport material, a preparation method thereof and application thereof in a perovskite solar cell.
In order to achieve the purpose, the invention designs a non-doping hole transport material containing phenazine dithiophene, which takes phenazine dithiophene with rigid planarization and electron-withdrawing characteristics as a molecular core and methoxyl triphenylamine as a peripheral modifying group, and the material has chemical structural formulas shown in formulas (5) and (8):
the invention further improves the scheme as follows:
the preparation method of the compound of the formula (5) comprises the following steps:
reacting a compound shown in a formula (1) with a compound shown in a formula (2) to generate a compound shown in a formula (3); the compound shown in the formula (3) and the compound shown in the formula (4) are subjected to Suzuki coupling reaction to generate the compound shown in the formula (5), namely, the doping-free hole transport material containing phenazine dithiophene, and the chemical reaction equation is as follows:
further, the preparation method comprises the following specific steps:
step one, reacting a compound shown as a formula (1) with a compound shown as a formula (2) in mixed solvents of ethanol and acetic acid under the protection of argon to generate a compound shown as a formula (3), wherein the compound is used in an amount of the substance, and the compound shown as the formula (1): compound of formula (2 =1: 1-2, the reaction temperature is 100-120 ℃, and the reaction time is 4-12 h;
and step two, enabling the compound shown in the formula (3) to perform Suzuki coupling reaction with the compound shown in the formula (4) in a tetrahydrofuran solvent under the protection of argon under the action of tetratriphenyl phosphorus palladium and potassium carbonate to generate a compound shown in the formula (5), namely, a doping-free hole transport material containing phenazine bithiophene, wherein the dosage of the compound is calculated by the amount of a substance, and the compound shown in the formula (3): a compound of formula (4): palladium tetratriphenylphosphine: potassium carbonate =1:4 to 8: 0.02-0.1: 4 to 10 ℃, the reaction temperature is 25 to 80 ℃, and the reaction time is 6 to 24 hours.
The invention has the further improved scheme that:
the preparation method of the compound of the formula (8) comprises the following steps:
reacting a compound of formula (1) with a compound of formula (6) to produce a compound of formula (7); the compound shown in the formula (7) and the compound shown in the formula (4) are subjected to Suzuki coupling reaction to generate the compound shown in the formula (8), namely, the doping-free hole transport material containing phenazine dithiophene, and the chemical reaction equation is as follows:
further, the preparation method comprises the following specific steps:
step one, reacting a compound shown as a formula (1) with a compound shown as a formula (6) in mixed solvents of ethanol and acetic acid under the protection of argon to generate a compound shown as a formula (7), wherein the compound is used in an amount of the substance, and the compound shown as the formula (1): compound of formula (6 =1: 1-2, the reaction temperature is 100-120 ℃, and the reaction time is 4-12 h;
and step two, enabling the compound shown in the formula (7) to perform Suzuki coupling reaction with the compound shown in the formula (4) in a tetrahydrofuran solvent under the protection of argon under the action of tetratriphenyl phosphorus palladium and potassium carbonate to generate a compound shown in the formula (8), namely, a doping-free hole transport material containing phenazine bithiophene, wherein the dosage of the compound is calculated by the amount of a substance, and the compound shown in the formula (7): a compound of formula (4): palladium tetrakistriphenylphosphine: potassium carbonate =1:4 to 8:0.02 to 0.1:4 to 10 ℃, the reaction temperature is 25 to 80 ℃, and the reaction time is 6 to 24 hours.
The invention has the further improvement scheme that:
the phenazine bithiophene-containing doping-free hole transport material is applied to the perovskite solar cell.
Compared with the prior art, the invention has the beneficial effects that:
according to the non-doping hole transport material containing phenazine dithiophene, provided by the invention, phenazine dithiophene is taken as a molecular core, and the electron-withdrawing property of the material can effectively reduce the HOMO energy level of hole molecules and improve the open-circuit voltage of a battery device; meanwhile, the rigid planarization molecular configuration of the material obviously enhances the pi-pi stacking effect among molecules, and can endow the hole transport material with high hole migration performance and high photo-thermal stability. The invention has simple synthetic route and low preparation cost, the synthesized material does not need to be doped with lithium salt, cobalt salt, tert-butylpyridine and other materials, the photoelectric conversion efficiency of more than 19 percent can be obtained when the material is applied to the perovskite solar cell, and the invention has high-efficiency stability and wide application prospect.
Drawings
FIG. 1 is a normalized graph of the UV-visible absorption spectrum and the fluorescence emission spectrum of the phenazine-containing bithiophene doping-free hole transport material prepared in examples 1 and 2 dissolved in a dichloromethane solution.
FIG. 2 is a differential pulse voltammetry curve for the phenazine-containing dithiophene doping-free hole transport materials prepared in examples 1 and 2.
FIG. 3 is a thermogram of the non-doped hole transporting material containing phenazine dithiophene prepared in examples 1 and 2.
FIG. 4 is a hydrogen spectrum of the non-doping hole-transporting material (5) containing phenazine dithiophene prepared in example 1.
FIG. 5 is a carbon spectrum of the non-doping hole-transporting material (5) containing phenazine dithiophene prepared in example 1.
FIG. 6 shows the hydrogen spectrum of the non-doping hole-transporting material (8) containing phenazine dithiophene prepared in example 2.
FIG. 7 is a carbon spectrum of a non-doping hole-transporting material (8) containing phenazine dithiophene prepared in example 2.
Fig. 8 is an I-V curve of the perovskite solar cells prepared in examples 3 and 4.
Fig. 9 is a schematic structural view of the perovskite solar cell prepared in examples 3 and 4, wherein 1 is a metal electrode, 2 is a hole transport layer, 3 is a perovskite photoactive layer, 4 is an electron transport layer, and 5 is a conductive glass.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Synthesis of hole transport Material formula (5)
The synthetic route is as follows:
the material used in this example (1) was prepared according to the document Arroyave, f.a.; richard, c.a.; reynolds, J.R.org.Lett.2012,14, 6138-6141; raw material (4) according to the document Rakstys, k.; abate, A.; ibrahim Dar, m.; gao, p.; jankauskas, v.; jacobin, g.; kamarauskas, e.; kazim, s.; ahmad, s.; gratzel, m.; nazeeruddi, M.K.J.Am.chem.Soc.2015,137, 16172-16178; other reagents are commercially available.
Synthesis of a compound of formula (3):
under the protection of argon, 280mg of the starting material (1), 296mg of the starting material (2), 10mL of ethanol and 1mL of acetic acid were added to a 100mL single-neck round-bottom flask, and the mixture was heated to 100 ℃ and reacted under reflux for 6 hours. After the reaction solution was cooled to room temperature, suction filtration was carried out, and the filter cake was washed with ethanol 3 times to obtain 391mg of the compound represented by the formula (3) as a yellowish green solid with a yield of 87%. MDLAI for C 16 H 4 N 2 S 2 Br 4 (M + ):calcd for 607.651.found:601.664.
Synthesis of hole-transporting Material (5):
385mg of the compound represented by the formula (3), 2.18g of the compound represented by the formula (4), 75mg of palladium tetratriphenylphosphine, 1.3g of potassium carbonate (2 mol/L) and 15mL of tetrahydrofuran are sequentially added into a 100mL three-neck round-bottom flask under the protection of argon; heating the reaction system to 80 ℃, reacting for 8h, cooling to room temperature, and distilling under reduced pressure to remove the solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane = 10/1-1/2) to yield 571mg of organic hole transport material (5) as a yellow solid with a yield of 60%. 1 H NMR(400MHz,CDCl 3 ):δ8.30(s,2H),7.95(s,2H),7.86(d,J＝8.4Hz,4H),7.58(d,J＝8.4Hz,4H),7.21(d,J＝8.8Hz,8H),7.16-7.13(m,12H),7.04(d,J＝8.4Hz,4H),6.90-6.85(m,16H),3.83(s,12H),3.76(m,12H). 13 C NMR(100MHz,CDCl 3 ):δ156.2,156.0,148.8,148.2,143.2,141.0,140.6,139.8,138.6,138.4,136.1,134.1,131.8,130.7,128.8,127.0,126.8,126.7,126.0,120.5,119.7,118.7,114.9,114.7,55.5,55.4.MALDI for C 96 H 76 N 6 O 8 S 2 (M + ):calcd for 1505.5200,found:1505.5196.
Example 2
Synthesis of hole transport Material formula (8)
The synthetic route is as follows:
synthesis of a compound of formula (7):
to a 100mL single neck round bottom flask, 280mg of starting material (1), 296mg of starting material (6), 10mL of ethanol, and 1mL of acetic acid were added under an argon blanket. The mixed solution is heated to 100 ℃ and is refluxed for 6 hours. And cooling the reaction liquid to room temperature, carrying out vacuum filtration, washing a filter cake for 3 times by using ethanol, and purifying to obtain 315mg of the compound shown as the formula (3), wherein the yellow green solid is obtained, and the yield is 70%. MALDI for C 16 H 4 Br 4 N 2 S 2 (M + ):calcd for 607.651,found:607.664.
Synthesis of hole-transporting Material (8):
385mg of the compound represented by the formula (3), 1.64g of the compound represented by the formula (4), 75mg of palladium tetratriphenylphosphine, 1.3g of potassium carbonate (2 mol/L) and 15mL of tetrahydrofuran are sequentially added into a 100mL three-neck round-bottom flask under the protection of argon; heating the reaction system to 80 ℃, reacting for 8h, cooling to room temperature, and distilling under reduced pressure to remove the solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane = 10/1-1/2) to obtain 523mg of a yellow solid, i.e., the hole transport material (8), in 55% yield. 1 H NMR(400MHz,CDCl 3 ):δ8.46(s,2H),8.29(s,2H),7.62(d,J＝8.6Hz,4h),7.16-7.09(m,20H),6.99(d,J＝8.4Hz,4H),6.90-6.85(m,20H),3.83(s,12H),3.81(s,12H). 13 C NMR(100MHz,CDCl 3 ):δ156.2,155.9,148.9,147.8,143.4,143.3,141.1,140.9,140.5,139.8,135.7,133.9,132.7,130.7,129.3,126.9126.8,126.7,125.8,120.1,129.8,118.5,114.9,114.8,55.5,55.4.MALDI for C 96 H 76 N 6 O 8 S 2 (M + ):calcd for 1505.5200,found:1505.5195.
Example 3
Using the organic hole transport material (5) prepared in example 1, according to the literature: cheng, y.; fu, q.; zong, x.; dong, y.; zhang, w.; wu, q.; liang, m.; sun, z.; liu, y.; xue, s.chemical Engineering Journal,2021,421,129823 a perovskite solar cell was prepared. Testing a light source: AM 1.5 (solar simulator-Oriel 91160-1000,300W), data collection used Keithley 2400 digital source table. The test results are shown in FIG. 8, open circuit voltage (V) of perovskite solar cell oc ) 1.109V, short-circuit current density (J) sc ) Is 22.86mAcm -2 The Fill Factor (FF) was 0.7522, and the photoelectric conversion efficiency was 19.07%.
Example 4
Using the organic hole transport material (8) prepared in example 2, according to the literature: cheng, y.; fu, q.; zong, x; dong, y.; zhang, w.; wu, q.; liang, m.; sun, z.; liu, y.; xue, s.chemical Engineering Journal,2021,421,129823 a perovskite solar cell was prepared. Testing a light source: AM 1.5 (solar simulator-Oriel 91160-1000,300W), data acquisition using Keithley 2400 digital Source Meter. The test results are shown in FIG. 8, open circuit voltage (V) of perovskite solar cell oc ) 1.025V, short-circuit current density (J) sc ) Is 13.63mAcm -2 The Fill Factor (FF) was 0.6128, and the photoelectric conversion efficiency was 8.56%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A non-doping hole transport material containing phenazine dithiophene is characterized by having a chemical structural formula shown in formula (5) or formula (8):
2. the method for preparing a non-doping hole transport material containing phenazine dithiophene according to claim 1, wherein the method for preparing the compound of formula (5) comprises the steps of:
reacting a compound shown in a formula (1) with a compound shown in a formula (2) to generate a compound shown in a formula (3); the compound shown in the formula (3) and the compound shown in the formula (4) are subjected to Suzuki coupling reaction to generate the compound shown in the formula (5), namely, the doping-free hole transport material containing phenazine dithiophene, and the chemical reaction equation is as follows:
3. the method for preparing the non-doping hole transport material containing phenazine dithiophene according to claim 2, which comprises the following steps:
step one, reacting a compound shown as a formula (1) with a compound shown as a formula (2) in mixed solvents of ethanol and acetic acid under the protection of argon to generate a compound shown as a formula (3), wherein the compound is used in an amount of the substance, and the compound shown as the formula (1): compound of formula (2 =1: 1-2, the reaction temperature is 100-120 ℃, and the reaction time is 4-12 h;
and step two, enabling the compound shown in the formula (3) to perform a Suzuki coupling reaction with the compound shown in the formula (4) in a tetrahydrofuran solvent under the protection of argon under the action of tetratriphenyl phosphorus palladium and potassium carbonate to generate a compound shown in the formula (5), namely a doping-free hole transport material based on phenazine dithiophene, wherein the dosage of the compound is calculated by the amount of a substance, and the compound shown in the formula (3): a compound of formula (4): palladium tetratriphenylphosphine: potassium carbonate =1:4 to 8:0.02 to 0.1:4 to 10, the reaction temperature is 25 to 80 ℃, and the reaction time is 6 to 24 hours.
4. The method for preparing a non-doping hole transport material containing phenazine dithiophene according to claim 1, wherein the method for preparing the compound of formula (8) comprises the steps of:
reacting a compound shown in a formula (1) with a compound shown in a formula (6) to generate a compound shown in a formula (7); the compound shown in the formula (7) and the compound shown in the formula (4) are subjected to Suzuki coupling reaction to generate the compound shown in the formula (8), namely, the doping-free hole transport material containing phenazine dithiophene, and the chemical reaction equation is as follows:
5. the method for preparing the non-doping hole transport material containing phenazine dithiophene according to claim 4, which comprises the following steps:
step one, reacting a compound shown as a formula (1) with a compound shown as a formula (6) in mixed solvents of ethanol and acetic acid under the protection of argon to generate a compound shown as a formula (7), wherein the compound is used in an amount of the substance, and the compound shown as the formula (1): compound of formula (6 =1: 1-2, the reaction temperature is 100-120 ℃, and the reaction time is 4-12 h;
and step two, enabling the compound shown in the formula (7) to perform a Suzuki coupling reaction with the compound shown in the formula (4) in a tetrahydrofuran solvent under the protection of argon under the action of tetratriphenyl phosphorus palladium and potassium carbonate to generate a compound shown in the formula (8), namely a doping-free hole transport material based on phenazine bithiophene, wherein the dosage of the compound is calculated by the amount of a substance, and the compound shown in the formula (7): a compound of formula (4): palladium tetratriphenylphosphine: potassium carbonate =1:4 to 8:0.02 to 0.1:4 to 10, the reaction temperature is 25 to 80 ℃, and the reaction time is 6 to 24 hours.
6. The method according to any one of claims 2 or 4, wherein the steps of the method further comprise a separation and purification step.
7. The use of a phenazine dithiophene-containing undoped hole-transporting material as claimed in claim 1 in perovskite solar cells.
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