CN110229315B - Wide band gap copolymer receptor material based on perylene diimide and preparation method thereof - Google Patents
Wide band gap copolymer receptor material based on perylene diimide and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of solar cell materials, and discloses a perylene diimide-based wide band gap copolymer receptor material and a preparation method thereof, wherein the perylene diimide-based porphyrin and thiophene terpolymer organic solar cell receptor material is a random copolymer organic solar cell receptor material with a D-A structure, and the structural general formula is as shown in formula I; the random copolymer organic solar cell acceptor structure with the D-A structure can be further shown as formula II and formula III. The wide-bandgap copolymer acceptor material for perylene diimide provided by the invention has the advantages of simple molecular structure, fewer and simple preparation steps, cheap and easily-obtained synthetic raw materials, and good visible light absorption range and absorption intensity; the perylene diimide copolymer molecule of the invention can be processed by a solution method, has better sunlight capturing capability and thermal stability, and is an ideal material of an all-polymer organic solar cell.
Description
Technical Field
The invention belongs to the field of organic photovoltaics, and particularly relates to a perylene diimide-based wide-bandgap copolymer acceptor material and a preparation method thereof.
Background
The energy problem is the problem of life and death of all human beings at present, and solar energy is clean energy with sufficient reserves, the widest distribution and no pollution, is already utilized by plants in hundreds of millions of years, and is one of the most promising energy sources. The solar cell is a device for directly converting solar energy into electric energy, and is always the focus of research of scientists, however, the current disadvantages of high cost, complex process, large volume, poor aesthetic property and the like lead people to move towards developing novel solar cell materials which are cheap and easy to obtain, have high stability and have excellent photovoltaic effect.
The organic solar cell as the third generation solar cell has the characteristics of low cost, flexibility, translucency, roll-to-roll printing and the like, and has wide prospect. Among them, the all-polymer solar cell has more excellent light trapping ability and good charge transport ability than small molecules, and is the focus of research in the present stage.
At present, the problem of low energy conversion efficiency of all-polymer batteries still exists, and therefore, the development of high-efficiency polymer donor materials and polymer acceptor materials becomes a research focus in the field. In the research of polymer batteries, there are many polymer donor materials capable of realizing high efficiency, and therefore, the development of high-efficiency polymer acceptor materials matched with the donor materials is urgent.
In summary, the problems of the prior art are as follows:
in the prior art, the preparation material of the organic solar cell has poor solubility and does not have good absorption spectrum complementary performance.
And the existing preparation materials of the organic solar cell do not have higher molar extinction coefficient and broadened spectrum, and can not realize higher short-circuit current function. And the existing perylene diimide polymer acceptor has narrow light absorption range and is not beneficial to photocurrent generation.
Disclosure of Invention
Aiming at the problems in the prior art, a perylene diimide-based wide-bandgap copolymer acceptor material and a preparation method thereof. The polymer receptor and the narrow-bandgap polymer donor material can form good absorption spectrum complementation and energy level matching so as to meet the requirement of the all-polymer photovoltaic cell receptor material.
The other purpose of the invention is to use the obtained diimide-porphyrin-3, 3 '-difluoro-2, 2' bithiophene random copolymer for preparing the full polymer photovoltaic cell, and the electron donating and light absorbing characteristics of porphyrin are utilized to enable the absorption spectrum to be red-shifted, so that the short circuit current of the full polymer photovoltaic cell is improved.
In order to achieve the above purpose, the invention adopts the following technical solutions: the organic solar cell receptor material based on the terpolymer of perylene diimide, porphyrin and thiophene is a random copolymer organic solar cell receptor material with a D-A structure, and the structural general formula is shown as the following formula I:
wherein 0< x <1, and n is the number of repeating units.
Further, D is an electron donating unit, and the structural formula is selected from the following structures:
further, the structure of the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell receptor material is shown as a formula II:
the invention also aims to provide a preparation method of the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell receptor material with the structure shown in the formula II, wherein the preparation method comprises the following steps:
further, the synthesis of compound 2 includes: compound 1 was dissolved in 10mL of dichloromethane and Br was added2Stirring for 3 days; slowly introducing the solution into an excessive saturated sodium thiosulfate solution in an ice bath, stirring for one hour, then washing the mixture for multiple times by using deionized water, extracting by using dichloromethane, drying by using anhydrous sodium sulfate, filtering, spin-drying a solvent, and performing column chromatography to obtain red crystals 2 by using petroleum ether and dichloromethane (4:1) as a developing agent;
synthesis of Compound 3: 2-octyl dodecanol and 120mL of dichloromethane were added, followed by PCC and reaction at room temperature for 4 hours. Directly extracting with dichloromethane, washing with saturated saline water, repeating for many times, spin-drying, purifying by silica gel column chromatography, and eluting with dichloromethane to obtain transparent liquid product 3;
synthesis of Compound 4: adding freshly distilled pyrrole and formaldehyde, slowly injecting trifluoroacetic acid under the protection of argon, reacting for 15 minutes at room temperature, adding 70mL of 0.1mol/L NaOH aqueous solution, and continuing to react for half an hour. Distilling under reduced pressure to remove the residual pyrrole to obtain a crude product, purifying by silica gel column chromatography, wherein an eluent is dichloromethane and petroleum ether in a ratio of 1:3, spin-drying, and drying in vacuum to obtain a white solid product;
synthesis of Compound 5: adding the compound 1 and the compound 2 under the protection of argon, adding 1L of dichloromethane, slowly adding trifluoroacetic acid in the dark, and gradually deepening the reaction liquid from colorless to light red in the injection process; reacting at room temperature for 2 hours, adding DDQ, continuing to react for 1 hour, adding 5mL of triethylamine to terminate the reaction, spin-drying, and passing through a column by using an eluent petroleum ether and dichloromethane (4:1) to obtain a purple solid product;
synthesis of Compound 6: under the protection of argon, adding 50mL of dichloromethane and a compound 3, dropwise adding bromosuccinimide dissolved in 30mL of dichloromethane under ice bath, reacting for 6 hours, quenching with acetone, spin-drying, extracting with dichloromethane, washing with saturated salt water, repeating for multiple times, spin-drying, purifying by silica gel column chromatography, eluting with petroleum ether, namely dichloromethane which is 6:1, and spin-drying to obtain a mauve solid product;
synthesis of compound 7: add Compound 4 and 60mL of dichloromethane, 30mL of methanol, and then Zn (OAc)2·2H2O, stirring for 4 hours at room temperature; spin-drying, extracting with dichloromethane, washing with saturated saline water repeatedly, spin-drying, purifying with silica gel column chromatography, eluting with petroleum ether and dichloromethane of 1:1, and spin-drying to obtain purple solid product;
synthesis of copolymer P1: under argon protection, compound 2, compound 7, (3,3 ' -difluoro- [2,2 ' -bithiophene ] -5,5 ' -diyl) bistrimethyltin, tetrakis (triphenylphosphine) palladium, 0.3mL of DMF and 1.2mL of toluene were added to a 10mL reaction flask, and stirred at 110 ℃ for 24 hours; separating out a product at the bottom of the bottle, stopping the reaction, cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering, and drying in vacuum; and sequentially extracting by acetone and petroleum ether through a Soxhlet extractor to remove small molecules and other byproducts, and extracting the target polymer by using chromatographic pure chloroform.
Further, the structure of the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell receptor material is as shown in formula III:
the invention also aims to provide a preparation method of the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell receptor material with the structure shown in the formula III, wherein the preparation method comprises the following steps:
further, synthesis of copolymer P2: under argon protection, compound 2, compound 7, (3,3 ' -difluoro- [2,2 ' -bithiophene ] -5,5 ' -diyl) bistrimethyltin (82.3mg, 0.16mmol), tetrakis (triphenylphosphine) palladium (9mg, 0.0078mmol), 0.3mL DMF and 1.2mL toluene were added to a 10mL reaction flask, and stirred at 110 ℃ for 24 hours; separating out a product at the bottom of the bottle, stopping the reaction, cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering, and drying in vacuum; sequentially extracting and removing micromolecules and other byproducts by acetone and petroleum ether through a Soxhlet extractor, and extracting the target polymer by using chromatographic pure chloroform; spin-drying to obtain the product.
The invention also aims to provide an all-polymer solar cell prepared by utilizing the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell acceptor material.
In summary, the advantages and positive effects of the invention are:
the synthesized perylene diimide-based wide-bandgap random copolymer acceptor has good solubility, and can be dissolved in most organic solvents, such as dichloromethane, trichloromethane, tetrahydrofuran, dichlorobenzene and the like.
The synthesized perylene diimide-based wide band gap random copolymer acceptor material can have good absorption spectrum complementation with a narrow band gap polymer donor material.
The synthesized perylene diimide-based wide band gap random copolymer acceptor material has a high molar extinction coefficient and a broadened spectrum, and can realize a higher short-circuit current.
Drawings
FIG. 1 is a UV-Vis plot of a polymer provided by an example of the present invention.
FIG. 2 is a C-V plot of a polymer provided by an example of the present invention.
FIG. 3 is a cyclic voltammetry test chart of a polymer on a film provided by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the prior art, the preparation material of the organic solar cell has poor solubility and does not have good absorption spectrum complementary performance. And the existing preparation materials of the organic solar cell do not have higher molar extinction coefficient and broadened spectrum, and can not realize higher short-circuit current function.
In view of the problems of the prior art, the present invention provides a perylene diimide-based wide band gap copolymer acceptor material and a preparation method thereof, and the present invention is described in detail below with reference to specific embodiments.
The perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell receptor material provided by the embodiment of the invention is a random copolymer organic solar cell receptor material with a D-A structure, and the structural general formula is shown as the following formula I:
wherein 0< x <1, and n is the number of repeating units.
D is an electron donor unit, and the structural formula is selected from the following structures:
the invention is further described with reference to specific examples.
Example 1
The perylene diimide-porphyrin-3, 3 '-difluoro-2, 2' bithiophene random copolymer receptor with porphyrin content of 10% provided by the embodiment of the invention has the following synthetic route:
synthesis of Compound 2: compound 1(3.002g, 3.98mmol) was dissolved in 10mL of dichloromethane in a 250mL two-necked flask, and Br was added2(10ml, 195.17mmol), and stirred at room temperature for 3 days. The solution was slowly introduced into an excess of saturated sodium thiosulfate solution in an ice bath, stirred for one hour, and then the mixture was washed several times with deionized water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, the solvent was dried by spinning, and the red crystals 2(762mg, 21%) were obtained by column chromatography using petroleum ether dichloromethane (v: v ═ 4:1) as a developing agent.1H NMR(400MHz,Chloroform-d)δ9.49(d,J＝8.2Hz,2H),9.04–8.85(m,2H),8.78–8.52(m,2H),5.30–5.03(m,2H),2.23(m,4H),1.84(m,4H),1.49–1.06(m,32H),0.92–0.72(m,12H)。
Synthesis of Compound 3: a250 mL two-necked round-bottomed flask was charged with 2-octyldodecanol (12g,40.19mmol) and 120mL of methylene chloride, followed by addition of PCC (16.8g,60.276mmol), and reacted at room temperature for 4 hours. Direct dichloromethane extraction, washing with saturated brine, repeated several times, spin-drying, and purification by silica gel column chromatography eluting with dichloromethane afforded product 3(11.2g, 94%) as a clear liquid. 1H NMR (400MHz, CDCl3) δ 9.57(d, J ═ 3.2Hz,1H),2.25(m,1H),1.71-1.53(m,5H),1.5-1.35(m,3H),1.28(s,21H),0.90(t, J ═ 6.7Hz, 10H).
Synthesis of Compound 4: a250 mL two-neck flask was charged with freshly distilled pyrrole (39.89g,595.35mmol) and formaldehyde (5.5g,18.337mmol), trifluoroacetic acid (295.9mg,2.6mmol) was slowly injected under argon shield, and after 15 minutes at room temperature, 70mL of 0.1mol/L aqueous NaOH was added and the reaction was continued for half an hour. Distilling under reduced pressure to remove residual pyrrole to obtain crude product, purifying with silica gel column chromatography, eluting with dichloromethane and petroleum ether (1:3), spin drying, and vacuum drying to obtain white solid product 7.5 g. 1HNMR (400MHz, CDCl3): delta 7.86(s,2H),6.65(s,2H),6.14(s,2H),6.03(s,2H),3.98(s, 2H).
Synthesis of Compound 5: under the protection of argon, compound 1(4.4g,14.9mmol) and compound 2(2.1g,14.385mmol) were added to a 3L two-necked round-bottomed flask, 1L of dichloromethane was added thereto, and trifluoroacetic acid (0.63mL,14.4mmol) was slowly added in the absence of light, and the reaction solution changed from colorless to pale red during injection, gradually deepening. After 2 hours at room temperature, DDQ (4.86g,21.577mmol) was added and the reaction was continued for 1 hour and then 5mL triethylamine was added to stop the reaction, which was spin-dried and passed through a column eluting with petroleum ether, dichloromethane (4:1), to give 1.97g of a purple solid product in 32.5% yield. 1H NMR (400MHz, CDCl3) δ 10.22(s,2H),9.70(d, J ═ 32.2Hz,4H),9.42(d, J ═ 3.2Hz,4H),5.18(s,2H),3.02-2.84(M,4H),2.84-2.62(M,4H),1.55(s,10H),1.26(s,60H), -2.45(s,2H) 13CNMR (100MHz, CDCl3) δ 149.56,149.41,147.11,146.98,144.62,144.36,142.40,142.16,132.11,132.01,129.01,128.79,128.37,128.13,122.93,104.80,104.40,104.00,46.33,42.35,31.94,31.87,30.06,29.71,29.62,29.54,29.33,22.74,22.67,14.21,14.16.MALDI-TOF-MS 843.77(M +).
Synthesis of Compound 6: 50mL of dichloromethane and compound 3(945mg,1.113mmol) were added to a 250mL two-necked round bottom flask under argon protection, bromosuccinimide (NBS) (439mg,2.457mmol) dissolved in 30mL of dichloromethane was added dropwise under ice bath, the reaction was carried out for 6 hours, and acetone was quenched,spin-drying, extracting with dichloromethane, washing with saturated saline solution repeatedly, spin-drying, purifying with silica gel column chromatography, eluting with petroleum ether and dichloromethane (6:1), and spin-drying to obtain mauve solid product 924mg with 83% yield. 1H NMR (400MHz, CDCl3) δ 9.72-9.51(m,8H),5.03(s,2H),2.85(t, J ═ 13.7,4H),2.72-2.64(m,4H),1.51(m,8H),1.51-1.04(m,48H),0.88(m,12H), -2.45(s,2H).13C NMR(100MHz,CDCl3)δ150.29,152.24,149.72,149.45,147.72,147.46,133.28,132.92,131.86,131.65,131.02,130.80,130.13,129.60,126.35,125.15,105.04,104.50,103.95,47.22,42.63,32.00,31.82,29.97,29.84,29.77,22.76,22.62,14.18,14.07.MALDI-TOF-MS 1000.53(M+)。
Synthesis of compound 7: in a 250mL single neck flask, compound 4(735mg,0.734mmol) and 60mL of methylene chloride, 30mL of methanol are added, followed by Zn (OAc)22H2O (1.73g,7.34mmol), stirring at room temperature for 4H. Spin-drying, extracting with dichloromethane, washing with saturated saline solution repeatedly, spin-drying, purifying with silica gel column chromatography, eluting with petroleum ether and dichloromethane (1:1), and spin-drying to obtain purple solid product 656mg with yield of 84%.1H NMR(400MHz,CDCl3)δ9.86-9.45(m,8H),5.18(s,2H),2.91(m,4H),2.74(m,4H),1.49(s,8H),1.38-0.96(m,48H),0.78(m12H).13C NMR(100MHz,CDCl3)δ152.58,152.52,150.30,149.71,149.43,147.70,147.43,133.28,132.91,131.87,131.66,131.05,130.82,126.36,104.46,47.26,42.66,31.84,31.78,30.01,29.88,29.55,29.51,29.24,22.65,22.58,14.11,14.05.MALDI-TOF MS(C58H86Br2N4Zn)MALDI-TOF-MS 1064.32(M+)。
Synthesis of copolymer P1: to a 10mL reaction flask, under argon protection, compound 2(128.1mg, 0.14mmol), compound 7(16.6mg, 0.016mmol), (3,3 ' -difluoro- [2,2 ' -bithiophene ] -5,5 ' -diyl) bistrimethyltin (82.3mg, 0.16mmol), tetrakis (triphenylphosphine) palladium (9mg, 0.0078mmol), 0.3mL of DMF and 1.2mL of toluene were added and stirred at 110 ℃ for 24 hours. And (3) precipitating a product at the bottom of the bottle, stopping the reaction, cooling the reaction solution to room temperature, sucking by using a dropper, dropwise adding into a methanol solution, filtering and drying in vacuum, wherein the reaction solution is accompanied by precipitation of a solid crude product. Sequentially extracting with acetone and petroleum ether by a Soxhlet extractor for one day to remove small molecules and other byproducts, and extracting with chromatographic pure chloroform to obtain the target polymer. Spin-dry to give 121.1mg of product, 79.9% yield. Number average molecular weight 16100, molecular weight dispersion index 2.13.
Example 2
The perylene diimide-porphyrin-3, 3 '-difluoro-2, 2' bithiophene random copolymer receptor with porphyrin content of 5% provided by the embodiment of the invention has the following synthetic route:
synthesis of copolymer P2: to a 10mL reaction flask, under protection of argon, compound 2(135.2mg, 0.15mmol), compound 7(8.3mg, 0.0078mmol), (3,3 ' -difluoro- [2,2 ' -bithiophene ] -5,5 ' -diyl) bistrimethyltin (82.3mg, 0.16mmol), tetrakis (triphenylphosphine) palladium (9mg, 0.0078mmol), 0.3mL DMF and 1.2mL toluene were added and stirred at 110 ℃ for 24 hours. And (3) precipitating a product at the bottom of the bottle, stopping the reaction, cooling the reaction solution to room temperature, sucking by using a dropper, dropwise adding into a methanol solution, filtering and drying in vacuum, wherein the reaction solution is accompanied by precipitation of a solid crude product. Sequentially extracting with acetone and petroleum ether by a Soxhlet extractor for one day to remove small molecules and other byproducts, and extracting with chromatographic pure chloroform to obtain the target polymer. Spin-dry to give 108.7mg, 72.3% yield. Number average molecular weight 6300, molecular weight dispersion index 1.65.
Example 3
Absorption spectra of perylene diimide-porphyrin-3, 3 '-difluoro-2, 2' bithiophene random copolymer receptors P1 and P2 provided in the examples of the present invention were tested as follows.
Fig. 1 and 2 are uv-vis absorption spectra of perylene diimide-porphyrin-3, 3 '-difluoro-2, 2' bithiophene random copolymer acceptors P1 and P2, respectively, on chloroform solution and quartz slides.
From fig. 2, it can be seen that the absorption maxima of the P1 and P2 films are around 346 nm, 439 nm, 566nm and 352 nm, 439 nm, 590nm, the peaks are around 719nm and 722nm, the optical band gaps are both 1.72eV (the optical band gap can be calculated according to the formula Eg 1240/λ onset, where Eg is the optical band gap, and is the maximum absorption side band value of λ onset film absorption), and the data are listed in table 1.
Example 4
Electrochemical tests of perylene diimide-porphyrin-3, 3 '-difluoro-2, 2' bithiophene random copolymer receptors P1 and P2 provided in the embodiments of the present invention are as follows.
FIG. 3 is a cyclic voltammetric measurement of perylene diimide-porphyrin-3, 3 '-difluoro-2, 2' bithiophene random copolymer acceptors P1 and P2 in thin films as an electrolyte solution of tetra-n-butyl ammonium hexafluorophosphate (0.1M) in anhydrous acetonitrile followed by deoxygenation by bubbling argon. A glassy carbon electrode was used as the working electrode, a platinum wire as the counter electrode and an Ag/Ag + electrode as the reference electrode. The donor or acceptor was wrapped on a glassy carbon electrode and all potentials were corrected using Fc/Fc +.
As can be seen from FIG. 3, the initial oxidation potentials of P1 and P2 were 1.50V and 1.52V, respectively, and the initial reduction potentials were-0.41V and-0.42V, respectively. By passing
eV and LUMO energy
equation for eV the HOMO levels of P1 and P2 were calculated to be-5.80 eV and-5.82 eV, respectively, and the LUMO levels were calculated to be-3.89 eV and-3.88 eV, respectively, as shown in Table 1.
TABLE 1 optical and electrochemical Properties of P1 and P2
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The organic solar cell receptor material based on the terpolymer of perylene diimide, porphyrin and thiophene is characterized in that the organic solar cell receptor material based on the terpolymer of perylene diimide, porphyrin and thiophene is a random copolymer organic solar cell receptor material with a D-A structure, and the structural general formula is shown as formula I:
wherein 0< x <1, n is the number of repeating units;
d is an electron-donating unit, and the structural formula is one of the following structures;
2. the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell acceptor material according to claim 1, wherein the structure of the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell acceptor material is shown in formula ii:
formula II:
3. a method for preparing an organic solar cell receptor material based on a perylene diimide, porphyrin and thiophene terpolymer having the structure of formula ii as defined in claim 2, wherein the method comprises:
4. the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell acceptor material of claim 1, wherein the structure of the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell acceptor material is according to formula iii:
5. a method for preparing the perylene diimide, porphyrin and thiophene terpolymer-based organic solar cell acceptor material having the structure of formula iii as defined in claim 4, wherein the method comprises the following steps:
6. the process according to claim 5, wherein the synthesis of copolymer P2: under argon protection, compound 2, compound 7, (3,3 ' -difluoro- [2,2 ' -bithiophene ] -5,5 ' -diyl) bistrimethyltin (82.3mg, 0.16mmol), tetrakis (triphenylphosphine) palladium (9mg, 0.0078mmol), 0.3mL DMF and 1.2mL toluene were added to a 10mL reaction flask, and stirred at 110 ℃ for 24 hours; separating out a product at the bottom of the bottle, stopping the reaction, cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering, and drying in vacuum; sequentially extracting and removing micromolecules and other byproducts by acetone and petroleum ether through a Soxhlet extractor, and extracting the target polymer by using chromatographic pure chloroform; spin-drying to obtain a product;
the compound 2 has the molecular formula:
the compound 7 has the molecular formula:
7. an all-polymer solar cell prepared using the perylene diimide, porphyrin and thiophene terpolymer based organic solar cell acceptor material of claim 1.
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