Benzodifuryl oligomer as well as synthesis method and application thereof
By synthesizing benzodifuranyl oligomers as organic solar cell active layer materials, the problem of petrochemical raw materials in the prior art is solved, and an efficient and environmentally friendly photoelectric conversion effect is achieved.
Patent Information
- Application Number
- CN202510395210.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-31
- Publication Date
- 2025-07-04
AI Technical Summary
Existing organic solar cell materials rely on petrochemical raw materials, resulting in non-renewable resource consumption and environmental pollution. It is necessary to develop semiconductor materials based on renewable resources to improve photoelectric conversion efficiency and stability.
The benzodifuranyl oligomer was synthesized, and the benzodifuranyl oligomer with a highly conjugated π electron system was purified by purifying compound reaction and post-treatment in a specific molar ratio, and the active layer material used in organic solar cells was prepared.
The open circuit voltage, short circuit current density and energy conversion efficiency of organic solar cells are significantly improved, simplified the synthesis process and reduced material costs.
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Figure CN120247933A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of fused-ring compounds, and specifically, to a benzodifuranyl oligomer, a synthesis method thereof, and applications thereof. Background Art
[0002] An organic solar cell is a device that converts light energy into electrical energy using organic semiconductor materials. Compared with traditional inorganic solar cells, organic solar cells have the advantages of being lightweight and flexible, low-cost and easy to process, and adjustable optical and electrical properties, making them applicable in multiple fields. Currently, high-efficiency electron donor materials mainly rely on polymer systems based on the benzodithiophene (BDT) backbone. However, the synthesis of BDT and its derivatives relies on petrochemical raw materials, resulting in the consumption of non-renewable resources and environmental pollution problems. Developing semiconductor materials based on renewable resources has become an important direction in the field. Furan-based compounds have attracted much attention due to their structural characteristics similar to those of thiophene and the advantages of biomass sources. Among them, benzodifuran (BDF)-based polymers show the potential to become green electron donors. Organic solar cell materials based on benzodifuran units have important application prospects in organic solar cells. By optimizing the structure and copolymerization strategy of benzodifuran units, the power conversion efficiency and stability of organic solar cells can be significantly improved. Currently, most research efforts are dedicated to developing organic solar cell materials based on benzodifuran units with higher performance and broader application prospects.
[0003] The article (Angew.Chem.Int.Ed.2022,61,e202200329.) reported a class of benzodithiophene-based oligomer molecules, their synthesis methods, and the application of such molecules as additives in the active layer materials of organic solar cells. The structure of benzodifuran was not involved in this article. Summary of the Invention
[0004] In the first aspect of the present invention, a benzodifuranyl oligomer is provided, and the general structural formula is shown in Formula 1:
[0005] wherein R is 2-ethylhexyl, and X is selected from one of the following elements: H, F, and Cl.
[0006] In the second aspect of the present invention, a synthesis method of a benzodifuranyl oligomer is provided, and the synthesis route is shown in Formula 2, including the following steps:
[0007]
[0008] wherein R in Compound I, Compound II, and Compound III is 2-ethylhexyl, and X in Compound III is selected from one of the following elements: H, F, and Cl;
[0009] Compound I was added to THF (tetrahydrofuran), and then NBS (N-bromosuccinimide) was added. The first reaction was carried out to obtain the crude product of Compound II, and Compound II was obtained after the first post-treatment; S2, Compound II, Compound III, and a catalyst were added to anhydrous toluene, and the second reaction was carried out to obtain the crude product of Compound III, and the second post-treatment was carried out.
[0010] The molar ratio of Compound II to Compound III is (2 - 3.5):1.
[0011] Optionally, the molar ratio of Compound II to Compound III is (2 - 3):1.
[0012] The molar ratio of Compound I to NBS is 1:(1 - 1.5).
[0013] Optionally, the molar ratio of Compound I to NBS is 1:(1 - 1.2).
[0014] The temperature of the first reaction is 0 - 30 °C, and the time is 1 - 3 h.
[0015] Optionally, the temperature of the first reaction is 20 - 30 °C, and the time is 2 - 3 h.
[0016] The first post-treatment includes: the crude product of Compound II was extracted with dichloromethane in ice water, and then purified by silica gel column chromatography.
[0017] The temperature of the second reaction is 70 - 100 °C, and the time is 8 - 20 h.
[0018] Optionally, the temperature of the second reaction is 70 - 90 °C, and the time is 8 - 15 h.
[0019] The second post-treatment includes: the crude product of Compound III was quenched with an aqueous KF solution, extracted with dichloromethane, and then purified by silica gel column chromatography.
[0020] The concentration of KF in the aqueous KF solution is 5 - 20 wt%.
[0021] The eluent used for silica gel column chromatography purification in the first post-treatment and the second post-treatment is petroleum ether and dichloromethane.
[0022] Optionally, the volume ratio of petroleum ether to dichloromethane in the first post-treatment is (4 - 6):1.
[0023] Optionally, the volume ratio of petroleum ether to dichloromethane in the second post-treatment is (3 - 5):1.
[0024] The catalyst includes Pd2(dba)3 and P(o-tol)3, and the molar ratio of Pd2(dba)3 to P(o-tol)3 is 1:(2 - 12).
[0025] Optionally, the molar ratio of Pd2(dba)3 to P(o-tol)3 is 1:(3 - 5).
[0026] The third aspect of the present invention provides an application of a benzodifuranyl oligomer in the preparation of an organic solar cell.
[0027] The application of the benzodifuranyl oligomer prepared in the present invention in a solar cell can significantly improve the open-circuit voltage, short-circuit current density, and energy conversion efficiency of the organic solar cell. The benzodifuranyl oligomer has a highly conjugated π-electron system, and this conjugated structure can effectively promote the delocalization of electrons, thereby improving the charge transport ability of the material. At the same time, this compound has good compatibility with the donor-acceptor materials in the solar cell, which is beneficial to improving the crystallinity of the active layer film, effectively enhancing the charge generation efficiency, reducing the recombination loss, and thus increasing the open-circuit voltage and short-circuit current density.
[0028] Optionally, the benzodifuranyl oligomer is applied as an additive in the preparation of the solar cell active layer material solution.
[0029] The content of the benzodifuranyl oligomer in the solar cell active layer material solution is 0.5 - 2 mg / mL.
[0030] Beneficial effects
[0031] 1. By limiting the molar ratio of Compound II to Compound III to (2 - 3.5):1, the present invention can effectively improve the yield of the benzodifuranyl oligomer.
[0032] 2. The benzodifuranyl oligomer of the present invention can be applied to a solar cell, and can simultaneously increase the open-circuit voltage and short-circuit current density of the solar cell.
[0033] 3. When the content of the benzodifuranyl oligomer in the solar cell is only 0.5 - 2 mg / mL, the energy conversion efficiency of the solar cell can be increased by about 1.6%.
[0034] 4. The synthesis method of the benzodifuranyl oligomer of the present invention is simple.
[0035] 5. The synthesis reaction conditions of the benzodifuranyl oligomer of the present invention are mild. Description of the drawings
[0036] Figure 1 1H NMR spectrum of Compound I in Example 1.
[0037] Figure 2 13C NMR spectrum of Compound I in Example 1
[0038] Figure 3 1H NMR spectrum of Compound II in Example 1
[0039] Figure 4 13C NMR spectrum of Compound II in Example 1
[0040] Figure 5 1H NMR spectrum of the benzodifuranyl oligomer prepared in Example 1
[0041] Figure 6 13C NMR spectrum of the benzodifuranyl oligomer prepared in Example 1
[0042] Figure 7 1H NMR spectrum of the benzodifuranyl oligomer prepared in Example 2
[0043] Figure 8 13C NMR spectrum of the benzodifuranyl oligomer prepared in Example 2
[0044] Figure 9 1H NMR spectrum of the benzodifuranyl oligomer prepared in Example 3
[0045] Figure 10 13C NMR spectrum of the benzodifuranyl oligomer prepared in Example 3 Detailed implementation mode
[0046] Example 1
[0047] A benzodifuranyl oligomer, the general structural formula is shown in Formula 3:
[0048]
[0049] A synthesis method of a benzodifuranyl oligomer, the synthesis route is shown in Formula 4, including the following steps:
[0050]
[0051] Wherein R in Compound I, Compound II and Compound III is 2-ethylhexyl, and X in Compound III is H.
[0052] Preparation of Compound I: Synthesized by the method of the literature (Macromol. Rapid Commun, DOI: 10.1002 / marc.201700547, refer to Figure Scheme 1).
[0053] Compound I (5.0 mmol) was added to a solution of tetrahydrofuran (50 mL). A solution of N-bromosuccinimide (5.0 mmol) in tetrahydrofuran (30 mL) was added at 0 °C. After stirring at room temperature for 2 h, a mixture was obtained. The mixture was poured into ice water and extracted with dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane volume ratio 5 / 1) to obtain compound II as a yellow solid (1.27 g, yield 37%);
[0054] Compound II (0.26 mmol), compound III (0.1 mol), Pd2(dba)3 (2 mol%), P(o-tol)3 (8 mol%) and anhydrous toluene (10 mL) were respectively added to a 50 mL oven-dried Schlenk tube equipped with a stir bar. Then the reaction was heated to 80 °C overnight (12 h) under a nitrogen atmosphere. After the reaction was completed, the reaction mixture was quenched with a 10 wt% aqueous KF solution, extracted with dichloromethane, and washed with water and brine. After concentration under reduced pressure, the crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane volume ratio 4 / 1) to obtain a benzodifuranyl oligomer (dark red solid, 63 mg, yield 36%), named ADA-H.
[0055] Example 2
[0056] The specific implementation manner was the same as that of Example 1; the difference was that the general structural formula of the benzodifuranyl oligomer described in Example 2 was as shown in Formula 5; the synthetic route was as shown in Formula 4, where X in compound III was F; the synthesis method of the benzodifuranyl oligomer was the same as that of Example 1, and a dark red solid product, 58 mg, yield 32%, was obtained, named ADA-F;
[0057] Example 3
[0058] The specific implementation manner was the same as that of Example 1; the difference was that the general structural formula of the benzodifuranyl oligomer described in Example 3 was as shown in Formula 6; the synthetic route was as shown in Formula 4, where X in compound III was Cl; the synthesis method of the benzodifuranyl oligomer was the same as that of Example 1, and a dark red solid product, 74 mg, yield 40%, was obtained, named ADA-Cl; Performance test method
[0059] 1. The products in the examples were verified by NMR:
[0060] As Figure 1 shown, it is the 1H NMR spectrum of compound I in Example 1; as Figure 2As shown, it is the carbon-13 NMR spectrum of Compound I in Example 1; as Figure 3 As shown, it is the proton NMR spectrum of Compound II in Example 1; as Figure 4 As shown, it is the carbon-13 NMR spectrum of Compound II in Example 1.
[0061] As Figure 5 shown, it is the proton NMR spectrum of the benzodifuranyl oligomer prepared in Example 1; as Figure 6 shown, it is the carbon-13 NMR spectrum of the benzodifuranyl oligomer prepared in Example 1; ( 1 H NMR(600MHz,Chloroform-d)δ7.78-7.76(m,2H),7.75(d,J=3.6Hz,1H),7.49-7.48(m,3H),7.10(dd,J=5.4,3.6Hz,1H),6.95(d,J=3.6Hz,1H),3.44-3.40(m,1H),3.31-3.27(m,3H),2.92(d,J=6.6Hz,2H),1.81-1.74(m,3H),1.48-1.29(m,24H),1.01-0.98(m,6H),0.96-0.93(m,6H),0.90-0.87(m,6H); 13 C NMR(151MHz,Chloroform-d)δ177.60,177.48,153.43,153.41,151.18,148.45,145.04,142.22,142.03,136.29,134.03,133.83,133.38,133.00,132.56,132.39,131.43,130.63,129.45,127.69,127.13,125.79,124.98,124.91,109.33,103.24,41.49,41.29,41.21,34.29,33.66,33.62,32.82,32.75,32.50,28.94,28.83,28.80,26.18,26.00,25.58,23.13,23.02,23.01,14.24,14.15,11.06,10.88; MS(ESI) calculation formula C 102 H 119 O6S 10 ([M+H] + ):1759.6208.Found:1759.6241).
[0062] As Figure 7 shown, it is the proton NMR spectrum of the benzodifuranyl oligomer prepared in Example 2; as Figure 8As shown, it is the carbon NMR spectrum of the benzodifuranyl oligomer prepared in Example 2;( 1 HNMR(600MHz,Chloroform-d)δ7.71-7.70(m,2H),7.53(s,1H),7.44(d,J=5.4Hz,1H),7.36(d,J=3.6Hz,1H),7.27(s,1H),7.06-7.04(m,1H),3.44-3.41(m,1H),3.26-3.20(m,3H),2.84(d,J=6.6Hz,2H),1.79-1.73(m,3H),1.48-1.29(m,24H),1.04-0.99(m,6H),0.96-0.93(m,6H),0.90-0.87(m,6H); 13 CNMR(151MHz,Chloroform-d)δ177.40,177.26,153.28,153.22,151.48,148.20,142.13,141.79,135.68,134.23,133.34,132.90,132.85,132.33,132.17,131.23,130.62,129.50,127.02,124.99,124.38,121.31,117.46,108.74,102.34,41.26,41.12,40.92,33.60,32.87,32.76,32.50,29.69,29.23,28.85,28.83,28.79,26.25,25.99,25.57,23.14,23.03,23.00,14.22,14.18,14.14,11.11,10.87,10.78;MS(ESI) calculation formula C 102 H 117 F2O6S 10 ([M+H] + ):1795.6020.Found:1795.6063).
[0063] As Figure 9 shown, it is the proton NMR spectrum of the benzodifuranyl oligomer prepared in Example 3; As Figure 10 shown, it is the carbon NMR spectrum of the benzodifuranyl oligomer prepared in Example 3;( 11H NMR (600 MHz, Chloroform-d) δ 7.76 (d, J = 4.2 Hz, 1H), 7.71 (d, J = 3.6 Hz, 1H), 7.61 (s, 1H), 7.46 (d, J = 5.4 Hz, 1H), 7.43 (d, J = 4.2 Hz, 1H), 7.29 (s, 1H), 7.07 - 7.06 (m, 1H), 3.43 - 3.39 (m, 1H), 3.27 - 3.21 (m, 3H), 2.88 (d, J = 7.2 Hz, 2H), 1.82 - 1.73 (m, 3H), 1.46 - 1.29 (m, 24H), 1.03 - 0.99 (m, 6H), 0.95 - 0.92 (m, 6H), 0.90 - 0.87 (m, 6H); 13 13C NMR (151 MHz, Chloroform-d) δ 177.43, 177.27, 153.35, 153.29, 151.56, 148.22, 142.22, 141.77, 137.36, 135.74, 134.32, 133.33, 132.92, 132.86, 132.66, 132.37, 132.30, 131.39, 130.65, 129.52, 127.58, 127.07, 125.16, 124.51, 123.30, 108.43, 102.42, 41.26, 41.13, 40.94, 33.63, 32.89, 32.77, 32.50, 32.10, 29.70, 28.86, 28.82, 28.81, 26.26, 26.01, 25.61, 23.14, 23.04, 23.00, 14.23, 14.16, 11.14, 10.89, 10.84; MS (ESI) Calculated for C 102 H 120 Cl2NO6S 10 ([M+NH4] + ): 1844.5694. Found: 1844.5306).
[0064] 2. Preparation of solar cells: The acceptor material L8-BO and the donor material D18-Fu were mixed and dissolved in chloroform (donor concentration: 7 mg / mL) at a mass ratio of 1:1.4. The benzodifuranyl oligomers (ADA-H, ADA-F, and ADA-Cl) prepared in Examples 1-3 were used as additives (1 mg / mL) and stirred for 1 h to obtain a mixed solution M. After the ITO glass electrode was cleaned and pretreated, a hole transport layer was first coated according to the conventional preparation method, and then the mixed solution M was spin-coated on the hole transport layer. After heat annealing at 100 °C, an active layer was obtained. Then, an electron transport layer was coated on it, and finally, a metal material negative electrode was prepared by the conventional metal evaporation method to obtain a solar cell device structure ITO / PEDOT:PSS / D18-Fu:L8-BO / PNDIT-F3N / Ag. Its performance parameters, open circuit voltage (V OC ), short circuit current density (J SC ), fill factor (FF), and power conversion efficiency (PCE) are shown in Table 1.
[0065] Performance test data
[0066] Table 1
[0067]
[0068]
[0069] The PCE (power conversion efficiency) of the solar cell device without additives was 17.4%, Voc was 0.887 V, Jsc was 24.9 mA cm -2 , and FF was 78.5%. By incorporating additives (ADA-H, ADA-F, and ADA-Cl) into the D18-Fu:L8-BO system, the PCE of the solar cell was significantly increased from 17.4% to 19.0%, and the overall parameters of the device were also improved.
Claims
1. A benzodifuranyl oligomer, characterized in that, The general structural formula is shown in Formula 1: Wherein R is 2-ethylhexyl, and X is selected from one of the following elements: H, F, and Cl.
2. A method for synthesizing the benzodifuranyl oligomer according to claim 1, characterized in that, The synthesis route is shown in Formula 2 and includes the following steps: Wherein R in Compound I, Compound II, and Compound III is 2-ethylhexyl, and X in Compound III is selected from one of the following elements: H, F, and Cl; Add Compound I to THF, then add NBS, and carry out the first reaction to obtain the crude product of Compound II, which is then subjected to the first post-treatment to obtain Compound II; S2, add Compound II, Compound III, and a catalyst to anhydrous toluene, carry out the second reaction to obtain the crude product of Compound III, and carry out the second post-treatment.
3. The synthesis method of the benzodifuranyl oligomer according to claim 2, characterized in that, The molar ratio of Compound II to Compound III is (2 - 3.5):
1.
4. The synthesis method of the benzodifuranyl oligomer according to claim 2, characterized in that, The molar ratio of Compound I to NBS is 1:(1 - 1.5).
5. The synthesis method of the benzodifuranyl oligomer according to claim 2, characterized in that, The temperature of the first reaction is 0 - 30 °C, and the time is 1 - 3 h.
6. The synthesis method of the benzodifuranyl oligomer according to claim 2, wherein The first post-treatment includes: extracting the crude product of Compound II with dichloromethane in ice water, and then purifying it by silica gel column chromatography.
7. The synthesis method of the benzodifuranyl oligomer according to claim 2, characterized in that, The temperature of the second reaction is 70 - 100 °C, and the time is 8 - 20 h.
8. The synthesis method of the benzodifuranyl oligomer according to claim 2, wherein The second post-treatment includes: quenching the crude product of Compound III with an aqueous KF solution, extracting with dichloromethane, and then purifying it using silica gel column chromatography.
9. The synthesis method of the benzodifuranyl oligomer according to claim 2, characterized in that, The catalyst includes Pd2(dba)3 and P(o-tol)3, and the molar ratio of Pd2(dba)3 to P(o-tol)3 is 1:(2 - 12).
10. Use of the benzodifuranyl oligomer according to claim 1, characterized in that, It is applied to the preparation of organic solar cells.