PM6 Derivatives, Their Preparation Methods, Solar Modules and Devices

Abstract

The present invention discloses PM6 derivatives, a preparation method thereof, a solar cell component and a device. The general structural formula of the derivatives is as follows: wherein R is selected from an alkyl chain with an acrylate group, an ether chain with an acrylate group, an alkyl chain with an alkynyl group, and an ether chain with an alkynyl group. The range of m is 20 - 100, and the range of n is 2 - 10. The solution of the present invention solves the problem of the stability of devices in non-fullerene system solar cells. It can crosslink under light and heat conditions by itself, has universal anti-solvent properties, and simplifies the device preparation process.

Description

Technical Field

[0001] The present invention relates to solar energy technology, and particularly to a PM6 derivative, a preparation method thereof, a solar component and a device. Background Art

[0002] Power conversion efficiency and device stability are two key technical factors restricting the commercialization of organic solar cells. In the past few decades, the power conversion efficiency of organic solar cells has been significantly improved, but the stability of devices in non-fullerene systems still needs to be solved. The Institute of Chemistry, Chinese Academy of Sciences designed a class of crosslinking agents containing bisaziridine substituents, and improved the stability of solar cells by adding crosslinking agents to the active layer (CN 114790171A). Recently, it has also been reported that in non-fullerene systems, epoxy resin-based crosslinking agents are used to improve the morphological stability of PM6:Y6 thin films, thereby improving the performance and stability of solar cells (ACS Appl. Mater. Interfaces 2022, 14, 1187-1194). The existing technologies all prepare thin films by doping with crosslinking agents, and the method of directly introducing crosslinking groups into the structure of the active layer material to cause self-crosslinking has not been reported yet.

[0003] The information disclosed in this background art section is only intended to enhance the overall understanding of the present invention and should not be regarded as an admission or any form of suggestion that this information constitutes prior art already known to those of ordinary skill in the art. Summary of the Invention

[0004] The purpose of the present invention is to provide a PM6 derivative, a preparation method thereof, a solar component and a device, which solve the problem of device stability in non-fullerene system solar cells, can crosslink itself under photothermal conditions, have universal anti-solvent properties, and simplify the device preparation process.

[0005] To achieve the above purpose, an embodiment of the present invention provides a PM6 derivative, and its structural general formula is as follows: Wherein R is selected from an alkyl chain with an acrylate group, an ether chain with an acrylate group, an alkyl chain with an alkynyl group, an ether chain with an alkynyl group, the range of m is 20-100, and the range of n is 2-10.

[0006] In one or more embodiments of the present invention, the derivative is selected from

[0007]

[0008] Wherein the range of m is 20-100 and the range of n is 2-10 。

[0009] In one or more embodiments of the present invention, a method for preparing a PM6 derivative includes the following steps: Prepare raw materials: monomer I, monomer II, and monomer III, as shown in the following formula: wherein monomer III is selected from R is an alkyl chain with an acrylate group, an ether chain with an acrylate group, an alkyl chain with an alkynyl group, or an ether chain with an alkynyl group; monomer I, monomer II, and monomer III (the feeding ratio of monomer I, monomer II, and monomer III can be 1:0.9:0.1) react in a system with toluene as the solvent and Pd(PPh3)4 (preferably, with a purity greater than 99%) as the catalyst (the catalyst dosage is 4%-5%) (the reaction conditions are: oil bath. Preferably, the internal temperature of the oil bath is 120°C) to obtain. Preferably, the feeding ratio of monomer I, monomer II, and monomer III is 1:0.9:0.1, and the catalyst is 4.5%.

[0010] In one or more embodiments of the present invention, the preparation of monomer III is as follows: one of the following methods is adopted:

[0011] (2,5-Dibromothiophen-3-yl) alcohol and triethylamine are stirred and reacted in a dichloromethane solvent, under a protective atmosphere, and in an ice-salt bath, then an appropriate amount of methacryloyl chloride is added dropwise and reacted. After sufficient reaction, the reaction is quenched, and the derivative with an acrylate group can be obtained by separation; or

[0012] (2,5-Dibromothiophen-3-yl) alcohol and a strong base are stirred and reacted in a DMSO solvent, under a protective atmosphere, and at 20°C, then an appropriate amount of bromopropyne is added dropwise and reacted. After sufficient reaction, the reaction is quenched, and the derivative with an alkynyl group can be obtained by separation. Preferably, the strong base is selected from potassium hydroxide, sodium hydroxide, etc.

[0013] In one or more embodiments of the present invention, (2,5-dibromothiophen-3-yl) alcohol is selected from (2,5-dibromothiophen-3-yl) hexanol, (2,5-dibromothiophen-3-yl) methyl ether diglycol.

[0014] In one or more embodiments of the present invention, the protective atmosphere is selected from a nitrogen atmosphere, an argon atmosphere, or a helium atmosphere.

[0015] In one or more embodiments of the present invention, the stirring time of the stirring reaction is 10 - 30 min. Here, the ice-salt bath stirring is to prevent the system temperature from being too high, and as long as there is no obvious heat release.

[0016] In one or more embodiments of the present invention, the quenching reaction is quenched by adding water.

[0017] In one or more embodiments of the present invention, after the addition of methacryloyl chloride is completed, the ice-salt bath is removed.

[0018] In one or more embodiments of the present invention, a solar module includes a functional component, such as a photovoltaic module of a solar cell, wherein the functional component includes the aforementioned PM6 derivative. The solar module herein may be a functional component incorporating the derivative of the present invention. These functional components may independently perform certain functions, such as photoelectric conversion, or may be combined with other components to form a larger device or apparatus.

[0019] In one or more embodiments of the present invention, a solar device includes the aforementioned solar module. The solar device herein refers to a device or module that can independently convert solar energy to meet a certain function, such as a solar panel.

[0020] Compared to the prior art, the PM6 derivatives and their preparation methods, solar modules, and devices according to embodiments of the present invention address device stability issues in non-fullerene solar cells. They can undergo self-crosslinking under photothermal conditions, exhibit universal solvent resistance, and simplify device manufacturing processes. The derivatives of the present invention are easily molded for production applications and can undergo self-crosslinking under 365nm ultraviolet light or heating. This allows for the formation of a denser, solvent-resistant film in the active layer of the solar cell, improving device stability and simplifying the device manufacturing process. DETAILED DESCRIPTION

[0021] The specific embodiments of the present invention are described in detail below in conjunction with the examples, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0022] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

[0023] Part 1: General molecular structure formula of PM6 derivatives with acrylate groups:

[0024]

[0025] Wherein R represents an alkyl chain with an acrylate group, or an ether chain with an acrylate group. According to the above general formula, the derivatives here can specifically be:

[0026]

[0027] The synthesis method is as follows:

[0028]

[0029] Synthesis of intermediates:

[0030] Monomer I, Monomer II, and Pd(PPh3)4 were directly obtained by purchasing commercially available products, and it was only necessary to meet the purity > 99%. Toluene was purified by double distillation, and the same applies hereinafter.

[0031] The synthesis method of Monomer III is as follows:

[0032] In a three-necked round-bottom flask, (2,5-dibromothiophen-3-yl) alcohol and triethylamine were added, and dichloromethane was added as a solvent. The reaction system was protected with argon and stirred in an ice-salt bath for 10 minutes. Subsequently, methacryloyl chloride was slowly added to the reaction system through a constant-pressure dropping funnel. After the addition was complete, the ice-salt bath was removed, and the reaction continued for 5 h. The reaction was quenched by adding water, and the mixture was extracted with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and a crude product was obtained. The crude product was sampled on silica gel and subjected to column chromatography to separate and obtain Monomer III. In this step, the alcohol group of (2,5-dibromothiophen-3-yl) alcohol determines the final product of Monomer III.

[0033] Synthesis of the compound:

[0034] Monomer I, Monomer II, and Monomer III were added to a three-necked flask, and Pd(PPh3)4 was added as a catalyst, and freshly distilled toluene was added as a solvent. The mixture was refluxed for 24 h. After the reaction was completed, the mixture was dropped into methanol to precipitate a crude product, which was filtered to obtain a crude product. The crude product was successively extracted with methanol, acetone, n-hexane, and chloroform by Soxhlet extraction. Finally, the solution obtained by chloroform Soxhlet extraction was dropped into methanol, and the compound was obtained by filtration.

[0035] Example 1

[0036]

[0037] In a three-necked round-bottom flask, (2,5-dibromothiophen-3-yl) hexanol (10 g, 29.21 mM) and triethylamine (5.92 g, 58.46 mM) were added, and 200 ml of dichloromethane was added as a solvent. The reaction system was protected with argon and stirred in an ice-salt bath for 10 minutes. Subsequently, methacryloyl chloride (4.58 g, 32.60 mM) was slowly added to the reaction system through a constant-pressure dropping funnel. After the addition was complete, the ice-salt bath was removed, and the reaction continued for 5 h. The reaction was quenched by adding water, and the mixture was extracted with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and a crude product was obtained. The crude product was sampled on silica gel and subjected to column chromatography to separate and obtain Monomer III (5.4 g, yield 45%).

[0038] 1H NMR (500 MHz): δ 6.7 (s, Ar-H, 1H), 6 - 6.5 (s, =CH2, 2H), 4.0 (t, O-CH2, 2H), 3.7 (t, Ar-CH, 1H), 2.05 (s, -CH3, 3H), 1.0 - 2.0 (m, -CH2, 8H).

[0039]

[0040] Monomer I (2 g, 2.13 mM), Monomer II (1.467 g, 1.91 mM) and Monomer III-1 (0.087 g, 0.21 mM) were added into a three-necked flask, and then Pd(PPh3)4 (0.11 g, 0.096 mM) was added as a catalyst, and freshly distilled toluene (53 ml) was added as a solvent. The reaction was refluxed for 24 h. After the reaction was completed, it was dropped into methanol to precipitate the crude product, filtered to obtain the crude product. The crude product was successively Soxhlet extracted with methanol, acetone, n-hexane and chloroform. Finally, the solution obtained by chloroform Soxhlet extraction was dropped into methanol, filtered, and dried to obtain 2.5 g of Compound 1.

[0041] GPC (THF): Mn = 2.53W, PDI = 3.09.

[0042] Example 2

[0043]

[0044] (2,5-Dibromothiophen-3-yl)methoxy diethylene glycol (10 g, 26.59 mM) and triethylamine (4.56 g, 5.38 mM) were added into a three-necked round-bottom flask, and 200 ml of dichloromethane was added as a solvent. The reaction system was protected by nitrogen and stirred in an ice-salt bath for 30 minutes. Subsequently, methacryloyl chloride (4.17 g, 39.88 mM) was slowly added to the reaction system through a constant pressure burette funnel. After the addition was completed, the ice-salt bath was removed and the reaction continued for 5 h. The reaction was quenched by adding water, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered to obtain the crude product. The crude product was sampled with silica gel and subjected to column chromatography to separate Monomer III-2. (4.7 g, yield 39.8%).

[0045] 1H NMR (500 MHz): δ 6.6 (s, Ar-H, 1H), 6 - 6.5 (s, =CH2, 2H), 4.9 (s, Ar-CH2-O, 2H), 4.3 (t, COO-CH2-, 2H), 3 - 4 (t, -CH3, 6H), 2.02 (s, -CH3, 3H).

[0046]

[0047] Monomer I (2 g, 2.13 mM), Monomer II (1.467 g, 1.91 mM) and Monomer III-2 (0.094 g, 0.21 mM) were added into a three-necked flask, and then Pd(PPh3)4 (0.11 g, 0.096 mM) was added as a catalyst, and freshly distilled toluene (53 ml) was added as a solvent. The mixture was refluxed for 24 h. After the reaction was completed, it was dropped into methanol to precipitate the crude product, which was filtered to obtain the crude product. The crude product was successively extracted with methanol, acetone, n-hexane and chloroform by Soxhlet extraction. Finally, the solution obtained by chloroform Soxhlet extraction was dropped into methanol, filtered, and dried to obtain 2.6 g of Compound 2.

[0048] GPC (THF): Mn = 2.48W, PDI = 2.22.

[0049] Part Two: General molecular structure formula of derivatives with alkynyl groups:

[0050]

[0051] R represents an alkyl chain with an alkynyl group or an ether chain with an alkynyl group.

[0052] Specifically:

[0053]

[0054]

[0055] The synthesis method is the same as above:

[0056]

[0057] Synthesis of intermediates:

[0058] Monomer I and Monomer II can be directly purchased, and the purity of both needs to be > 99%.

[0059] The synthesis method of Monomer III is as follows:

[0060] In a three-necked round-bottom flask, crushed KOH was added, and DMSO was added as a solvent. The reaction system was protected with helium. At an internal temperature of 20 °C, (2,5-dibromothiophen-3-yl) alcohol diluted with DMSO was added dropwise through a constant-pressure burette, and the mixture was stirred and reacted. Subsequently, propargyl bromide was slowly added to the reaction system through a constant-pressure burette. After the addition was completed, the reaction was continued overnight. The reaction was quenched by pouring it into water, and it was extracted with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the crude product was obtained. The crude product was sampled with silica gel and subjected to column chromatography to separate and obtain Monomer III.

[0061] Synthesis of compounds:

[0062] Monomer Ⅰ, Monomer Ⅱ and Monomer Ⅲ were added into a three-necked flask, and then Pd(PPh3)4 was added as a catalyst and freshly distilled toluene was used as a solvent. The reaction was refluxed for 24 h. After the reaction was completed, the reaction mixture was dropped into methanol to precipitate the crude product. The crude product was filtered to obtain the crude product. The crude product was successively extracted with methanol, acetone, n-hexane and chloroform by Soxhlet extraction. Finally, the solution obtained by chloroform Soxhlet extraction was dropped into methanol, and the compound was obtained by filtration.

[0063] Example 3

[0064]

[0065] In a three-necked round-bottom flask, crushed KOH (2.95 g, 52.62 mM) was added, and 200 ml of DMSO was used as a solvent. The reaction system was protected by argon. At an internal temperature of 20 °C, (2,5-dibromothiophen-3-yl)hexanol (12 g, 35.08 mM) diluted with 50 ml of DMSO was added dropwise through a constant-pressure burette funnel and reacted for 20 min. Subsequently, propargyl bromide (8.35 g, 70.16 mM) was slowly added to the reaction system through a constant-pressure burette funnel. After the addition was completed, the reaction was continued overnight. The reaction was quenched by pouring it into water, and it was extracted with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the crude product was obtained. The crude product was sampled with silica gel and subjected to column chromatography to separate Monomer Ⅲ-1 (4 g, yield 30%).

[0066] 1H NMR (500 MHz): δ 7.12 (s, Ar-H, 1H), 4.20 (s, O-CH2, 2H), 3.40 (t, CH2-O, 2H), 3.37 (S, ≡CH, 1H), 2.70 (t, Ar-CH2, 2H), 1.0 - 1.6 (m, -CH2, 8H).

[0067]

[0068] Monomer Ⅰ (2 g, 2.13 mM), Monomer Ⅱ (1.467 g, 1.91 mM) and Monomer Ⅲ-1 (0.081 g, 0.21 mM) were added into a three-necked flask, and then Pd(PPh3)4 (0.11 g, 0.096 mM) was added as a catalyst and freshly distilled toluene (53 ml) was used as a solvent. The reaction was refluxed for 24 h. After the reaction was completed, the reaction mixture was dropped into methanol to precipitate the crude product. The crude product was filtered to obtain the crude product. The crude product was successively extracted with methanol, acetone, n-hexane and chloroform by Soxhlet extraction. Finally, the solution obtained by chloroform Soxhlet extraction was dropped into methanol, filtered, and dried to obtain 2 g of Compound 3.

[0069] GPC (THF): Mn = 2.31W, PDI = 2.61.

[0070] Example 4

[0071]

[0072] In a three-necked round-bottom flask, crushed KOH (2.68 g, 47.86 mM) was added, and 200 ml of DMSO was added as a solvent. The reaction system was protected with argon. At an internal temperature of 20 °C, (2,5-dibromothiophen-3-yl)methoxydiethylene glycol (12 g, 31.91 mM) diluted with 50 ml of DMSO was added dropwise through a constant-pressure dropping funnel. The reaction was carried out for 0.5 h. Subsequently, propargyl bromide (7.59 g, 63.81 mM) was slowly added to the reaction system through a constant-pressure dropping funnel. After the addition was completed, the reaction was continued overnight. The reaction was quenched by pouring it into water, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and a crude product was obtained. The crude product was sampled with silica gel and subjected to column chromatography to separate the monomer Ⅲ-2 (3.5 g, yield 26.5%).

[0073] 1H NMR (500 MHz): δ 6.61 (s, Ar-H, 1H), 4.90 (s, Ar-CH2, 2H), 4.22 (s, O-CH2, 2H), 3.0 - 3.60 (m, -CH2, 8H), 3.36 (S, ≡CH, 1H)).

[0074]

[0075] Monomer Ⅰ (2 g, 2.13 mM), monomer Ⅱ (1.467 g, 1.91 mM) and monomer Ⅲ-2 (0.088 g, 0.21 mM) were added to a three-necked flask, and Pd(PPh3)4 (0.11 g, 0.096 mM) was added as a catalyst, and freshly distilled toluene (53 ml) was added as a solvent. The reaction was refluxed for 24 h. After the reaction was completed, it was dropped into methanol to precipitate a crude product, which was filtered to obtain a crude product. The crude product was successively Soxhlet extracted with methanol, acetone, n-hexane and chloroform. Finally, the solution obtained by Soxhlet extraction with chloroform was dropped into methanol, filtered, and dried to obtain 2.2 g of compound 4.

[0076] GPC (THF): Mn = 2.63W, PDI = 2.38.

[0077] Including but not limited to the derivatives shown in the above embodiments, when applied to solar cell devices, they have extremely high application convenience, stability and affinity.

[0078] The foregoing description of the specific exemplary embodiments of the present invention is for purposes of illustration and exemplification. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is apparent that many modifications and variations are possible in light of the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the invention and its practical applications, so that those skilled in the art can implement and utilize the various different exemplary embodiments of the invention, as well as various different selections and modifications. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A self-crosslinking solvent-stable PM6 derivative applied to a solar cell, and its structural general formula is as follows: Wherein R is selected from an alkyl chain with acrylate groups, an ether chain with acrylate groups, an alkyl chain with alkynyl groups, and an ether chain with alkynyl groups, the range of m is 20 - 100, and the range of n is 2 - 10.

2. The self-crosslinking solvent-stable PM6 derivative applied to a solar cell according to claim 1, wherein The derivatives are selected from where the range of m is 20 - 100 and the range of n is 2 - 10 。 3. The preparation method of the self-crosslinking solvent-stable PM6 derivative applied to a solar cell according to claim 1 or 2, comprising the following steps: Prepare raw materials: monomer I, monomer II and monomer III, as shown in the following formula: wherein monomer III is selected from R is an alkyl chain with an acrylate group, an ether chain with an acrylate group, an alkyl chain with an alkynyl group, or an ether chain with an alkynyl group; monomer I, monomer II and monomer III are obtained by reacting in a system using toluene as a solvent and Pd(PPh3)4 as a catalyst.

4. The preparation method of the self-crosslinking solvent-stable PM6 derivative applied to a solar cell according to claim 3, characterized in that, The preparation of the monomer III is carried out by adopting one of the following methods: (2,5-Dibromothiophen-3-yl) alcohol and triethylamine are stirred and reacted under a dichloromethane solvent, a protective atmosphere and an ice-salt bath, then an appropriate amount of methacryloyl chloride is added dropwise and reacted. After sufficient reaction, the reaction is quenched and separated to obtain a derivative with an acrylate group; or (2,5-Dibromothiophen-3-yl) alcohol and a strong base are stirred and reacted under a DMSO solvent, a protective atmosphere and at 20 °C, then an appropriate amount of propargyl bromide is added dropwise and reacted. After sufficient reaction, the reaction is quenched and separated to obtain a derivative with an alkynyl group.

5. The preparation method of the self-crosslinking and solvent-stable PM6 derivative applied to a solar cell according to claim 4, characterized in that, The (2,5-dibromothiophen-3-yl) alcohol is selected from (2,5-dibromothiophen-3-yl) hexanol, (2,5-dibromothiophen-3-yl) methyl ether diethylene glycol.

6. The preparation method of the self-crosslinking solvent-stable PM6 derivative applied to a solar cell according to claim 4, characterized in that, The protective atmosphere is selected from an argon atmosphere, a helium atmosphere, a nitrogen atmosphere.

7. The preparation method of the self-crosslinking solvent-stable PM6 derivative applied to a solar cell according to claim 4, characterized in that, The stirring time of the stirring reaction is 10-30 min.

8. The preparation method of the self-crosslinking solvent-stable PM6 derivative applied to a solar cell according to claim 4, characterized in that, The quenching reaction is quenched with water; After the addition of methacryloyl chloride is completed, the ice-salt bath is removed.

9. A solar module, comprising a functional component, and the functional component comprises the self-crosslinking solvent-stable PM6 derivative applied to a solar cell according to claim 1 or 2.

10. A solar device, comprising the solar module according to claim 9.

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