A pcbm, a method for preparing the same, and an apparatus for preparing the same

Abstract

The application provides a PCBM, a preparation method and application thereof, and a device for preparing the PCBM, and belongs to the field of photovoltaic material design, manufacturing and application. The preparation method comprises the following steps: synthesizing an azide compound solution; providing a fullerene solution; adding the azide compound solution into the fullerene solution; reacting the azide compound and the fullerene to obtain a reaction product; and post-treating the reaction product to obtain the PCBM. The method can improve the yield of the PCBM, and reduce the residual amount of the fullerene and the amount of by-products.

Description

Technical Field

[0001] The present invention belongs to the field of photovoltaic material design, manufacturing and application, and relates to a PCBM and a preparation method and application thereof, as well as a device for preparing the PCBM. Background Art

[0002] PCBM ([6,6]-phenyl-C 61 -methyl butyrate) has good solubility and high electron mobility and has been widely used in the fields of organic solar cells and perovskite solar cells.

[0003] Currently, the most common method for preparing PCBM involves reacting methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate with sodium methoxide at 80°C to form an azide compound, which is then cooled to 70°C. A prepared fullerene solution is then added dropwise to the reaction system, and the mixture is stirred for 24-48 hours. Post-reaction purification is performed by column chromatography, followed by recrystallization to yield pure PCBM. Existing synthesis methods suffer from issues such as excessive excess fullerenes and numerous polyaddition product byproducts. This ultimately results in low PCBM yields, difficulty in separation and purification, and high manufacturing costs.

[0004] The reasons for these shortcomings are as follows: First, because the fullerene solution is a room-temperature solution, adding it to the azide reaction system rapidly lowers the system temperature, resulting in insufficient reactivity and ultimately an excess of fullerene. Second, when the fullerene solution is added to the reaction system, the fullerene ratio in the system is too low at the beginning of the reaction, causing each fullerene molecule to react with multiple azides, forming multiple addition byproducts. These two factors ultimately lead to low PCBM yields.

[0005] Due to the low solubility of fullerenes and their excessive excess in the reaction system, they are very likely to cross-contaminate PCBM during subsequent column chromatography purification. To obtain a high-purity product, the column chromatography filler and solvent usage must be increased, prolonging the chromatographic separation time and ultimately driving up purification costs.

[0006] The above problems ultimately lead to high prices of PCBM, making it difficult to achieve large-scale industrialization.

[0007] Therefore, in the art, it is desired to develop a method for preparing PCBM, which can not only reduce the residual amount of fullerenes and the amount of polyaddition by-products generated, but also improve the yield of PCBM. Summary of the Invention

[0008] To address the shortcomings of existing technologies (low reactivity of the raw material fullerenes, low conversion rates, and excessive residual content; high yields and production of polyaddition byproducts; and a large residual fullerene content that complicates separation and purification, increasing purification costs), the present invention aims to provide PCBM, a preparation method and application thereof, and an apparatus for preparing PCBM. This invention optimizes the reaction process, enhances the reactivity of fullerenes, increases the yield of PCBM, reduces the residual fullerene content and the amount of polyaddition byproducts generated, reduces the difficulty and cost of subsequent separation, and lowers the manufacturing cost of PCBM, facilitating large-scale industrial production.

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a method for preparing PCBM, the method comprising the following steps:

[0011] Synthesize azide solution;

[0012] providing a fullerene solution;

[0013] adding the azide solution to the fullerene solution;

[0014] The azide compound reacts with the fullerene to obtain a reaction product;

[0015] The reaction product is post-treated to obtain the PCBM.

[0016] The flow chart of the preparation method of PCBM provided by the present invention is as follows Figure 1 shown.

[0017] The present invention provides a novel PCBM reaction process and method. By back-adding an azide compound to a fullerene solution, not only can the residual amount of fullerene and the amount of polyaddition by-products generated be reduced, but the yield of PCBM can also be increased. The increased yield can greatly reduce the difficulty of subsequent separation and purification, and can also significantly reduce the manufacturing cost of PCBM.

[0018] Preferably, the azide compound solution is prepared by the following method:

[0019] Mixing methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate, an organic solvent, and an alkaline reagent;

[0020] Methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)pentanoate reacts with an alkaline reagent to obtain the azide compound solution.

[0021] Preferably, the organic solvent includes any one of pyridine, pyrimidine, quinoline, and pyrrole, or a combination of at least two of them.

[0022] Preferably, the alkaline reagent includes any one of sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide, or a combination of at least two of them.

[0023] Preferably, the molar ratio of the methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate to the alkaline agent is (1-2):1, for example, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, etc.

[0024] Preferably, the reaction of methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and an alkaline reagent comprises:

[0025] Methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and the alkaline reagent are reacted at 70°C to 90°C (e.g., 70°C, 75°C, 80°C, 85°C, 90°C, etc.) for 30 minutes to 60 minutes (e.g., 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, etc.).

[0026] Preferably, the mass ratio of the fullerene to methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate is (2-4):1, for example, 2:1, 2.2:1, 2.4:1, 2.5:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.5:1, 3.6:1, 3.8:1, 4:1, etc.

[0027] Preferably, the fullerene comprises C 60 and / or C 70 .

[0028] Preferably, the solvent in the fullerene solution includes any one of toluene, xylene, chlorobenzene, o-dichlorobenzene (ODCB), or a combination of at least two of them.

[0029] Preferably, the concentration of the fullerene solution is 1% to 3%, for example, 1%, 1.5%, 2%, 2.5%, 3%, etc.

[0030] Preferably, the step of adding the azide compound solution to the fullerene solution comprises:

[0031] An azide solution at 50°C to 80°C (e.g., 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc.) is added to a fullerene solution at 50°C to 80°C (e.g., 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc.).

[0032] As a preferred technical solution of the present invention, by adding an azide compound solution at a specific temperature to a fullerene solution at a specific temperature, and controlling the azide compound solution and the fullerene solution to have the same temperature range (it is not required that the two have exactly the same temperature), the residual amount of fullerene and the amount of polyaddition by-products generated can be further reduced, thereby further improving the yield of PCBM.

[0033] Preferably, the step of adding the azide compound solution at 50°C to 80°C to the fullerene solution at 50°C to 80°C comprises:

[0034] The azide compound solution at 50°C to 80°C is added dropwise to the fullerene solution at 50°C to 80°C at a drop rate of 100 drops / min to 200 drops / min (e.g., 100 drops / min, 120 drops / min, 140 drops / min, 150 drops / min, 160 drops / min, 180 drops / min, 200 drops / min, etc.).

[0035] The azide compound and fullerene react, comprising:

[0036] First, the azide compound and the fullerene are reacted at 50°C to 80°C (for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc.) for 20 h to 30 h (for example, 20 h, 22 h, 24 h, 26 h, 28 h, 30 h, etc.), and then the azide compound and the fullerene are refluxed at 140°C to 160°C (for example, 140°C, 145°C, 150°C, 155°C, 160°C, etc.) for 24 h to 48 h (for example, 24 h, 26 h, 28 h, 30 h, 32 h, 34 h, 36 h, 38 h, 40 h, 42 h, 44 h, 46 h, 48 h, etc.).

[0037] Preferably, the post-processing of the reaction product comprises:

[0038] The reaction product is subjected to the following treatments: separation and purification by column chromatography, elution, concentration, recrystallization and drying.

[0039] Taking sodium methoxide as an alkaline reagent, the reasonable mechanism diagram of PCBM provided by the present invention is as follows: Figure 2 shown.

[0040] In a second aspect, the present invention provides a PCBM, which is prepared using the preparation method described in the first aspect.

[0041] In a third aspect, the present invention provides an electron transport layer, wherein the electron transport layer comprises PCBM prepared by the preparation method described in the first aspect.

[0042] In a fourth aspect, the present invention provides a perovskite solar cell, comprising a substrate, an organic layer and an electrode layer, wherein the organic layer comprises PCBM prepared by the preparation method described in the first aspect.

[0043] In a fifth aspect, the present invention provides a device for preparing PCBM, comprising:

[0044] a first reaction vessel for synthesizing and containing an azide compound solution;

[0045] a second reaction container, for containing at least the fullerene solution and the synthesized PCBM;

[0046] A connecting mechanism for connecting the first reaction vessel and the second reaction vessel; or a transfer structure for adding the azide compound solution in the first reaction vessel to the fullerene solution in the second reaction vessel.

[0047] The structural block diagram of the device for preparing PCBM provided by the present invention is as follows Figure 3 shown.

[0048] It should be noted that the present invention does not limit the positional relationship between the first reaction container and the second container, as long as the azide compound solution in the first reaction container can be added to the fullerene solution in the second reaction container.

[0049] As a preferred technical solution of the present invention, the first reaction container is arranged above the second reaction container.

[0050] Preferably, a first condenser is installed on the first reaction container, a second condenser is installed on the second reaction container, and the first condenser and the second condenser are connected via a conduit.

[0051] Preferably, the first reaction container is placed in a first heating container, or the first reaction container is connected to a first heating system.

[0052] Preferably, the second reaction container is placed in a second heating container, or the second reaction container is connected to a second heating system.

[0053] Preferably, a stirring device is installed on the second reaction container.

[0054] Compared with the prior art, the present invention has the following beneficial effects:

[0055] The present invention provides a novel PCBM reaction process and method. By dropwise adding an azide compound, a product of 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate and an alkaline reagent, to a fullerene solution, the method can not only reduce the residual amount of fullerene and the amount of generated polyaddition by-products, but also increase the yield of PCBM. The increased yield can significantly reduce the difficulty of subsequent separation and purification, and can also significantly reduce the manufacturing cost of PCBM. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 The present invention provides a flow chart of the method for preparing PCBM.

[0057] Figure 2 The figure is a schematic diagram of the reasonable mechanism of PCBM provided by the present invention, taking sodium methoxide as an alkaline reagent as an example.

[0058] Figure 3 This is a structural block diagram of the device for preparing PCBM provided by the present invention.

[0059] Figure 4 This is a graph showing the liquid chromatography purity test results of the PCBM prepared in Example 1 of the present invention and commercially available PCBM. DETAILED DESCRIPTION

[0060] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0061] Example 1

[0062] In this embodiment, a method for preparing PCBM is provided, and the method comprises the following steps:

[0063] (1) Providing an apparatus, the apparatus comprising:

[0064] a first reaction vessel for synthesizing and containing an azide compound solution, on which a first condenser is installed;

[0065] A second reaction vessel is used to contain the fullerene solution and the synthesized PCBM, and a second condenser is installed on the second reaction vessel. The first condenser and the second condenser are connected by a conduit;

[0066] The first reaction container is connected to the heating system, the second reaction container is placed in the heating container, and a stirring device is installed on the second reaction container.

[0067] (2) Add 20 g C 60 Dissolve in 900 mL of o-xylene to obtain a fullerene solution, place the fullerene solution in a second reaction vessel, and heat to 70°C;

[0068] 10.52 g of methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate (0.028 mol), 100 mL of pyridine, and 1.65 g of sodium methoxide were added to a first reaction vessel. The atmosphere in the first reaction vessel was replaced with nitrogen three times, heated to 70°C, and stirred for 50 minutes to allow methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and sodium methoxide to react to form an azide compound. The system solution turned red, yielding an azide compound solution. The temperature of the azide compound solution was then adjusted to 65°C.

[0069] The azide compound solution in the first reaction vessel was slowly added dropwise (dropping rate: 120 drops / minute) to the fullerene solution in the second reaction vessel. After the addition, the temperature was maintained at 70°C for 24 hours, and then the temperature was raised to 140°C for reflux reaction for 24 hours. The reaction was stopped to obtain PCBM.

[0070] (3) The obtained PCBM is separated and purified by column chromatography. The fullerene is eluted first, and then the PCBM is eluted. The solvent is concentrated to obtain the crude PCBM.

[0071] (4) The crude PCBM product is recrystallized and dried to obtain pure PCBM.

[0072] Example 2

[0073] In this embodiment, a method for preparing PCBM is provided, and the method comprises the following steps:

[0074] (1) Providing an apparatus, the apparatus comprising:

[0075] a first reaction vessel for synthesizing and containing an azide compound solution, on which a first condenser is installed;

[0076] A second reaction vessel is used to contain the fullerene solution and the synthesized PCBM, and a second condenser is installed on the second reaction vessel. The first condenser and the second condenser are connected by a conduit;

[0077] The first reaction container is connected to the heating system, the second reaction container is placed in the heating container, and a stirring device is installed on the second reaction container.

[0078] (2) 20g C 60 Dissolve in 900 mL of o-xylene to obtain a fullerene solution, place the fullerene solution in a second reaction vessel, and heat to 70°C;

[0079] 10.52 g of methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate (0.028 mol), 100 mL of pyridine, and 1.65 g of sodium methoxide were added to a first reaction vessel. The atmosphere in the first reaction vessel was replaced with nitrogen four times, heated to 80° C., and stirred for 40 minutes to allow methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and sodium methoxide to react to form an azide compound. The system solution turned red, yielding an azide compound solution. The temperature of the azide compound solution was then adjusted to 75° C.

[0080] The azide compound solution in the first reaction vessel was slowly added dropwise (dropping rate: 120 drops / minute) to the fullerene solution in the second reaction vessel. After the addition, the temperature was maintained at 70°C for 24 hours, and then the temperature was raised to 140°C for reflux reaction for 24 hours. The reaction was stopped to obtain PCBM.

[0081] (3) The obtained PCBM is separated and purified by column chromatography. The fullerene is eluted first, and then the PCBM is eluted. The solvent is concentrated to obtain the crude PCBM.

[0082] (4) The crude PCBM product is recrystallized and dried to obtain pure PCBM.

[0083] Example 3

[0084] In this embodiment, a method for preparing PCBM is provided, and the method comprises the following steps:

[0085] (1) Providing an apparatus, the apparatus comprising:

[0086] a first reaction vessel for synthesizing and containing an azide compound solution, on which a first condenser is installed;

[0087] A second reaction vessel is used to contain the fullerene solution and the synthesized PCBM, and a second condenser is installed on the second reaction vessel. The first condenser and the second condenser are connected by a conduit;

[0088] The first reaction container is connected to the heating system, the second reaction container is placed in the heating container, and a stirring device is installed on the second reaction container.

[0089] (2) 20g C 60 Dissolve in 900 mL of o-xylene to obtain a fullerene solution, place the fullerene solution in a second reaction vessel, and heat to 80°C;

[0090] 10.52 g of methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate (0.028 mol), 100 mL of pyridine, and 1.65 g of sodium methoxide were added to a first reaction vessel. The atmosphere in the first reaction vessel was replaced with nitrogen five times, heated to 90° C., and stirred for 30 minutes to allow methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and sodium methoxide to react to form an azide compound. The system solution turned red, yielding an azide compound solution. The temperature of the azide compound solution was then adjusted to 75° C.

[0091] The azide compound solution in the first reaction vessel was slowly added dropwise (dropping rate: 120 drops / minute) to the fullerene solution in the second reaction vessel. After the addition, the temperature was maintained at 80°C for 24 hours, and then the temperature was raised to 140°C for reflux reaction for 24 hours. The reaction was stopped to obtain PCBM.

[0092] (3) The obtained PCBM is separated and purified by column chromatography. The fullerene is eluted first, and then the PCBM is eluted. The solvent is concentrated to obtain the crude PCBM.

[0093] (4) The crude PCBM product is recrystallized and dried to obtain pure PCBM.

[0094] Example 4

[0095] In this embodiment, a method for preparing PCBM is provided, and the preparation method comprises the following steps:

[0096] (1) Providing an apparatus, the apparatus comprising:

[0097] a first reaction vessel for synthesizing and containing an azide compound solution, on which a first condenser is installed;

[0098] The second reaction vessel is used to contain the fullerene solution and the synthesized PCBM, and a second condenser is installed on the second reaction vessel. The first condenser and the second condenser are connected by a conduit;

[0099] The first reaction container is connected to the heating system, the second reaction container is placed in the heating container, and a stirring device is installed on the second reaction container.

[0100] (2) 20g C 60 Dissolve in 900 mL of o-xylene to obtain a fullerene solution, and place the fullerene solution in a second reaction vessel at 25°C;

[0101] 10.52 g of methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate (0.028 mol), 100 mL of pyridine, and 1.65 g of sodium methoxide were added to a first reaction vessel. The atmosphere in the first reaction vessel was replaced with nitrogen three times, heated to 70°C, and stirred for 50 minutes to allow methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and sodium methoxide to react to form an azide compound. The system solution turned red, yielding an azide compound solution. The temperature of the azide compound solution was then adjusted to 65°C.

[0102] The azide compound solution in the first reaction vessel was slowly added dropwise (dropping rate: 120 drops / minute) to the fullerene solution in the second reaction vessel. After the addition, the temperature was maintained at 25°C for 24 hours. The temperature was then raised to 140°C for reflux reaction for 24 hours. The reaction was stopped to obtain PCBM.

[0103] (3) The obtained PCBM is separated and purified by column chromatography. The fullerene is eluted first, and then the PCBM is eluted. The solvent is concentrated to obtain the crude PCBM.

[0104] (4) The crude PCBM product is recrystallized and dried to obtain pure PCBM.

[0105] Comparative Example 1

[0106] In this comparative example, a method for preparing PCBM (an existing method for synthesizing PCBM) is provided. The preparation method comprises the following steps:

[0107] (1) Dissolve 10.52g of 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate and 1.65g of sodium methoxide in 100mL of pyridine, stir at 75℃ for 30min to generate azide compound, and the solution turns red. Then reduce the system temperature to 70℃; then add the room temperature solution containing fullerene (20g C 60 The 1,2-dihydro-1,3-dihydro-2-nitropropene (1,2-dihydro-1,3-dihydro-2-nitropropene) was added dropwise to the azide compound reaction system, stirred at 75°C for 24 hours, and then heated to 140°C for 24 hours to obtain PCBM.

[0108] (2) PCBM is separated and purified by column chromatography. Fullerene is eluted first, and then PCBM is eluted. The solvent is concentrated to obtain crude PCBM.

[0109] (3) The crude PCBM product is recrystallized and dried to obtain pure PCBM.

[0110] Comparative Example 2

[0111] In this comparative example, a method for preparing PCBM is provided, and the preparation method comprises the following steps:

[0112] (1) Providing an apparatus, the apparatus comprising:

[0113] a first reaction vessel, for containing the fullerene solution, on which a first condenser is installed;

[0114] A second reaction vessel is used for synthesizing the azide compound solution and synthesizing PCBM, and a second condenser is installed on the second reaction vessel, and the first condenser and the second condenser are connected by a conduit;

[0115] The first reaction container is connected to the heating system, the second reaction container is placed in the heating container, and a stirring device is installed on the second reaction container.

[0116] (2) 20g C 60 Dissolve in 900 mL of o-xylene to obtain a fullerene solution, place the fullerene solution in a first reaction vessel, and heat to 70°C;

[0117] 10.52 g of methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate (0.028 mol), 100 mL of pyridine, and 1.65 g of sodium methoxide were added to a second reaction vessel. The atmosphere in the second reaction vessel was replaced with nitrogen three times, heated to 70°C, and stirred for 50 minutes to allow methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and sodium methoxide to react to form an azide compound. The system solution turned red, thereby obtaining an azide compound solution. The temperature of the azide compound solution was then controlled to 65°C.

[0118] The fullerene solution in the first reaction vessel was slowly added dropwise (at a rate of 120 drops / minute) to the azide solution in the second reaction vessel. After the addition, the reaction was maintained at 70°C for 24 hours, and then the temperature was raised to 140°C for reflux reaction for 24 hours. The reaction was stopped to obtain PCBM.

[0119] (3) The obtained PCBM is separated and purified by column chromatography. The fullerene is eluted first, and then the PCBM is eluted. The solvent is concentrated to obtain the crude PCBM.

[0120] (4) The crude PCBM product is recrystallized and dried to obtain pure PCBM.

[0121] The synthesis process results of PCBM provided in the examples of the present invention and the comparative examples are shown in Table 1.

[0122] Table 1

[0123]

[0124] The test method for the residual fullerene rate in Table 1 is as follows: unreacted fullerene is collected during the purification process. This substance is first separated during the column chromatography extraction process. The residual fullerene amount can be accurately weighed. The ratio of the residual fullerene amount to the amount of fullerene reaction feed is the residual fullerene rate.

[0125] The polyaddition byproduct rate is determined by separating the polyaddition byproducts, unreacted fullerenes, and PCBM by column chromatography. The amounts of unreacted fullerenes and PCBM are then accurately weighed to calculate their respective amounts. The amount of polyaddition byproducts is calculated by subtracting the amounts of unreacted fullerenes and PCBM from the amount of fullerenes fed into the reaction. The polyaddition byproduct rate is calculated as the ratio of the amount of polyaddition byproducts to the amount of fullerenes fed into the reaction.

[0126] As can be seen from Table 1, when PCBM is prepared using the preparation method provided by the present invention, the yield of PCBM is significantly improved, the residual fullerene rate and the rate of polyaddition by-products are significantly reduced, and the column chromatography purification time can be shortened.

[0127] The PCBM prepared in Example 1 of the present invention and the commercially available PCBM (Merck Photonics Materials (Shanghai) Co., Ltd., product number: 684430-1G) were subjected to liquid chromatography purity testing. The test results are as follows: Figure 4 As shown in the results, the purity of both products is higher than 98.5%, which indicates that the PCBM synthesized by the preparation method provided by the present invention can meet the demand.

[0128] To further verify the performance of PCBM prepared using the preparation method provided herein, perovskite solar cell devices were prepared and tested. A conventional perovskite solar cell device structure was employed: FTO / NiOx / PVSK / ETL / Ag. The NiOx layer had a thickness of 20 nm, the PVSK layer had a thickness of 550 nm, and the ETL layer, composed of both the PCBM synthesized in the present invention and commercially available PCBM, had a thickness of 25 nm. The test results are shown in Table 2.

[0129] Table 2

[0130]

[0131] As can be seen from Table 2, under the same experimental conditions, the photoelectric conversion efficiency of the PCBM synthesized in the embodiment of the present invention is 17.12%~17.38%, the open circuit voltage (Voc) is 1.012 V~1.013 V, and the short circuit current (Jsc) is 21.22 mA·cm -2 ~21.55 mA·cm -2 , the fill factor (FF) is 79.14~79.79; the photoelectric conversion efficiency of the PCBM purchased on the market is 17.04%, the open circuit voltage (Voc) is 1.013V, and the short circuit current (Jsc) is 21.19 mA·cm -2The fill factor (FF) is 79.32, indicating that the performance of the PCBM synthesized by the preparation method provided by the present invention is basically the same as that of the PCBM purchased on the market.

[0132] The applicant states that the present invention uses the above-described embodiments to illustrate the PCBM, its preparation method, and application, as well as the apparatus for preparing PCBM. However, the present invention is not limited to the above-described embodiments, and this does not necessarily mean that the present invention must rely on the above-described embodiments for implementation. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the raw materials used, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for preparing PCBM, characterized in that: The preparation method comprises the following steps: Synthesize azide solution; providing a fullerene solution; adding the azide solution dropwise to the fullerene solution; The azide compound reacts with the fullerene to obtain a reaction product; The reaction product is post-treated to obtain the PCBM.

2. The preparation method according to claim 1, characterized in that The azide compound solution is prepared by the following method: Mixing methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate, an organic solvent, and an alkaline reagent; 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate reacts with an alkaline reagent to obtain the azide compound solution; The organic solvent includes any one or a combination of at least two of pyridine, pyrimidine, quinoline, and pyrrole; The alkaline reagent includes any one of sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide, or a combination of at least two thereof; The molar ratio of the 5-phenyl-5-(p-toluenesulfonylhydrazide) valerate and the alkaline reagent is (1-2):1; The 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate reacts with an alkaline reagent, comprising: Methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and an alkaline reagent are reacted at 70°C to 90°C for 30 to 60 minutes.

3. The preparation method according to claim 2, characterized in that The mass ratio of the fullerene to 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate is (2-4):

1.

4. The preparation method according to claim 1, characterized in that The fullerene includes C 60 and / or C 70 ; The solvent in the fullerene solution includes any one of toluene, xylene, chlorobenzene, and o-dichlorobenzene, or a combination of at least two thereof; The concentration of the fullerene solution is 1% to 3%.

5. The preparation method according to claim 1, characterized in that The step of adding the azide compound solution to the fullerene solution comprises: Add an azide solution at 50°C to 80°C to a fullerene solution at 50°C to 80°C; The step of adding an azide compound solution at a temperature of 50° C. to a fullerene solution at a temperature of 50° C. to 80° C. comprises: Adding the azide compound solution at 50°C to 80°C into the fullerene solution at 50°C to 80°C at a dropping rate of 100 drops / min to 200 drops / min; The azide compound and fullerene react, comprising: First, the azide compound and fullerene are reacted at 50°C to 80°C for 20 h to 30 h, and then the azide compound and fullerene are refluxed at 140°C to 160°C for 24 h to 48 h; The post-processing of the reaction product comprises: The reaction product is subjected to the following treatments: separation and purification by column chromatography, elution, concentration, recrystallization and drying.

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