阅读说明：本技术 一种非对称非富勒烯化合物及其制备方法与应用 (Asymmetric non-fullerene compound and preparation method and application thereof ) 是由 李刚 曾乐娇 刘焘 罗正辉 崔官伟 唐波 于 2020-11-09 设计创作，主要内容包括：本公开属于有机化合物合成及有机太阳能电池器件制备技术领域,具体涉及一种非对称非富勒烯化合物及其制备方法与应用。所述非对称非富勒烯化合物通式如下所示,(The disclosure belongs to the technical field of organic compound synthesis and organic solar cell device preparation, and particularly relates to an asymmetric non-fullerene compound and a preparation method and application thereof. The general formula of the asymmetric non-fullerene compound is shown as follows,)

1. A compound represented by the formula 1, wherein,

wherein D1 is

In the above-mentioned manner, the first and second substrates are,

wherein, Y₁Is selected from the group consisting of alkyl groups,one of (1); y is₂Selected from S or Se, Y₃Is selected fromOne of (1);

d2 is

In the above-mentioned manner, the first and second substrates are,

wherein, Y₄Selected from O, N-R₁S, Se, Y5 is selected from S, Se, Te, N-R, R1-C-R2,

R1-Ge-R2, R1-Si-R2, Y6 or Y7 is selected fromIn the above-mentioned manner, the first and second substrates are,

y8 is selected from the group consisting of alkyl,in the above-mentioned manner, the first and second substrates are,

y9 is selected from the group consisting of alkyl,one of (1);

preferably, wherein D1 is

D2 is

One of (1);

r in D1 or D2 is both alkyl or alkoxy.

2. A compound represented by the formula 2,

3. a compound represented by the formula 3,

4. a compound represented by the formula 4,

5. a process for preparing a compound of formula 2, comprising the following reaction,

preferably, the method comprises the steps of:

under the protection of nitrogen, sequentially adding a double bromine reagent, 2, 5-bistrimethyltin thiophene, palladium tetratriphenylphosphine and anhydrous toluene, and introducing nitrogen into the solution for a period of time; heating the system and keeping the temperature for a period of time; cooling to room temperature, adding methanol, and sequentially extracting the obtained solid with methanol, n-hexane, acetone and chloroform in a Soxhlet extractor to obtain the final product;

further preferably, the mass ratio of the double bromine reagent, the 2, 5-bistrimethyltin thiophene and the palladium tetratriphenylphosphine is 150-;

further preferably, the duration of introducing nitrogen is 8-15min, preferably 10 min;

further preferably, the system is heated to 100-150 ℃ for 3-5 hours;

even more preferably, the system is warmed to 110 ℃ for 4 hours.

6. A process for preparing a compound of formula 3, comprising the following reaction,

preferably, the method comprises the steps of:

adding a bisstannum reagent, 2, 5-bistrimethylstannoselenophene, Pd (PPh)4 and anhydrous toluene under the protection of nitrogen, introducing nitrogen into the solution for a period of time, and heating the system for a period of time; cooling to room temperature, adding methanol, and sequentially extracting the obtained solid with methanol, n-hexane, acetone and chloroform in a Soxhlet extractor to obtain the final product;

more preferably, the mass ratio of the double tin reagent, the 2, 5-double trimethyl tin selenophene, the Pd (PPh)4 and the anhydrous toluene is 150-;

further preferably, the duration of introducing nitrogen is 8-15min, preferably 10 min;

further preferably, the system is heated to 100-150 ℃ for 3-5 hours;

even more preferably, the system is warmed to 110 ℃ for 4 hours.

7. A process for preparing a compound of formula 4, comprising the following reaction,

preferably, the method comprises the steps of:

adding a bistin reagent, 1, 4-bistrimethyl tin benzene, Pd (PPh)4 and anhydrous toluene in sequence under the protection of nitrogen, introducing nitrogen into the solution for a period of time, and heating the system for a period of time; cooling to room temperature, adding methanol, and sequentially extracting the obtained solid with methanol, n-hexane, acetone and chloroform in a Soxhlet extractor to obtain the final product;

more preferably, the mass ratio of the double tin reagent, the 1, 4-double trimethyl tin benzene and the Pd (PPh)4 is 150-.

8. An organic solar cell photoactive layer, characterized in that it comprises a compound according to any one of claims 1 to 4 or a product of a process for the preparation of a compound according to any one of claims 5 to 7, and a donor material; preferably, the donor material is PM 6.

9. An organic solar cell comprising a compound according to any one of claims 1 to 4 or a product obtained by a method for producing a compound according to any one of claims 5 to 7 or a photoactive layer of an organic solar cell according to claim 9.

10. A preparation method of an organic solar cell is characterized in that a substrate with the surface roughness less than 1nm and composed of a transparent substrate layer and a transparent conductive cathode ITO is cleaned and then dried by nitrogen; coating conductive polyelectrolyte on the surface of a transparent conductive cathode ITO (indium tin oxide) to prepare an anode buffer layer, and carrying out thermal annealing on the formed film; preparing a donor PM6 and a compound of any one of claims 1 to 4 or a product prepared by the preparation method of the compound of any one of claims 5 to 7 on an anode buffer layer to be used as an acceptor mixed active layer, and spin-coating a cathode buffer layer on the surface of a photoactive layer; evaporating a metal cathode on the cathode buffer layer;

preferably, the mass ratio of the donor PM6 to the acceptor is 1: 1;

preferably, the metal cathode is aluminum.

Technical Field

The disclosure belongs to the technical field of organic compound synthesis and organic solar cell device preparation, and particularly relates to an asymmetric non-fullerene compound and a preparation method and application thereof.

Background

The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.

The increasing demand for renewable energy has led to the rapid development of photovoltaic technology, and solar energy is currently the largest carbon neutral energy and also the fastest growing renewable and clean energy. Among the numerous cell technologies, polymer solar cells (OPVs) are based on the earth's abundance of non-toxic materials, with great potential for shorter energy recovery times and reduced energy homogenization costs. Furthermore, OPVs technology has flexible variability, it can be manufactured at low temperature using high-throughput processes, and is expected to be applied to next-generation third-generation photovoltaic technologies. Traditionally, organic photovoltaic donor materials are mainly conjugated polymers or acceptor materials are mainly fullerenes and their derivatives or non-fullerene electron acceptors. Fullerenes have been found to have unusual properties, for example, they have a strong electron-withdrawing ability and a high electron mobility; fullerenes have three-dimensional electron transport properties and the ability to form a good blend morphology to balance the generation and transport of charge. Despite these excellent properties, fullerene has significant drawbacks. For example, fullerenes do not absorb visible light strongly; the main body part of the fullerene main body is difficult to chemically modify, so that lower structural flexibility and higher photoelectric property adjustment difficulty are caused, the synthesis complexity is increased, the possibility of obtaining polymer donor complementary light by the fullerene is reduced, and the light stability of an original film and a mixed film in the air is poor when the fullerene material is made into a device. Thus, non-fullerene acceptor materials are produced.

Since the development of efficient electron-withdrawing-electron-donating-electron-withdrawing (a-D-a) structure acceptor molecules in the prior art, research on non-fullerenes has risen globally, new a-D-a acceptor molecules and new polymer donors are continuously combined by different topics, and the Photoelectric Conversion Efficiency (PCE) which represents the most important parameter of solar cells is also frequently innovative. Currently, PCEs have exceeded 16%, with great promise for large-scale commercialization. However, the inventors found that the stability efficiency of the current batteries is generally below 12% after 100 hours of heat aging or light aging, and is relatively low, and the stability of the batteries is a bottleneck problem of whether the OPV can be applied on a large scale.

Disclosure of Invention

Aiming at the problems of poor stability of the solar cell and poor energy efficiency of a non-fullerene compound in the prior art.

In one or more embodiments of the present disclosure, there is provided a compound of formula 1,

wherein D1 is

In the above-mentioned manner, the first and second substrates are,

wherein, Y₁Is selected from the group consisting of alkyl groups,one of (1); y is₂Selected from S or Se, Y₃Is selected fromOne of (1);

d2 is

In the above-mentioned manner, the first and second substrates are,

wherein, Y₄Selected from O, N-R₁S, Se, Y5 is selected from S, Se, Te, N-R, R1-C-R2, R1-Ge-R2, R1-Si-R2, Y6 or Y7 is selected fromIn the above-mentioned manner, the first and second substrates are,

y8 is selected from the group consisting of alkyl,in the above-mentioned manner, the first and second substrates are,

y9 is selected from the group consisting of alkyl,one kind of (1).

In one or some embodiments of the disclosure, there is provided a compound of formula 2,

in one or some embodiments of the present disclosure, there is provided a compound of formula 3,

in one or some embodiments of the present disclosure, there is provided a compound of formula 4,

in one or some embodiments of the present disclosure, there is provided a method for preparing a compound of formula 2, comprising the reaction of,

in one or some embodiments of the present disclosure, there is provided a method for preparing a compound of formula 3, comprising the reaction of,

in one or some embodiments of the present disclosure, there is provided a method for preparing a compound of formula 4, comprising the reaction of,

in one or some embodiments of the disclosure, there is provided the use of the above-described compounds or the products made by the above-described methods of making the compounds as battery materials.

In one or some embodiments of the present disclosure, there is provided an organic solar cell photoactive layer comprising the above compound or a product made by the above compound preparation method, and a donor material.

In one or some embodiments of the present disclosure, there is provided an organic solar cell comprising the above compound or a product obtained by the above compound preparation method or the above organic solar cell photoactive layer.

In one or more embodiments of the present disclosure, a method for manufacturing an organic solar cell is provided, which includes cleaning a substrate having a surface roughness of less than 1nm and composed of a transparent substrate layer and a transparent conductive cathode ITO, and drying the substrate with nitrogen gas; coating conductive polyelectrolyte on the surface of a transparent conductive cathode ITO (indium tin oxide) to prepare an anode buffer layer, and carrying out thermal annealing on the formed film; preparing a donor PM6 and a compound of any one of claims 1 to 4 or a product prepared by the preparation method of the compound of any one of claims 5 to 7 on an anode buffer layer to be used as an acceptor mixed active layer, and spin-coating a cathode buffer layer on the surface of a photoactive layer; evaporating a metal cathode on the cathode buffer layer;

preferably, the mass ratio of the donor PM6 to the acceptor is 1: 1;

preferably, the metal cathode is aluminum.

One or some of the above technical solutions have the following advantages or beneficial effects:

1) the asymmetric polymer acceptor material provided by the disclosure makes up the defects that the conventional polymer acceptor has weaker molecular binding energy and smaller molecular dipole moment, is beneficial to enhancing intermolecular interaction, has excellent light absorption and carrier transmission performance, and can realize higher short-circuit current (Jsc) and energy conversion efficiency (PCE) in an organic solar cell.

2) In the disclosure, the asymmetric polymer receptor material has good solubility, is easily soluble in common organic solvents, has high electron mobility, is used for preparing organic solar cells with high short-circuit current and high energy conversion efficiency, is a receptor material with excellent performance, has huge potential application value in the photoelectric field, and provides deeper knowledge for adopting an asymmetric polymer receptor strategy.

3) The present disclosure provides a novel organic polymer receptor system-asymmetric polymer receptor material, which is blended with conventional polymer donor materials to prepare full-polymer solar cells, the preparation method of the receptor is simple, the conditions are mild, and the solar cells obtained by preparation simultaneously obtain the highest short-circuit current density J through device optimization_SC＝20.47mA cm^-2The cell efficiency PCE is 14.89%, the stability in the air after packaging is greatly improved, and after 100 hours, the device can still keep 90% of the efficiency of the original device, which exceeds 13%, so that the application range of the device in the photoelectric field is greatly improved, and the device has good practical application value.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this disclosure, illustrate embodiments of the disclosure and, together with the description, serve to explain the disclosure and not to limit the disclosure.

Figure 1 is a hydrogen spectrum of polymer 1 in example 1 of the present disclosure.

Figure 2 is a hydrogen spectrum of polymer 2 in example 2 of the present disclosure.

Figure 3 is a hydrogen spectrum of polymer 3 in example 3 of the present disclosure.

FIG. 4 is a graph of current versus voltage for a cell formed from a donor and a different polymer acceptor in example 4 of the present disclosure.

FIG. 5 is a graph of IPCE profiles for cells of donor and different polymer acceptors in example 4 of the disclosure.

Fig. 6 is a graph of the encapsulation stability of cells composed of donors and different polymer acceptors in example 4 of the disclosure.

Detailed Description

The technical solutions in the embodiments of the present disclosure will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the disclosure without making any creative effort, shall fall within the protection scope of the disclosure.

Aiming at the problems of poor stability of the solar cell and poor energy efficiency of a non-fullerene compound in the prior art.

In one or more embodiments of the present disclosure, there is provided a compound of formula 1,

wherein D1 is

In the above-mentioned manner, the first and second substrates are,

wherein, Y₁Is selected from the group consisting of alkyl groups,one of (1); y is₂Selected from S or Se, Y₃Is selected fromOne of (1);

d2 is

In the above-mentioned manner, the first and second substrates are,

wherein, Y₄Selected from O, N-R₁S, Se, Y5 is selected from S, Se, Te, N-R, R1-C-R2, R1-Ge-R2, R1-Si-R2, Y6 or Y7 is selected fromIn the above-mentioned manner, the first and second substrates are,

y8 is selected from the group consisting of alkyl,in the above-mentioned manner, the first and second substrates are,

y9 is selected from the group consisting of alkyl,one of (1);

preferably, wherein D1 is

D2 is

One of (1);

r in D1 or D2 is both alkyl or alkoxy.

In one or some embodiments of the disclosure, there is provided a compound of formula 2,

in one or some embodiments of the present disclosure, there is provided a compound of formula 3,

in one or some embodiments of the present disclosure, there is provided a compound of formula 4,

in one or some embodiments of the present disclosure, there is provided a method for preparing a compound of formula 2, comprising the reaction of,

preferably, the method comprises the steps of:

under the protection of nitrogen, sequentially adding a double bromine reagent, 2, 5-bistrimethyltin thiophene, palladium tetratriphenylphosphine and anhydrous toluene, and introducing nitrogen into the solution for a period of time; heating the system and keeping the temperature for a period of time; cooling to room temperature, adding methanol, and sequentially extracting the obtained solid with methanol, n-hexane, acetone and chloroform in a Soxhlet extractor to obtain the final product;

further preferably, the mass ratio of the double bromine reagent, the 2, 5-bistrimethyltin thiophene and the palladium tetratriphenylphosphine is 150-;

further preferably, the duration of introducing nitrogen is 8-15min, preferably 10 min;

further preferably, the system is heated to 100-150 ℃ for 3-5 hours;

even more preferably, the system is warmed to 110 ℃ for 4 hours.

In one or some embodiments of the present disclosure, there is provided a method for preparing a compound of formula 3, comprising the reaction of,

preferably, the method comprises the steps of:

adding a bistin reagent, 2, 5-bistrimethylstannoselenophene, palladium tetratriphenylphosphine and anhydrous toluene under the protection of nitrogen, introducing nitrogen into the solution for a while, and heating the system for a while; cooling to room temperature, adding methanol, and sequentially extracting the obtained solid with methanol, n-hexane, acetone and chloroform in a Soxhlet extractor to obtain the final product;

further preferably, the mass ratio of the double tin reagent, the 2, 5-double trimethyl tin selenophene, the palladium tetratriphenylphosphine and the anhydrous toluene is 150: 160:40-50: 7-9;

further preferably, the duration of introducing nitrogen is 8-15min, preferably 10 min;

further preferably, the system is heated to 100-150 ℃ for 3-5 hours;

even more preferably, the system is warmed to 110 ℃ for 4 hours.

In one or some embodiments of the present disclosure, there is provided a method for preparing a compound of formula 4, comprising the reaction of,

preferably, the method comprises the steps of:

under the protection of nitrogen, adding a bistin reagent, 1, 4-bistrimethyl tin benzene, tetratriphenylphosphine palladium and anhydrous toluene in sequence, introducing nitrogen into the solution for a while, and heating the system for a while; cooling to room temperature, adding methanol, and sequentially extracting the obtained solid with methanol, n-hexane, acetone and chloroform in a Soxhlet extractor to obtain the final product;

more preferably, the mass ratio of the double tin reagent, the 1, 4-double trimethyl tin benzene and the tetratriphenylphosphine palladium is 150-160:40-45: 7-9.

In one or some embodiments of the present disclosure, there is provided use of the above-described compound or a product produced by the above-described method for producing the compound as a battery material;

preferably, the cell is an organic solar cell;

preferably, the application is in particular an organic solar active material.

The application is an organic solar cell light active layer material.

In one or some embodiments of the present disclosure, there is provided an organic solar cell photoactive layer comprising the above compound or a product made by the above compound preparation method, and a donor material; preferably, the donor material is PM 6.

In one or some embodiments of the present disclosure, there is provided an organic solar cell comprising the above compound or a product obtained by the above compound preparation method or the above organic solar cell photoactive layer.

In one or more embodiments of the present disclosure, a method for manufacturing an organic solar cell is provided, which includes cleaning a substrate having a surface roughness of less than 1nm and composed of a transparent substrate layer and a transparent conductive cathode ITO, and drying the substrate with nitrogen gas; coating conductive polyelectrolyte on the surface of a transparent conductive cathode ITO (indium tin oxide) to prepare an anode buffer layer, and carrying out thermal annealing on the formed film; preparing a donor PM6 and a compound of any one of claims 1 to 4 or a product prepared by the preparation method of the compound of any one of claims 5 to 7 on an anode buffer layer to be used as an acceptor mixed active layer, and spin-coating a cathode buffer layer on the surface of a photoactive layer; evaporating a metal cathode on the cathode buffer layer;

preferably, the mass ratio of the donor PM6 to the acceptor is 1: 1;

preferably, the metal cathode is aluminum.

Example 1

Synthesis of polymeric asymmetric receptor 1: to a 100ml three-necked flask were added a bisbromine reagent (152.3mg,0.1mmol), 2, 5-bistrimethylstannothiophene (40.9mg,0.1mmol), Pd (PPh)4(8mg), and anhydrous toluene (10ml) in this order under nitrogen protection, and then the solution was purged with nitrogen for 10 min. The system was warmed to 110 ℃ for 4 hours. Then, the mixture was cooled to room temperature, 200ml of methanol was added thereto, and the obtained solid was extracted with methanol, n-hexane, acetone and chloroform in this order using a Soxhlet extractor. Finally the chloroform fraction was subjected to rotary evaporation to remove the solvent to yield 91mg of dark solid product (75% yield), as can be seen in FIG. 1, this example successfully produced an asymmetric polymer acceptor material.

Example 2

Synthesis of polymeric asymmetric receptor 1: to a 100ml three-necked flask were added, in order, a bistin reagent (152.3mg,0.1mmol), 2, 5-bistrimethylstannoselenophene (45.6mg,0.1mmol), Pd (PPh)4(8mg), and anhydrous toluene (10ml) under nitrogen, and the solution was purged with nitrogen for 10 min. The system was warmed to 110 ℃ for 4 hours. Then, the mixture was cooled to room temperature, 200ml of methanol was added thereto, and the obtained solid was extracted with methanol, n-hexane, acetone and chloroform in this order using a Soxhlet extractor. Finally the chloroform fraction was subjected to rotary evaporation to remove the solvent to yield 97mg of a dark solid product (78% yield), as can be seen in reference to FIG. 2, this example successfully produced an asymmetric polymer acceptor material.

Example 3

Synthesis of polymeric asymmetric receptor 1: to a 100ml three-necked flask were added, in order under nitrogen protection, a bistin reagent (153.2mg,0.1mmol), 1, 4-bistrimethylstannylbenzene (40.3mg,0.1mmol), Pd (PPh)4(8mg), and anhydrous toluene (10ml), and then the solution was purged with nitrogen for 10 min. The system was warmed to 110 ℃ for 4 hours. Then, the mixture was cooled to room temperature, 200ml of methanol was added thereto, and the obtained solid was extracted with methanol, n-hexane, acetone and chloroform in this order using a Soxhlet extractor. Finally the chloroform fraction was subjected to rotary evaporation to remove the solvent to yield 99mg of dark solid product (76% yield), as can be seen in FIG. 3, the asymmetric polymer acceptor material was successfully prepared in this example.

Example 4

The photoactive layer was prepared as follows: dissolving a polymer donor PM6 and asymmetric polymer acceptors 1-3 respectively in anhydrous chloroform according to a weight ratio of D/A of 1:1, wherein the PM6 has the following structure:

placing the mixture in a glove box, stirring for 12 hours at room temperature to obtain a blending solution of a donor and a receptor, and spin-coating the blending solution to form a film by a spin coater at the rotating speed of 2400rpm, wherein the thickness of an optical active layer is 100 nm.

The preparation process of the organic solar cell comprises the following steps:

cleaning a substrate with the surface roughness less than 1nm and composed of a transparent substrate layer and a transparent conductive cathode ITO, and drying the substrate by using nitrogen after cleaning; and (3) rotationally coating a commercially available conductive polyelectrolyte (poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid) (4500rpm, 40s, 40nm) to prepare the anode buffer layer, and the formed film is thermally annealed (100 ℃, 10 min); preparing a donor PM6 and an acceptor mixed active layer (2000rpm, 60s and 95nm) on the anode buffer layer by adopting spin coating, wherein the mass ratio is 1: 1; spin coating cathode buffer layer zirconium acetylacetonate (2mg/ml ethanol solution, 5000rpm/min, 8nm) on the surface of the photoactive layer; the metal cathode Al (100nm) was evaporated on the cathode buffer layer the properties measured under standard test conditions AM 1.5, 100mW/cm2 are shown in Table 1, the current-voltage curve is shown in Table 4, the IPCE curve is shown in FIG. 5, and the 100 hour stability curve is shown in FIG. 6.

Table 1 solar cell device parameters based on asymmetric polymer acceptor photoactive materials

From the above data we can see that the photoelectric conversion efficiencies of all three asymmetric cores are above 10%, especially for polymer 1, with efficiencies approaching 15%, which is currently the highest efficiency except for the Y6-based polymer. As can be seen from the stability graph 6, the three polymer materials still maintain 90% of the initial efficiency after 100 hours of encapsulation, and are the best stable battery materials at present.

The disclosure of the present invention is not limited to the specific embodiments, but rather to the specific embodiments, the disclosure is to be accorded the widest scope consistent with the principles and novel features disclosed herein.