A polyfullerene macromolecule, a preparation method thereof and application thereof in solar cells

Abstract

The application relates to the technical field of material preparation, and discloses a polyfullerene polymer, a preparation method thereof and application of the polyfullerene polymer in solar cells. The structure of the polyfullerene polymer is shown in formula (1). The photoelectric device containing the polyfullerene polymer provided by the application has higher battery efficiency and service life, and has important significance for promoting industrialization. Formula (1).

Description

Technical Field

[0001] This invention relates to the field of materials preparation technology, specifically to a polyfullerene polymer, its preparation method, and its application in solar cells. Background Technology

[0002] Fullerenes are allotropes of carbon, known for their unique spherical, elliptical, or tubular structures. Due to their excellent electron transport properties, fullerenes have been widely used in optoelectronic devices, especially perovskite solar cells.

[0003] Currently, C60 and methyl [6,6]-phenyl-C61-butyrate (PCBM) are the most commonly used fullerene electron transport materials. Due to its low solubility, C60 is usually prepared by thermal evaporation; while PCBM has good solution processability and is suitable for the all-solution method to prepare perovskite solar cells, which is of great significance for reducing manufacturing costs and promoting industrialization.

[0004] However, the stability of PCBM has always been a significant factor limiting device performance. Under light and high temperature conditions, PCBM molecules are prone to dimerization, diffusion, and aggregation, thus affecting electron collection and transport capabilities and the morphological stability of the device. Furthermore, the interaction between PCBM and the perovskite layer also leads to device degradation. Specifically, PCBM molecules diffuse into the perovskite layer, while iodide ions in the perovskite layer also diffuse into the PCBM layer. This interdiffusion causes interfacial reactions in the device, thereby accelerating device degradation.

[0005] CN115838480A discloses a polyfullerene polymer material, its preparation method, and its applications. The structure of the polyfullerene polymer material provided by this invention is shown below. This prior art also provides a method for preparing the polyfullerene polymer material, comprising: adding fullerene and a compound containing aromatic groups in a molar ratio of 1:0.01–10.0 to a reaction solvent; and, under the catalysis of a cuprous bromide catalyst, reacting at a temperature of 0–200°C for 0.1–72 h with stirring to obtain the polyfullerene polymer. Preparing thin films from this polyfullerene polymer material or incorporating it into a light-absorbing layer to prepare optoelectronic devices incorporating the polyfullerene material can improve the stability of perovskite solar cells and modules. However, the polyfullerene material prepared by this prior art still has drawbacks such as poor solubility, a narrow processing window, and a tendency to localize during large-area processing, limiting its application in large-area devices.

[0006]

[0007] In summary, developing novel electron transport materials with higher stability, better energy level matching, and stronger interfacial compatibility to replace PCBM and improve the efficiency and lifetime of perovskite solar cells is key to enhancing the stability of perovskite solar cells and promoting their industrialization. Summary of the Invention

[0008] The purpose of this invention is to solve the problem that the electron transport layer of PCBM small molecules is prone to diffusion and dimerization, which affects the efficiency and stability of perovskite solar cells.

[0009] To achieve the above objectives, a first aspect of the present invention provides a polyfullerene polymer, the structure of which is shown in formula (1):

[0010] Equation (1),

[0011] In equation (1), R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from H, C4-C. 40 Aryl, C1-C 40 Straight-chain alkyl, C3-C 40 Branched alkyl, C3-C 40 cycloalkyl, -XR x Any one of the following; R1, R2, R3, R4, R5, R6, R7 and R8 are not all H, and R1, R2, R3, R4, R5, R6, R7 or R8 may optionally contain at least one substituent from F, Cl, Br, I, CN;

[0012] X is -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -C(R0)=C(R 00 At least one of -C≡C-;

[0013] R x C4-C 40 Aryl, C1-C 40 Straight-chain alkyl, C3-C 40 Branched alkyl or C3-C 40 Any one of the cycloalkyl groups;

[0014] R0 and R 00 Each is independently selected from C1-C 40 Straight-chain alkyl, C3-C 40 Branched alkyl, C3-C 40 At least one of the cycloalkyl groups;

[0015] n is an integer from 1 to 10,000,000.

[0016] In some embodiments, in formula (1), R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from H, C4-C. 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl, C3-C 30 cycloalkyl, -XR x R1, R2, R3, R4, R5, R6, R7 and R8 are not all H, and R1, R2, R3, R4, R5, R6, R7 or R8 may optionally contain at least one substituent from F, Cl, Br, I, CN;

[0017] X is -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -C(R0)=C(R 00 At least one of -C≡C-;

[0018] R x C4-C 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl or C3-C 30 Any one of the cycloalkyl groups;

[0019] R0 and R 00 Each is independently selected from C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl, C3-C 30 At least one of the cycloalkyl groups;

[0020] n is an integer from 1 to 10,000,000.

[0021] In some implementations, in equation (1), R1, R4, R5, and R8 are all H;

[0022] R2 and R3 are the same, which is -OR x R6 and R7 are the same, which is -OR x ;

[0023] R in R2 and R6 x Each is independently selected from C4-C 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl groups and C3-C 30 Any one of the cycloalkyl groups;

[0024] n is an integer from 1 to 10,000,000.

[0025] According to a specific implementation, in equation (1), R1, R4, R5, and R8 are all H; R2 and R3 are the same, being -OR. x R6 and R7 are the same, which is -OR x R in R2 and R6 x Each can be independently selected from any of the following:

[0026] ,

[0027] n is an integer from 1 to 10,000,000.

[0028] According to one specific embodiment, the polyfullerene polymer is PFBP-4OEH, and its structure is shown in formula (2):

[0029] Equation (2),

[0030] n is an integer from 1 to 10,000,000.

[0031] A second aspect of the present invention provides a method for preparing the polyfullerene polymer PFBP-4OEH described in the first aspect, the method comprising:

[0032] (1) In the presence of a solvent and under alkaline conditions, the first raw material and the second raw material are subjected to a first mixed reaction to obtain intermediate 1; the first raw material is o-methylhydroquinone and the second raw material is bromoisooctane;

[0033] (2) In the presence of a protective atmosphere, the intermediate 1 is subjected to a second mixing reaction with carbon tetrachloride to obtain intermediate 2;

[0034] (3) In the presence of a protective atmosphere, the intermediate 2 is subjected to a third mixing reaction with bis-(1,5-cyclooctadiene)nickel to obtain intermediate 3;

[0035] (4) In the presence of a solvent, the intermediate 3 is mixed with C60 in a fourth mixing reaction to obtain the polyfullerene polymer.

[0036] In some embodiments, in step (2), the second mixing reaction is carried out in the presence of N-bromosuccinimide and azobisisobutyronitrile.

[0037] A third aspect of the present invention provides an application of the polyfullerene polymer described in the first aspect in the fabrication of optoelectronic device structures.

[0038] In some embodiments, the polyfullerene polymer is used to prepare the optoelectronic device by at least one of the following processes: spin coating, blade coating, slot coating, dip coating, and spray coating.

[0039] In some embodiments, the optoelectronic device is selected from at least one of solar cells, field-effect transistors, photodetectors, radiation detectors, and light-emitting diodes.

[0040] According to one specific embodiment, the solar cell is an organic solar cell and / or a perovskite solar cell.

[0041] A fourth aspect of the present invention provides an organic solar cell comprising an electrode layer, a hole transport layer, an organic light-absorbing layer, an electron transport layer, and a substrate layer;

[0042] The electron transport layer and / or the organic light-absorbing layer contain the polyfullerene polymer described in the first aspect.

[0043] In some embodiments, the organic solar cell includes the electrode layer, the hole transport layer, the organic light-absorbing layer, the electron transport layer, and the substrate layer, which are stacked sequentially.

[0044] In some embodiments, the organic solar cell contains the electrode layer, the electron transport layer, the organic light-absorbing layer, the hole transport layer, and the substrate layer stacked sequentially.

[0045] According to one specific embodiment, the material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

[0046] According to one specific embodiment, the material forming the hole transport layer is selected from at least one of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetratetra(N,N-di-p-methoxyphenylamine)-9,9'-spirodifluorene, poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), 2,2',7,7'-tetratetra(N,N-di-p-ethoxyphenylamine)-9,9'-spirodifluorene, poly(3-hexylthiophene), NiO, MoO3, and V2O5.

[0047] According to one specific embodiment, the material forming the electron transport layer is selected from at least one of fullerene, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, methyl [6,6]-phenyl-C61-butyrate, indene-C60 diadduct, zirconium acetylacetonate, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene, poly(9,9-dioctylfluorene-alt-bipyridine), ZnO, LiF, TiO2, SnO2, and Nb2O5.

[0048] The fifth aspect of the present invention provides a perovskite solar cell comprising an electrode layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and a substrate layer arranged in sequence.

[0049] The perovskite light-absorbing layer contains the polyfullerene polymer described in the first aspect.

[0050] In some embodiments, the material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

[0051] According to one specific embodiment, the material forming the perovskite light-absorbing layer includes a metal halide perovskite with the chemical formula ABX3;

[0052] Wherein, A is at least one of methylamine ion, formamidinium ion, cesium ion, rubidium ion, potassium ion, sodium ion, methylammonium ion, ethylamine ion, propylamine ion, butylamine ion, aniline ion, benzylamine ion, and phenethylamine ion;

[0053] B is at least one of lead ion, tin ion, cadmium ion, germanium ion, zinc ion, and nickel ion;

[0054] X is at least one of fluoride ion, chloride ion, bromide ion, and iodide ion.

[0055] This invention provides a high-performance, stable, solution-processable polyfullerene polymer to replace traditional small-molecule fullerene materials. The entanglement of the polyfullerene polymer chains and the steric hindrance between C60 units suppress the easy diffusion and dimerization problems between molecules in traditional PCBM-type small-molecule materials, thereby improving the stability of perovskite solar cells and modules.

[0056] The method for preparing polyfullerene polymer provided by this invention is simple, rapid, and uses mild reaction conditions. Furthermore, using this polyfullerene polymer to prepare perovskite solar cells can improve their efficiency and lifespan, which is of great significance for promoting their industrialization. Attached Figure Description

[0057] Figure 1 This is a current-voltage curve of an inverted perovskite solar cell based on PFBP-4OEH and PCBM electron transport layer according to a preferred embodiment.

[0058] Figure 2 This is a stability test diagram of an inverted perovskite solar cell based on PFBP-4OEH and PCBM electron transport layer according to a preferred embodiment. Detailed Implementation

[0059] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0060] The following is an explanation of the terminology used in this invention:

[0061] "-----" indicates the key position;

[0062] PTAA: Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine];

[0063] Spiro-OMeTAD: 2,2',7,7'-tetra(N,N-di-p-methoxyphenylamine)-9,9'-spirodifluorene;

[0064] PEDOT:PSS: Poly(3,4-ethylenedioxythiophene): Poly(styrene sulfonate);

[0065] Poly-TPD: Poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine);

[0066] EH44: 2,2',7,7'-tetra(N,N-di-p-ethoxyphenylamine)-9,9'-spirodifluorene;

[0067] P3HT: Poly(3-hexylthiophene);

[0068] C60: Fullerene;

[0069] BCP: 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline;

[0070] PCBM: [6,6]-Phenylated-C61-Butyrate Methyl Ester;

[0071] ICBA: Indene-C60 diadduct;

[0072] ZrAcac: Zirconium acetylacetonate;

[0073] TPBI: 1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene;

[0074] PFN: Poly(9,9-dioctylfluorene-alt-bipyridine).

[0075] To achieve the above objectives, a first aspect of the present invention provides a polyfullerene polymer, the structure of which is shown in formula (1):

[0076] Equation (1),

[0077] In equation (1), R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from H, C4-C. 40 Aryl, C1-C 40 Straight-chain alkyl, C3-C 40 Branched alkyl, C3-C 40 cycloalkyl, -XR x Any one of the following; R1, R2, R3, R4, R5, R6, R7 and R8 are not all H, and R1, R2, R3, R4, R5, R6, R7 or R8 may optionally contain at least one substituent from F, Cl, Br, I, CN;

[0078] X is -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -C(R0)=C(R 00 At least one of -C≡C-;

[0079] R x C4-C 40 Aryl, C1-C 40 Straight-chain alkyl, C3-C 40 Branched alkyl or C3-C 40 Any one of the cycloalkyl groups;

[0080] R0 and R 00 Each is independently selected from C1-C 40 Straight-chain alkyl, C3-C 40 Branched alkyl, C3-C 40 At least one of the cycloalkyl groups;

[0081] n is an integer from 1 to 10,000,000.

[0082] In some embodiments, in formula (1), R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from H, C4-C. 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl, C3-C 30 cycloalkyl, -XR x R1, R2, R3, R4, R5, R6, R7 and R8 are not all H, and R1, R2, R3, R4, R5, R6, R7 or R8 may optionally contain at least one substituent from F, Cl, Br, I, CN;

[0083] X is -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -C(R0)=C(R 00 At least one of -C≡C-;

[0084] R x C4-C 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl or C3-C 30 Any one of the cycloalkyl groups;

[0085] R0 and R 00 Each is independently selected from C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl, C3-C 30 At least one of the cycloalkyl groups;

[0086] n is an integer from 1 to 10,000,000.

[0087] In some implementations, in equation (1), R1, R4, R5, and R8 are all H;

[0088] R2 and R3 are the same, which is -OR x R6 and R7 are the same, which is -OR x ;

[0089] R in R2 and R6 x Each is independently selected from C4-C 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl groups and C3-C 30 Any one of the cycloalkyl groups;

[0090] n is an integer from 1 to 10,000,000.

[0091] According to a specific implementation, in equation (1), R1, R4, R5, and R8 are all H; R2 and R3 are the same, being -OR. x R6 and R7 are the same, which is -OR x R in R2 and R6 x Each can be independently selected from any of the following:

[0092] ,

[0093] n is an integer from 1 to 10,000,000.

[0094] According to one specific embodiment, the polyfullerene polymer is PFBP-4OEH, and its structure is shown in formula (2):

[0095] Equation (2),

[0096] n is an integer from 1 to 10,000,000.

[0097] In some implementations, n is an integer from 1 to 1,000,000.

[0098] In some implementations, n is an integer from 1 to 10000.

[0099] In some embodiments, the number-average molecular weight of the polyfullerene polymer is 7500-9500.

[0100] As previously stated, a second aspect of the present invention provides a method for preparing the polyfullerene polymer PFBP-4OEH described in the first aspect, the method comprising:

[0101] (1) In the presence of a solvent and under alkaline conditions, the first raw material and the second raw material are subjected to a first mixed reaction to obtain intermediate 1; the first raw material is o-methylhydroquinone and the second raw material is bromoisooctane;

[0102] (2) In the presence of a protective atmosphere, the intermediate 1 is subjected to a second mixing reaction with carbon tetrachloride to obtain intermediate 2;

[0103] (3) In the presence of a protective atmosphere, the intermediate 2 is subjected to a third mixing reaction with bis-(1,5-cyclooctadiene)nickel to obtain intermediate 3;

[0104] (4) In the presence of a solvent, the intermediate 3 is mixed with C60 in a fourth mixing reaction to obtain the polyfullerene polymer.

[0105] In one specific embodiment, the present invention also provides a method for preparing the polyfullerene polymer described in the first aspect, the method comprising:

[0106] Formula (I-1): Equation (I-2): R 50 -Br,

[0107] Formula (I-3): Equation (II):

[0108] Formula (III):

[0109] (1) In the presence of a solvent and under alkaline conditions, the first raw material shown in formula (I-1) and the second raw material shown in formula (I-2) are subjected to a first mixing reaction to obtain intermediate 1 shown in formula (I-3);

[0110] (2) In the presence of a protective atmosphere, the intermediate 1 is subjected to a second mixing reaction with carbon tetrachloride to obtain intermediate 2 as shown in formula (II);

[0111] (3) In the presence of a protective atmosphere, the intermediate 2 is subjected to a third mixing reaction with bis-(1,5-cyclooctadiene)nickel to obtain intermediate 3 as shown in formula (III);

[0112] (4) In the presence of a solvent, the intermediate 3 is subjected to a fourth mixing reaction with C60 to obtain the polyfullerene polymer;

[0113] The definitions of substituents in formulas (I-3), (II), and (III) correspond to the definitions in the first aspect of this invention;

[0114] R in equation (I-1) 10 R 20 R 30 and R 40 R in equation (I-2) 50 Together, R1, R2, R3 and R4 in equation (I-3) are provided respectively.

[0115] This invention will not refer to R here. 10 R 20 R 30 and R 40 and R 50 The specific range of options is limited, and those skilled in the art can determine the appropriate type of R based on the required R1, R2, R3, and R4, combined with known knowledge in the field of organic synthesis. 10 R 20 R 30 and R 40 and R 50 .

[0116] It should be noted that when the first raw material shown in formula (I-1) is o-methylhydroquinone and the second raw material shown in formula (I-2) is bromoisooctane, R1 and R5 are the same, R2 and R6 are the same, R3 and R7 are the same, and R4 and R8 are the same. The structures of intermediate 1, intermediate 2, and intermediate 3 are shown below, thereby preparing the polyfullerene polymer PFBP-4OEH:

[0117] Intermediate 1: Intermediate 2: Intermediate 3: .

[0118] The present invention does not have any special requirements for the solvent mentioned in step (1). For example, it can be acetonitrile, tetrahydrofuran, etc.

[0119] The present invention does not have any special requirements for the alkaline conditions described in step (1). For example, the alkaline conditions can be provided by anhydrous potassium carbonate.

[0120] In some embodiments, in step (1), the conditions for the first mixing reaction include a temperature of 65-70°C and a time of 5-10 hours.

[0121] According to a specific embodiment, in step (1), the conditions for the first mixed reaction further include: filtering and purifying the product obtained after the first mixed reaction. The present invention does not have special requirements for the filtering and purification conditions, and these will not be elaborated upon here. Those skilled in the art should not interpret this as a limitation of the present invention. For example, the reaction product can be cooled to room temperature, added to cold water at 5°C, filtered, and then purified by column chromatography.

[0122] The present invention does not have any special requirements for the protective atmosphere described in step (2). For example, it may be nitrogen and / or argon, etc.

[0123] In some embodiments, in step (2), the second mixing reaction is carried out in the presence of N-bromosuccinimide and azobisisobutyronitrile.

[0124] In some embodiments, in step (2), the conditions for the second mixing reaction include a temperature of 20-30°C and a time of 0.5-3h.

[0125] According to a specific embodiment, in step (2), the conditions for the second mixed reaction further include: filtering and recrystallizing the product obtained after the second mixed reaction. The present invention does not have special requirements for the filtering and recrystallization conditions, which will not be elaborated upon here, and should not be construed as a limitation of the present invention by those skilled in the art. Exemplarily, after the reaction product cools to room temperature, the solution is filtered using filter paper. The filtered filter cake is dried, hexane is added, and then filtered again to obtain the filtered product.

[0126] According to one specific embodiment, in step (2), the conditions for the second mixing reaction further include: dissolving the filtered product in tetrahydrofuran, adding N-bromosuccinimide, refluxing under vigorous stirring, and then recrystallizing with hexane to obtain intermediate II.

[0127] In some embodiments, the present invention does not have special requirements for the protective atmosphere described in step (3). For example, it may be nitrogen and / or argon, etc.

[0128] According to a particularly preferred embodiment, in step (3), the third mixing reaction is carried out in the presence of bis-(1,5-cyclooctadiene)nickel, 2,2'-bipyridine, and N,N-dimethylformamide. The inventors have found that, in this preferred embodiment, the polyfullerene polymer obtained by the present invention exhibits higher stability.

[0129] In some embodiments, in step (3), the conditions for the third mixing reaction include: a temperature of 50-100°C and a time of 0.5-4h.

[0130] According to a specific embodiment, in step (3), the conditions for the third mixed reaction further include: extracting, washing, and purifying the product obtained after the third mixed reaction. The present invention does not impose special requirements on the extraction, washing, and purification conditions, and these will not be elaborated upon here. Those skilled in the art should not interpret this as a limitation of the present invention. For example, ethyl acetate can be used for extraction, and the product can be washed three times with 0.1M EDTA-2Na solution and distilled water, followed by column purification.

[0131] In some embodiments, in step (4), the solvent is selected from at least one of ultra-dry toluene, chlorobenzene, and o-dichlorobenzene.

[0132] According to a particularly preferred embodiment, in step (4), the fourth mixing reaction is carried out in the presence of cuprous bromide and 2,2'-bipyridine. The inventors of this invention have found that, in this preferred embodiment, the polyfullerene polymer obtained by the present invention exhibits stronger interfacial compatibility.

[0133] In some embodiments, in step (4), the conditions for the fourth mixing reaction include a temperature of 90-120°C and a time of 24-48h.

[0134] According to a specific embodiment, in step (4), the conditions for the fourth mixing reaction further include: separating and purifying the product obtained after the fourth mixing reaction. The present invention does not have special requirements for the separation and purification conditions, which will not be elaborated upon here, and should not be construed as a limitation of the present invention by those skilled in the art. Exemplarily, the product can first be rotary evaporated to remove the solvent, then dissolved in o-dichlorobenzene, precipitated with methanol, and then extracted with acetone and n-hexane.

[0135] According to one specific embodiment, the method of the present invention includes:

[0136] (1) In the presence of acetonitrile, o-methylhydroquinone, anhydrous potassium carbonate and bromoisooctane were subjected to a first mixed reaction, and then filtered and purified to obtain intermediate 1;

[0137] (2) Under a protective atmosphere, intermediate 1, N-bromosuccinimide, azobisisobutyronitrile and carbon tetrachloride were subjected to a second mixed reaction, and then filtered; tetrahydrofuran and N-bromosuccinimide were added, and the mixture was refluxed for 1 h under stirring, and then recrystallized to obtain intermediate 2.

[0138] (3) In the presence of a protective atmosphere, intermediate 2, bis-(1,5-cyclooctadiene)nickel, 2,2'-bipyridine and N,N-dimethylformamide were subjected to a third mixed reaction, followed by extraction, washing and purification to obtain intermediate 3;

[0139] (4) In the presence of ultra-dry toluene, intermediate 3, C60, cuprous bromide and 2,2'-bipyridine were subjected to a fourth mixed reaction, followed by precipitation and extraction to obtain polyfullerene polymer.

[0140] As previously stated, a third aspect of the present invention provides an application of the polyfullerene polymer described in the first aspect in the fabrication of optoelectronic device structures.

[0141] In some embodiments, the polyfullerene polymer is used to prepare the optoelectronic device by at least one of the following processes: spin coating, blade coating, slot coating, dip coating, and spray coating.

[0142] According to one specific embodiment, the optoelectronic device is prepared by at least one of the following processes: spin coating, blade coating, and spray coating.

[0143] In some embodiments, the optoelectronic device is selected from at least one of solar cells, field-effect transistors, photodetectors, radiation detectors, and light-emitting diodes.

[0144] According to one specific embodiment, the solar cell is an organic solar cell and / or a perovskite solar cell.

[0145] As mentioned above, a fourth aspect of the present invention provides an organic solar cell comprising an electrode layer, a hole transport layer, an organic light-absorbing layer, an electron transport layer, and a substrate layer.

[0146] The electron transport layer and / or the organic light-absorbing layer contain the polyfullerene polymer described in the first aspect.

[0147] In some embodiments, the organic solar cell includes the electrode layer, the hole transport layer, the organic light-absorbing layer, the electron transport layer, and the substrate layer, which are stacked sequentially.

[0148] In some embodiments, the organic solar cell contains the electrode layer, the electron transport layer, the organic light-absorbing layer, the hole transport layer, and the substrate layer stacked sequentially.

[0149] According to one specific embodiment, the material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

[0150] According to one specific embodiment, the material forming the hole transport layer is selected from at least one of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetratetra(N,N-di-p-methoxyphenylamine)-9,9'-spirodifluorene, poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), 2,2',7,7'-tetratetra(N,N-di-p-ethoxyphenylamine)-9,9'-spirodifluorene, poly(3-hexylthiophene), NiO, MoO3, and V2O5.

[0151] According to a particularly preferred embodiment, the material forming the electron transport layer is selected from at least one of fullerene, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, methyl [6,6]-phenyl-C61-butyrate, indene-C60 diadduct, zirconium acetylacetonate, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene, poly(9,9-dioctylfluorene-alt-bipyridine), ZnO, LiF, TiO2, SnO2, and Nb2O5. In this preferred embodiment, the organic solar cell provided by the present invention has a photoelectric conversion efficiency of not less than 15%.

[0152] As mentioned above, the fifth aspect of the present invention provides a perovskite solar cell comprising an electrode layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and a substrate layer arranged in sequence.

[0153] The perovskite light-absorbing layer contains the polyfullerene polymer described in the first aspect.

[0154] In some embodiments, the material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

[0155] In some embodiments, the material forming the electrode layer is selected from at least one of copper, aluminum, carbon, and chromium.

[0156] According to a particularly preferred embodiment, the material forming the perovskite light-absorbing layer includes a metal halide perovskite with the chemical formula ABX3;

[0157] Wherein, A is at least one of methylamine ion, formamidinium ion, cesium ion, rubidium ion, potassium ion, sodium ion, methylammonium ion, ethylamine ion, propylamine ion, butylamine ion, aniline ion, benzylamine ion, and phenethylamine ion;

[0158] B is at least one of lead ion, tin ion, cadmium ion, germanium ion, zinc ion, and nickel ion;

[0159] X is at least one of fluoride ions, chloride ions, bromide ions, and iodide ions. In this preferred embodiment, the perovskite solar cell provided by the present invention has a photoelectric conversion efficiency of not less than 20%.

[0160] In some embodiments, the perovskite light-absorbing layer is MA 0.7 FA 0.3 PbI3 perovskite polycrystalline thin film. The MA 0.7 FA 0.3 The PbI3 perovskite polycrystalline thin film contains lead iodide (PbI2), formamidine iodide (FAI), and methylamine iodide (MAI).

[0161] In some embodiments, the substrate layer is indium tin oxide (ITO) conductive glass.

[0162] According to one specific embodiment, the method for fabricating the perovskite solar cell includes:

[0163] The ITO conductive glass is pretreated, then PTAA is coated onto its surface, followed by MA coating. 0.7 FA 0.3 A polycrystalline PbI3 perovskite film was then coated with polyfullerene PFBP-4OEH polymer, followed by the vapor deposition of BCP and copper electrodes to obtain a perovskite solar cell.

[0164] The present invention will be described in detail below through embodiments. Unless otherwise specified, the raw materials used in the following embodiments are all commercially available products.

[0165] The room temperature or normal temperature mentioned in this article means 25±2℃;

[0166] C60, purchased from Anhui Zesheng Technology Co., Ltd., brand name A17160.

[0167] Bis-(1,5-cyclooctadiene)nickel was purchased from Anhui Zesheng Technology Co., Ltd., with trade name E063628.

[0168] Indium tin oxide (ITO) conductive glass, purchased from Suzhou Shangyang Solar Energy Technology Co., Ltd., brand name TX 07-12.

[0169] PTAA, purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., brand name P3179.

[0170] Preparation of MA 0.7 FA 0.3The raw materials MAI for PbI3 perovskite polycrystalline thin films were purchased from Greatcell, with the trade name SKUMS101000; FAI was purchased from Greatcell, with the trade name SKU MS150000; and PbI2 was purchased from Sigma-Aldrich, with the trade name 900168.

[0171] BCP, purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., brand name B2694.

[0172] PCBM, purchased from Nanjing Zhiyan Technology Co., Ltd., brand name PCBM(60).

[0173] Example 1

[0174] (1) Dissolve 1.24 g of o-methylhydroquinone and 4.1 g of anhydrous potassium carbonate in 40 mL of acetonitrile, heat under reflux for 30 minutes, then add 4.0 g of bromoisooctane and reflux for 8 h. After cooling to room temperature, add cold water at 5 °C, filter to obtain the product, and purify the product by column chromatography to obtain 3.1 g of intermediate 1 (1,4-bis((2-ethylhexyl)oxy)-2-methylbenzene).

[0175] (2) In a nitrogen-protected flask, add 1.0 g of intermediate 1, 0.51 g of N-bromosuccinimide, 0.13 g of azobisisobutyronitrile, and 10 mL of carbon tetrachloride, and heat under reflux for 1 h. Then cool the solution to room temperature and filter it with filter paper. Dry the filter cake, add 60 mL of hexane, and filter again. Dissolve the filtered product in 10 mL of tetrahydrofuran, add 0.51 g of N-bromosuccinimide, reflux under vigorous stirring for 1 h, and then recrystallize with 60 mL of hexane to obtain 1.25 g of intermediate 2.

[0176] (3) In a dry flask under nitrogen protection, 0.30 g of bis-(1,5-cyclooctadiene)nickel, 0.20 g of 2,2'-bipyridine, and 20 mL of N,N-dimethylformamide were heated to 80 °C and activated for 30 minutes. Then, 1.0 g of intermediate 2 was added, and the reaction was carried out at 80 °C for 2 h. After the reaction was completed, the product was extracted with ethyl acetate and washed three times with 0.1 M EDTA-2Na solution and distilled water, respectively. The product was purified by column chromatography to obtain 0.77 g of intermediate 3.

[0177] (4) Add 72 mL of ultra-dry toluene, 120 mg of C60, 48 mg of cuprous bromide, and 105 mg of 2,2'-bipyridine to a dry flask and stir at room temperature for 2 hours. After the C60 dissolves, add 142 mg of intermediate 3 and then heat under reflux for 24 hours. After the reaction is complete, cool to room temperature, remove the toluene solvent by rotary evaporation, dissolve the reaction product in o-dichlorobenzene, precipitate with methanol, and then extract with acetone and n-hexane in a Soxhlet extractor. The final product is a dark brown polyfullerene polymer, named PFBP-4OEH, with a number average molecular weight of 9000.

[0178] The structure of intermediate 1 is as follows: The NMR results are as follows: 1 ¹H NMR (400 MHz, DMSO-D6) δ(ppm): 6.91 - 6.86 (m, 3H), 3.96-3.88 (m, 4H), 2.12 (s, 3H), 1.82-1.78 (m, 2H), 1.53-1.56 (m, 4H), 1.31 - 1.20 (m, 12H), 0.99 (t, J = 6.9 Hz, 6H), 0.88 (t, J = 6.8 Hz, 6H). Mass spectrometry results: HRMS (Maldi-tof) m / z: [M] found 348.30375.

[0179] The structure of intermediate 2 is as follows: The structure of intermediate 3 is as follows:

[0180] The structure of PFBP-4OEH is as follows:

[0181] Example 2

[0182] Indium tin oxide (ITO) conductive glass (substrate) was treated in a UV ozone cleaner for 15 minutes, then a 7nm thick PTAA (hole transport layer) was coated on its surface, followed by a 300nm thick MA layer. 0.7 FA 0.3 A PbI3 perovskite polycrystalline thin film (perovskite light-absorbing layer) is then coated with a 10 nm thick polyfullerene PFBP-4OEH polymer (electron transport layer) on the film surface. Finally, a 5 nm BCP (electron transport layer) and a 100 nm copper electrode (electron layer) are deposited to obtain a perovskite solar cell based on the PFBP-4OEH electron transport layer.

[0183] Comparative Example

[0184] Indium tin oxide (ITO) conductive glass (substrate) was treated in a UV ozone cleaner for 15 minutes, then a 7nm thick PTAA (hole transport layer) was coated on its surface, followed by a 300nm thick MA layer. 0.7 FA 0.3 A PbI3 perovskite polycrystalline thin film (perovskite light-absorbing layer) is then coated on the film surface with a 10 nm thick PCBM (electron transport layer). Finally, a 5 nm BCP (electron transport layer) and a 100 nm copper electrode (electron layer) are deposited to obtain a perovskite solar cell based on the PCBM electron transport layer.

[0185] Test case

[0186] The JV characteristics of the solar apparatus were measured in air using an LED 3A solar simulator (BG-LED3A-100S, AAA-grade solar simulator), with the simulated light power calibrated to 100 mW using a silicon reference cell (Newport 91150V). All equipment used a Keithley 2400 source meter at room temperature in air, with a JV of 0.1 V / s. -1 The scanning rate was measured with a delay of 10 ms. The aperture area was 7.5 mm. 2 The test results are shown in Table 1 and Figure 1 As shown.

[0187] The light stability of the device was evaluated using an automatic maximum power point tracker (91 PVKSOLAR). The system was tested under ambient conditions of 85°C and 50 ± 10% relative humidity using a solar simulator (100 mW cm⁻¹). -2 The packaged device was measured under continuous illumination, and the test results are as follows: Figure 2 As shown.

[0188] Table 1

[0189]

[0190] In summary, this invention provides a high-performance, stable, solution-processable polyfullerene polymer to replace traditional small-molecule fullerene materials. Optoelectronic devices incorporating this polyfullerene polymer, such as perovskite solar cells, exhibit higher battery efficiency and longer lifespan.

[0191] Specifically, through Table 1 and Figure 1 The results show that the photoelectric conversion efficiency of the perovskite solar cell based on PFBP-4OEH in this invention exceeds that of the perovskite solar cell based on PCBM. Figure 2 The results show that the stability of perovskite solar cells has been greatly improved.

[0192] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polyfullerene polymer, characterized in that, The structure of the polyfullerene polymer is shown in formula (1): Equation (1), In equation (1), R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from H, C4-C. 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl, C3-C 30 cycloalkyl, -XR x R1, R2, R3, R4, R5, R6, R7 and R8 are not all H, and R1, R2, R3, R4, R5, R6, R7 or R8 may optionally contain at least one substituent from F, Cl, Br, I, CN; X is -O-, -S-, -C(O)-, -C(O)-O-, -OC(O)-, -OC(O)-O-, -C(R0)=C(R 00 At least one of -C≡C-; R x C4-C 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl or C3-C 30 Any one of the cycloalkyl groups; R0 and R 00 Each is independently selected from C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl, C3-C 30 At least one of the cycloalkyl groups; n is an integer from 1 to 10,000,000.

2. The polyfullerene polymer according to claim 1, characterized in that, In equation (1), R1, R4, R5, and R8 are all H; R2 and R3 are the same, which is -OR x R6 and R7 are the same, which is -OR x ; R in R2 and R6 x Each is independently selected from C4-C 30 Aryl, C1-C 30 Straight-chain alkyl, C3-C 30 Branched alkyl groups and C3-C 30 Any one of the cycloalkyl groups; n is an integer from 1 to 10,000,000.

3. The polyfullerene polymer according to claim 2, characterized in that, In equation (1), R1, R4, R5, and R8 are all H; R2 and R3 are the same, being -OR. x R6 and R7 are the same, which is -OR x R in R2 and R6 x Each can be independently selected from any of the following: ， n is an integer from 1 to 10,000,000.

4. The polyfullerene polymer according to claim 3, characterized in that, The polyfullerene polymer is PFBP-4OEH, and its structure is shown in formula (2): Equation (2), n is an integer from 1 to 10,000,000.

5. A method for preparing the polyfullerene polymer PFBP-4OEH as described in claim 4, characterized in that, The method includes: (1) In the presence of a solvent and under alkaline conditions, the first raw material and the second raw material are subjected to a first mixed reaction to obtain intermediate 1; the first raw material is o-methylhydroquinone and the second raw material is bromoisooctane; (2) In the presence of a protective atmosphere, the intermediate 1 is subjected to a second mixing reaction with carbon tetrachloride to obtain intermediate 2; (3) In the presence of a protective atmosphere, the intermediate 2 is subjected to a third mixing reaction with bis-(1,5-cyclooctadiene)nickel to obtain intermediate 3; (4) In the presence of a solvent, the intermediate 3 is subjected to a fourth mixing reaction with C60 to obtain the polyfullerene polymer.

6. The method according to claim 5, characterized in that, In step (2), the second mixing reaction is carried out in the presence of N-bromosuccinimide and azobisisobutyronitrile.

7. The application of the polyfullerene polymer according to any one of claims 1-4 in the preparation of optoelectronic device structures.

8. The application according to claim 7, characterized in that, The optoelectronic device is prepared by at least one of the following processes: spin coating, blade coating, slot coating, dip coating, and spray coating.

9. The application according to claim 7, characterized in that, The optoelectronic device is selected from at least one of solar cells, field-effect transistors, photodetectors, radiation detectors, and light-emitting diodes.

10. The application according to claim 9, characterized in that, The solar cell is an organic solar cell and / or a perovskite solar cell.

11. An organic solar cell, characterized in that, This organic solar cell contains an electrode layer, a hole transport layer, an organic light-absorbing layer, an electron transport layer, and a substrate layer; The electron transport layer and / or the organic light-absorbing layer contain the polyfullerene polymer as described in any one of claims 1-4.

12. The organic solar cell according to claim 11, characterized in that, The organic solar cell contains the electrode layer, the hole transport layer, the organic light-absorbing layer, the electron transport layer, and the substrate layer, which are stacked sequentially.

13. The organic solar cell according to claim 11, characterized in that, The organic solar cell contains the electrode layer, the electron transport layer, the organic light-absorbing layer, the hole transport layer, and the substrate layer, which are stacked sequentially.

14. The organic solar cell according to any one of claims 11-13, characterized in that, The material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

15. The organic solar cell according to any one of claims 11-13, characterized in that, The material forming the hole transport layer is selected from at least one of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetratetra(N,N-di-p-methoxyphenylamine)-9,9'-spirodifluorene, poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), 2,2',7,7'-tetratetra(N,N-di-p-ethoxyphenylamine)-9,9'-spirodifluorene, poly(3-hexylthiophene), NiO, MoO3, and V2O5.

16. The organic solar cell according to any one of claims 11-13, characterized in that, The material forming the electron transport layer is selected from at least one of fullerene, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, methyl [6,6]-phenyl-C61-butyrate, indene-C60 diadduct, zirconium acetylacetonate, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene, poly(9,9-dioctylfluorene-alt-bipyridine), ZnO, LiF, TiO2, SnO2, and Nb2O5.

17. A perovskite solar cell, characterized in that, The perovskite solar cell contains an electrode layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and a substrate layer stacked sequentially. The perovskite light-absorbing layer contains the polyfullerene polymer as described in any one of claims 1-4.

18. The perovskite solar cell according to claim 17, characterized in that, The material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

19. The perovskite solar cell according to claim 17, characterized in that, The materials forming the perovskite light-absorbing layer include metal halide perovskites with the chemical formula ABX3; Wherein, A is at least one of methylamine ion, formamidinium ion, cesium ion, rubidium ion, potassium ion, sodium ion, methylammonium ion, ethylamine ion, propylamine ion, butylamine ion, aniline ion, benzylamine ion, and phenethylamine ion; B is at least one of lead ion, tin ion, cadmium ion, germanium ion, zinc ion, and nickel ion; X is at least one of fluoride ion, chloride ion, bromide ion, and iodide ion.

Images