Polyfullerene polymer, preparation method thereof and application of polyfullerene polymer in solar cell

Abstract

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

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of material preparation, in particular to a polyfullerene polymer, a preparation method thereof and application thereof in solar cells. BACKGROUND

[0002] Fullerene is a carbon allotrope known for its unique spherical, ellipsoidal or tubular structure. Due to its excellent electron transport performance, fullerene has been widely used in optoelectronic devices, especially in perovskite solar cells.

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

[0004] However, the stability of PCBM has always been an important factor restricting the performance of devices. Under light and high temperature conditions, PCBM molecules are prone to dimerization, diffusion and aggregation, thereby affecting the electron collection and transport capacity, the morphology stability of the device. In addition, the interaction between PCBM and the perovskite layer can also cause the degradation of the device. Specifically, PCBM molecules will diffuse to the perovskite layer, and iodine ions in the perovskite layer will also diffuse to the PCBM layer. This mutual diffusion will cause the interfacial reaction of the device, thereby accelerating the degradation of the device.

[0005] CN115838480A discloses a polyfullerene polymer material, a preparation method thereof and application thereof. The structure of the polyfullerene polymer material provided by the present application is shown below. The prior art also provides a preparation method of a polyfullerene polymer material, which comprises: adding fullerene and a compound containing an aromatic group in a molar ratio of 1:0.01-10.0 to a reaction solvent, and catalyzing under the catalysis of cuprous bromide catalyst, the reaction temperature is 0-200℃, and the stirring reaction is 0.1-72h, to obtain a polyfullerene polymer. The polyfullerene polymer material is prepared into a thin film or added to an optical absorption layer to prepare an optoelectronic device introducing a polyfullerene material, which can improve the stability of perovskite solar cells and modules. However, the polyfullerene material prepared by the prior art still has poor solubility, a narrow processing window, and the disadvantage of easy local aggregation in large-area processing, which limits its application in large-area devices.

[0006]

[0007] In summary, developing a new electron transport material with higher stability, better energy level matching and stronger interface compatibility to replace PCBM to improve the efficiency and life of perovskite solar cells is the key to improving the stability of perovskite solar cells and promoting their industrialization. SUMMARY

[0008] The purpose of the present application is to solve the problem that the current PCBM small molecule electron transport layer is easy to diffuse and dimerize, affecting the efficiency and stability of perovskite solar cells.

[0009] To achieve the above-mentioned purpose, the first aspect of the present application provides a polyfullerene polymer, the structure of which is shown in formula (1): Formula (1), In formula (1), R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from H, C4-C 40 aryl, C1-C 40 linear alkyl, C3-C 40 branched alkyl, C3-C 40 cycloalkyl, -X-R x Any one of them; R1, R2, R3, R4, R5, R6, R7, and R8 are not H at the same time, and R1, R2, R3, R4, R5, R6, R7, or R8 optionally contains at least one substituent selected from F, Cl, Br, I, CN; X is at least one of -O-, -S-, -C(O)-, -C(O-)-O-, -O-C(O)-, -OC(O)-O-, -C(R0)=C(R 00 )-, -C≡C-; R x is any one of C4-C 40 aryl, C1-C 40 linear alkyl, C3-C 40 branched alkyl, or C3-C 40 cycloalkyl; R0and R 00 are each independently selected from at least one of C1-C 40 linear alkyl, C3-C 40 branched alkyl, C3-C 40 cycloalkyl; n is an integer from 1 to 10000000.

[0010] 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 30linear alkyl, C3-C 30 branched alkyl, C3-C 30 cycloalkyl, -X-R x ; R1, R2, R3, R4, R5, R6, R7and R8are not simultaneously H, and R1, R2, R3, R4, R5, R6, R7or R8optionally contain at least one substituent selected from F, Cl, Br, I, CN; X is at least one of -O-, -S-, -C(O)-, -C(O-)-O-, -O-C(O)-, -OC(O)-O-, -C(R0)=C(R 00 )-, -C≡C-; R x is at least one of C4-C 30 aryl, C1-C 30 linear alkyl, C3-C 30 branched alkyl, or C3-C 30 cycloalkyl; R0and R 00 are each independently selected from at least one of C1-C 30 linear alkyl, C3-C 30 branched alkyl, C3-C 30 cycloalkyl; n is an integer from 1 to 10000000.

[0011] In some embodiments, in formula (1), R1, R4, R5, R8are each H; R2and R3are identical and are -O-R x ; R6and R7are identical and are -O-R x ; R x in R2and R6are each independently selected from at least one of C4-C 30 aryl, C1-C 30 linear alkyl, C3-C 30 branched alkyl, and C3-C 30 cycloalkyl; n is an integer from 1 to 10000000.

[0012] According to a specific embodiment, in formula (1), R1, R4, R5, R8are each H; R2and R3are identical and are -O-R x ; R6and R7are identical and are -O-R x ; R x in R2and R6are each independently selected from at least one of C4-C , n is an integer from 1 to 10000000.

[0013] According to a specific embodiment, the polyfullerene polymer is PFBP-40EH, and the structure is shown in formula (2): Formula (2), n is an integer from 1 to 10000000.

[0014] The second aspect of the present application provides a method for preparing the polyfullerene polymer PFBP-40EH of the first aspect, which comprises: (1) under the presence of a solvent, a first raw material and a second raw material are subjected to a first mixing reaction under basic conditions to obtain an intermediate 1; the first raw material is o-methyl-p-hydroquinone, and the second raw material is bromoiso-octane; (2) under the presence of a protective atmosphere, the intermediate 1 is subjected to a second mixing reaction with carbon tetrachloride to obtain an intermediate 2; (3) under the presence of a protective atmosphere, the intermediate 2 is subjected to a third mixing reaction with bis-(1,5-cyclooctadiene) nickel to obtain an intermediate 3; (4) under the presence of a solvent, the intermediate 3 is subjected to a fourth mixing reaction with C60 to obtain the polyfullerene polymer.

[0015] In some embodiments, in step (2), the second mixing reaction is carried out in the presence of N-bromosuccinimide and azobisisobutyronitrile.

[0016] The third aspect of the present application provides an application of the polyfullerene polymer of the first aspect in the preparation of a photoelectric device structure.

[0017] In some embodiments, the polyfullerene polymer is used to prepare the photoelectric device by at least one process selected from spin coating, blade coating, slot coating, dip coating, and spray coating.

[0018] In some embodiments, the photoelectric device is selected from at least one of a solar cell, a field effect transistor, a photodetector, a radiation detector, and a light emitting diode.

[0019] According to a specific embodiment, the solar cell is an organic solar cell and / or a perovskite solar cell.

[0020] The fourth aspect of the present application provides an organic solar cell, which comprises an electrode layer, a hole transport layer, an organic light-absorbing layer, an electron transport layer, and a base layer. The electron transport layer and / or the organic light-absorbing layer comprises the polyfullerene polymer of the first aspect.

[0021] In some embodiments, the organic solar cell comprises the electrode layer, the hole transport layer, the organic light-absorbing layer, the electron transport layer, and the base layer arranged in sequence.

[0022] In some embodiments, the organic solar cell comprises the electrode layer, the electron transport layer, the organic light-absorbing layer, the hole transport layer, and the base layer arranged in sequence.

[0023] According to a specific embodiment, the material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

[0024] According to a 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'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), 2,2',7,7'-tetrakis(N,N-di-p-ethoxyphenylamine)-9,9'-spirobifluorene, poly(3-hexylthiophene), NiO, MoO3, and V2O5.

[0025] According to a 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, [6,6]-phenyl-C61-butyric acid methyl ester, indene-C60 bisadduct, 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.

[0026] A fifth aspect of the present application provides a perovskite solar cell comprising an electrode layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and a base layer arranged in sequence. The perovskite light-absorbing layer comprises the polyfullerene polymer of the first aspect.

[0027] In some embodiments, the material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

[0028] According to a specific embodiment, the material forming the perovskite light-absorbing layer comprises a metal halide perovskite of 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.

[0029] This invention provides a high-performance, stable, solution-processable polyfullerene polymer that replaces traditional small-molecule fullerene materials. The entanglement of the polyfullerene polymer chains and the steric hindrance between C60 units suppress the intermolecular diffusion and dimerization issues of traditional PCBM-based small-molecule materials, thereby improving the stability of perovskite solar cells and modules.

[0030] The polyfullerene polymer preparation method provided by the present invention is simple and rapid, and the reaction conditions are mild. Furthermore, using the polyfullerene polymer to prepare perovskite solar cells can improve the efficiency and lifespan of perovskite solar cells, which is of great significance for promoting their industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a current-voltage curve of an inverse perovskite solar cell based on PFBP-4OEH and a PCBM electron transport layer according to a preferred embodiment; Figure 2 This is a stability test diagram of an inverse perovskite solar cell based on PFBP-4OEH and PCBM electron transport layer according to a preferred embodiment. DETAILED DESCRIPTION

[0032] The endpoints of the ranges and any values ​​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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0033] The following is an explanation of the terms of the present invention: “-----” indicates the key position; PTAA: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]; Spiro-OMeTAD: 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene; PEDOT:PSS: poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate); Poly-TPD: poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine); EH44: 2,2',7,7'-tetra(N,N-di-p-ethoxyphenylamine)-9,9'-spirobifluorene; P3HT: poly(3-hexylthiophene); C60: fullerene; BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; PCBM: [6,6]-phenyl-C61-butyric acid methyl ester; ICBA: indene-C60 bisadduct; ZrAcac: zirconium acetylacetonate; TPBI: 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene; PFN: poly(9,9-dioctylfluorene-alt-bipyridine).

[0034] To achieve the above object, a first aspect of the present application provides a polyfullerene polymer, the structure of which is shown in formula (1): Formula (1), wherein, in formula (1), R1, R2, R3, R4, R5, R6, R7, R8 are each independently selected from H, C4-C 40 aryl, C1-C 40 linear alkyl, C3-C 40 branched alkyl, C3-C 40 cycloalkyl, -X-R x any one of them; R1, R2, R3, R4, R5, R6, R7 and R8 are not simultaneously H, and R1, R2, R3, R4, R5, R6, R7 or R8 optionally contains at least one substituent selected from F, Cl, Br, I, CN; X is at least one of -O-, -S-, -C(O)-, -C(O-)-O-, -O-C(O)-, -OC(O)-O-, -C(R0)=C(R 00 )-, -C≡C-; R x is any one of C4-C 40 aryl, C1-C 40 linear alkyl, C3-C 40 branched alkyl, or C3-C 40 cycloalkyl; R0and R 00 are each independently selected from at least one of C1-C 40 linear alkyl, C3-C 40 branched alkyl, C3-C 40 cycloalkyl; n is an integer from 1 to 10,000,000.

[0035] In some embodiments, in formula (1), R1, R2, R3, R4, R5, R6, R7, R8 are each independently selected from H, C4-C 30 aryl, C1-C 30 linear alkyl, C3-C 30 branched alkyl, C3-C 30 cycloalkyl, -X-R x ; R1, R2, R3, R4, R5, R6, R7, and R8 are not simultaneously H, and R1, R2, R3, R4, R5, R6, R7, or R8 optionally contains at least one substituent selected from F, Cl, Br, I, CN; X is at least one of -O-, -S-, -C(O)-, -C(O-)-O-, -O-C(O)-, -OC(O)-O-, -C(R0)=C(R 00 )-, -C≡C-; R x is C4-C 30 aryl, C1-C 30 linear alkyl, C3-C 30 branched alkyl, or C3-C 30 cycloalkyl; R0and R 00 are each independently selected from C1-C 30 linear alkyl, C3-C 30 branched alkyl, C3-C 30 cycloalkyl; n is an integer from 1 to 10,000,000.

[0036] In some embodiments, in formula (1), R1, R4, R5, R8 are each H; R2and R3are the same, -O-R x ; R6and R7are the same, -O-R x ; R x is each independently selected from C4-C 30 aryl, C1-C 30 linear alkyl, C3-C 30 branched alkyl, and C3-C 30 cycloalkyl; n is an integer from 1 to 10,000,000.

[0037] According to a specific embodiment, in formula (1), R1, R4, R5, R8 are each H; R2and R3are the same, -O-R x; R6 and R7 are the same, -O-R x ; R2 and R6 are the same, -O-R x each independently is selected from any one of the following: , n is an integer from 1 to 10000000.

[0038] According to a specific embodiment, the polyfullerene macromolecule is PFBP-4OEH, and the structure is shown in formula (2): Formula (2), n is an integer from 1 to 10000000.

[0039] In some embodiments, n is an integer from 1 to 1000000.

[0040] In some embodiments, n is an integer from 1 to 10000.

[0041] In some embodiments, the number average molecular weight of the polyfullerene macromolecule is 7500-9500.

[0042] As described above, the second aspect of the present application provides a method for preparing the polyfullerene macromolecule PFBP-4OEH of the first aspect, and the method comprises: (1) under the presence of a solvent, a first raw material and a second raw material are subjected to a first mixing reaction under basic conditions to obtain an intermediate 1; the first raw material is o-methyl hydroquinone, and the second raw material is bromoiso-octane; (2) under the presence of a protective atmosphere, the intermediate 1 is subjected to a second mixing reaction with carbon tetrachloride to obtain an intermediate 2; (3) under the presence of a protective atmosphere, the intermediate 2 is subjected to a third mixing reaction with bis-(1,5-cyclooctadiene) nickel to obtain an intermediate 3; (4) under the presence of a solvent, the intermediate 3 is subjected to a fourth mixing reaction with C60 to obtain the polyfullerene macromolecule.

[0043] In a specific embodiment, the present application further provides a method for preparing the polyfullerene macromolecule of the first aspect, and the method comprises: Formula (I-1): , formula (I-2): R 50 -Br, Formula (I-3): , formula (II):

[0044] Formula (III):

[0045] (1) a first raw material shown in formula (I-1) is mixed with a second raw material shown in formula (I-2) under basic conditions in the presence of a solvent to obtain an intermediate 1 shown in formula (I-3); (2) the intermediate 1 is mixed with carbon tetrachloride under the presence of a protective atmosphere to obtain an intermediate 2 shown in formula (II); (3) the intermediate 2 is mixed with bis-(1,5-cyclooctadiene) nickel under the presence of a protective atmosphere to obtain an intermediate 3 shown in formula (III); (4) the intermediate 3 is mixed with C60 in the presence of a solvent to obtain the polyfullerene macromolecule; the definitions of the substituents in formula (I-3), formula (II) and formula (III) are the same as those in the first aspect of the present application; R 10 , R 20 , R 30 and R 40 in formula (I-1) are the same as R 50 in formula (I-2) to provide R1, R2, R3 and R4 in formula (I-3) respectively.

[0046] The present application does not limit the specific optional ranges of R 10 , R 20 , R 30 and R 40 and R 50 herein, and those skilled in the art can determine the appropriate types of R 10 , R 20 , R 30 and R 40 and R 50 according to the required R1, R2, R3 and R4 and in combination with the known knowledge in the field of organic synthesis.

[0047] It should be noted that when the first raw material shown in formula (I-1) is ortho-methyl hydroquinone and the second raw material shown in formula (I-2) is bromoiso-octane, R1 is the same as R5, R2 is the same as R6, R3 is the same as R7, and R4 is the same as R8, and the structures of the intermediate 1, the intermediate 2 and the intermediate 3 are shown as follows respectively, thereby preparing the polyfullerene macromolecule PFBP-4OEH: Intermediate 1: , intermediate 2: , and intermediate 3: .

[0048] The present application does not have special requirements for the solvent in step (1), and exemplarily, it can be acetonitrile, tetrahydrofuran, etc.

[0049] The present invention has no particular requirements for the alkaline conditions in step (1). For example, the alkaline conditions can be provided by anhydrous potassium carbonate.

[0050] In some embodiments, in step (1), the conditions of the first mixing reaction include: temperature of 65-70° C. and time of 5-10 h.

[0051] According to a specific embodiment, in step (1), the conditions of the first mixing reaction further include: filtering and purifying the product obtained after the first mixing reaction. The present invention has no particular requirements for the conditions of the filtration and purification, and the present invention will not elaborate on them here. Those skilled in the art should not interpret them as limiting the present invention. For example, the reaction product can be cooled to room temperature, added to 5°C cold water, filtered, and then purified by column chromatography.

[0052] The present invention has no special requirements for the protective atmosphere in step (2). For example, it can be nitrogen and / or argon.

[0053] In some embodiments, in step (2), the second mixing reaction is carried out in the presence of N-bromosuccinimide and azobisisobutyronitrile.

[0054] In some embodiments, in step (2), the conditions of the second mixing reaction include: temperature of 20-30° C. and time of 0.5-3 h.

[0055] According to a specific embodiment, in step (2), the conditions of the second mixing reaction further include: filtering and recrystallizing the product obtained after the second mixing reaction. The present invention has no particular requirements for the conditions of the filtration and recrystallization, and the present invention will not be described in detail herein. Those skilled in the art should not interpret these conditions as limitations of the present invention. For example, the reaction product is cooled to room temperature, and the solution is filtered using filter paper. The filtered filter cake is dried, hexane is added, and then filtered again to obtain a filtered product.

[0056] According to a specific embodiment, in step (2), the conditions of the second mixing reaction further include: dissolving the filtered product in tetrahydrofuran, adding N-bromosuccinimide, refluxing under vigorous stirring, and then recrystallizing using hexane to obtain the intermediate II.

[0057] In some embodiments, the present invention has no particular requirements for the protective atmosphere in step (3). For example, it can be nitrogen and / or argon.

[0058] 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 case, the scheme of the present application provides the obtained polyfullerene macromolecule with higher stability.

[0059] In some embodiments, in step (3), the third mixing reaction is carried out under conditions including: temperature of 50-100°C, time of 0.5-4h.

[0060] According to a specific embodiment, in step (3), the third mixing reaction is further carried out under conditions including: after the third mixing reaction is completed, the obtained product is subjected to extraction, washing, purification and the like. The present application does not have special requirements for the conditions of the extraction, washing, purification, which will not be described herein again and should not be understood as a limitation to the present application. Exemplarily, ethyl acetate can be used for extraction, and the product can be washed with 0.1M EDTA-2Na solution and distilled water respectively three times, and purified by column.

[0061] In some embodiments, in step (4), the solvent is selected from at least one of super dry toluene, chlorobenzene, o-dichlorobenzene.

[0062] 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 the present application have found that, in this preferred case, the scheme of the present application provides the obtained polyfullerene macromolecule with stronger interfacial compatibility.

[0063] In some embodiments, in step (4), the fourth mixing reaction is carried out under conditions including: temperature of 90-120°C, time of 24-48h.

[0064] According to a specific embodiment, in step (4), the fourth mixing reaction is further carried out under conditions including: after the fourth mixing reaction is completed, the obtained product is subjected to separation and purification. The present application does not have special requirements for the conditions of the separation and purification, which will not be described herein again and should not be understood as a limitation to the present application. Exemplarily, the product can be first spin-evaporated to remove the solvent, then dissolved in o-dichlorobenzene, precipitated with methanol, and extracted with acetone and n-hexane.

[0065] According to a specific embodiment, the method of the present application comprises: (1) carrying out a first mixing reaction of o-methyl hydroquinone, anhydrous potassium carbonate and bromoiso-octane in the presence of acetonitrile, and then filtering and purifying to obtain an intermediate 1; (2) in the presence of a protective atmosphere, intermediate 1, N-bromosuccinimide, azobisisobutyronitrile, carbon tetrachloride are subjected to a second mixed reaction, and then filtered; tetrahydrofuran, N-bromosuccinimide are added, and refluxed for 1h under stirring, and then recrystallized to obtain intermediate 2; (3) in the presence of a protective atmosphere, intermediate 2, bis- (1, 5-cyclooctadiene) nickel, 2, 2'-bipyridine, N, N-dimethylformamide are subjected to a third mixed reaction, and then extracted, washed and purified to obtain intermediate 3; (4) in the presence of super-dry toluene, intermediate 3, C60, cuprous bromide, 2, 2'-bipyridine are subjected to a fourth mixed reaction, and then precipitated and extracted to obtain a polyfullerene macromolecule.

[0066] As described above, the third aspect of the present application provides an application of the polyfullerene macromolecule of the first aspect in preparing a photoelectric device structure.

[0067] In some embodiments, the polyfullerene macromolecule is used to prepare the photoelectric device by at least one of spin coating, blade coating, slot coating, dip coating and spray coating.

[0068] According to a specific embodiment, the polyfullerene macromolecule is used to prepare the photoelectric device by at least one of spin coating, blade coating and spray coating.

[0069] In some embodiments, the photoelectric device is selected from at least one of a solar cell, a field effect transistor, a photodetector, a radiation detector and a light emitting diode.

[0070] According to a specific embodiment, the solar cell is an organic solar cell and / or a perovskite solar cell.

[0071] As described above, the fourth aspect of the present application provides an organic solar cell, which comprises an electrode layer, a hole transport layer, an organic light absorption layer, an electron transport layer and a base layer. The electron transport layer and / or the organic light absorption layer comprises the polyfullerene macromolecule of the first aspect.

[0072] In some embodiments, the organic solar cell comprises the electrode layer, the hole transport layer, the organic light absorption layer, the electron transport layer and the base layer which are sequentially stacked.

[0073] In some embodiments, the organic solar cell comprises the electrode layer, the electron transport layer, the organic light absorption layer, the hole transport layer and the base layer which are sequentially stacked.

[0074] According to a specific embodiment, the material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

[0075] According to a 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'-tetra(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), 2,2',7,7'-tetra(N,N-di-p-ethoxyphenylamine)-9,9'-spirobifluorene, poly(3-hexylthiophene), NiO, MoO3, V2O5.

[0076] 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, [6,6]-phenyl-C61-butyric acid methyl ester, indene-C60 bisadduct, zirconium acetylacetonate, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene, poly(9,9-dioctylfluorene-alt-bipyridine), ZnO, LiF, TiO2, SnO2, Nb2O5. In this preferred case, the organic solar cell provided by the solution of the present application has a photoelectric conversion efficiency of no less than 15%.

[0077] As previously described, the fifth aspect of the present application provides a perovskite solar cell, which contains an electrode layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and a base layer arranged in sequence. The perovskite light-absorbing layer contains the polyfullerene polymer of the first aspect.

[0078] In some embodiments, the material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

[0079] In some embodiments, the material forming the electrode layer is selected from at least one of copper, aluminum, carbon, and chromium.

[0080] According to a particularly preferred embodiment, the material forming the perovskite light-absorbing layer comprises a metal halide perovskite of 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, phenethylamine ion; B is at least one of lead ion, tin ion, cadmium ion, germanium ion, zinc ion, nickel ion; X is at least one of fluoride ion, chloride ion, bromide ion, iodide ion. In this preferred case, the perovskite solar cell provided by the scheme of the present application has a photoelectric conversion efficiency of no less than 20%.

[0081] In some embodiments, the perovskite light-absorbing layer is MA 0.7 FA 0.3 PbI3perovskite polycrystalline thin film. The MA 0.7 FA 0.3 PbI3perovskite polycrystalline thin film contains lead iodide (PbI2), formamidinium iodide (FAI), and methylammonium iodide (MAI).

[0082] In some embodiments, the substrate layer is indium tin oxide (ITO) conductive glass.

[0083] According to a specific embodiment, the method for preparing the perovskite solar cell comprises: The ITO conductive glass is pretreated, then PTAA is scraped on the surface of the ITO conductive glass, then MA 0.7 FA 0.3 PbI3perovskite polycrystalline thin film, then polyfullerene PFBP-40EH polymer is scraped on the surface of the thin film, and finally BCP and copper electrode are evaporated to obtain the perovskite solar cell.

[0084] The present application will be described in detail by way of examples below. In the following examples, the raw materials are all commercially available unless otherwise specified.

[0085] Room temperature or normal temperature as used herein means 25±2℃. C60, commercially available from Anhui Zesheng Science and Technology Co., Ltd., with a trade name of A17160.

[0086] Bis-(1,5-cyclooctadiene) nickel, commercially available from Anhui Zesheng Science and Technology Co., Ltd., with a trade name of E063628.

[0087] Indium tin oxide (ITO) conductive glass, commercially available from Suzhou Shangyang Solar Technology Co., Ltd., with a trade name of TX 07-12.

[0088] PTAA, commercially available from Lixi'ai (Shanghai) Chemical Industry Development Co., Ltd., with a trade name of P3179.

[0089] MA 0.7 FA 0.3PbI3perovskite polycrystalline thin film raw material MAI was purchased from Greatcell, with product brand SKU MS101000; FAI was purchased from Greatcell, with product brand SKU MS150000; PbI2was purchased from Sigma-Aldrich, with product brand 900168.

[0090] BCP, purchased from Tiando (Shanghai) Chemical Industry Development Co., Ltd., with product brand B2694.

[0091] PCBM, purchased from Nanjing Zhiyan Technology Co., Ltd., with product brand PCBM(60).

[0092] Example 1 (1) 1.24 g of o-methyl-p-hydroquinone, 4.1 g of anhydrous potassium carbonate were dissolved in 40 mL of acetonitrile, heated to reflux for 30 minutes, then 4.0 g of bromoiso-octane was added, and refluxed for 8 h. After cooling to room temperature, add cold water at 5 ℃, filter 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).

[0093] (2) In a nitrogen-protected flask, 1.0 g of intermediate 1, 0.51 g of N-bromosuccinimide, 0.13 g of azobisisobutyronitrile and 10 mL of carbon tetrachloride were added, heated to reflux for 1 h. Then the temperature of the solution was lowered to room temperature, and then the solution was filtered with filter paper. The filter cake after filtration was dried, 60 mL of hexane was added, and then filtered again. The filtered product was dissolved in 10 mL of tetrahydrofuran, and then 0.51 g of N-bromosuccinimide was added, and refluxed for 1 h with vigorous stirring, then recrystallized with 60 mL of hexane to obtain 1.25 g of intermediate 2.

[0094] (3) In a nitrogen-protected dry flask, 0.30 g of bis-(1,5-cyclooctadiene) nickel, 0.20 g of 2,2'-bipyridine and 20 mL of N,N-dimethylformamide were added, and heated to 80 ℃ for 30 minutes. Then 1.0 g of intermediate 2 was added, and reacted at 80 ℃ for 2 h. After the reaction was completed, the product was extracted with ethyl acetate and washed with 0.1 M EDTA-2Na solution and distilled water three times, respectively, and purified by column to obtain 0.77 g of intermediate 3.

[0095] (4) In a dry flask, 72 mL of super dry toluene, 120 mg of C60, 48 mg of cuprous bromide, 105 mg of 2,2'-dipyridyl were added, and stirred at room temperature for 2 hours. After C60 was dissolved, 142 mg of intermediate 3 was added, and then heated to reflux for 24 h. After the reaction was completed and cooled to room temperature, the toluene solvent was removed by rotary evaporation, and the reaction product was dissolved in o-dichlorobenzene and then precipitated with methanol, and then placed in a Soxhlet extractor and extracted with acetone and n-hexane, respectively. The final product was a black-brown polyfullerene polymer, named PFBP-4OEH, with a number average molecular weight of 9000.

[0096] The structure of intermediate 1 is: , and the nuclear magnetic resonance result is: 1 H 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 spectrum result: HRMS (Maldi-tof) m / z: [M] found 348.30375.

[0097] The structure of intermediate 2 is: , and the structure of intermediate 3 is:

[0098] The structure of PFBP-4OEH is:

[0099] Example 2 The indium tin oxide (ITO) conductive glass (substrate layer) was treated in an ultraviolet ozone cleaning machine for 15 minutes, and then 7 nm thick PTAA (hole transport layer) was scraped on the surface, and then 300 nm thick MA 0.7 FA 0.3 PbI3 perovskite polycrystalline thin film (perovskite light absorbing layer), then 10 nm thick polyfullerene PFBP-4OEH polymer (electron transport layer) was scraped on the surface of the thin film, and finally 5 nm of BCP (electron transport layer) and 100 nm of copper electrode (electrode layer) were evaporated, to obtain a perovskite solar cell based on PFBP-4OEH electron transport layer.

[0100] Comparative Example The indium tin oxide (ITO) conductive glass (substrate layer) is placed in an ultraviolet ozone cleaning machine for 15 minutes, and then a 7nm-thick PTAA (hole transport layer) is scraped on the surface of the ITO conductive glass, and then a 300nm-thick MA 0.7 FA 0.3 PbI3 perovskite polycrystalline thin film (perovskite light-absorbing layer), then a 10nm-thick PCBM (electron transport layer) is scraped on the surface of the thin film, and finally, 5nm of BCP (electron transport layer) and 100nm of copper electrode (electrode layer) are evaporated, to obtain a perovskite solar cell based on the PCBM electron transport layer.

[0101] Test Example The J-V characteristics of the solar device were measured in air using an LED 3A solar simulator (BG-LED3A-100S, AAA class solar simulator), the power of the simulated light was calibrated to 100 mW using a silicon reference cell (Newport 91150V). All devices were measured using a Keithley 2400 source meter at room temperature in air at a scan rate of 0.1 V s -1 , with a delay time of 10 ms. The aperture area was 7.5 mm 2 , and the test results are shown in Table 1 and Figure 1 .

[0102] The light stability of the device was evaluated using an automatic maximum power point tracker (91 PVKSOLAR). The encapsulated device was measured under continuous illumination with a solar simulator (100 mW cm -2 ) at 85℃ in air with a relative humidity of 50±10%, and the test results are shown in Figure 2 .

[0103] Table 1

[0104] In summary, the present application provides a high-performance, stable, solution-processed polyfullerene macromolecule, which replaces the traditional small-molecule fullerene material. The photovoltaic device, such as a perovskite solar cell, introduced with the polyfullerene macromolecule has higher cell efficiency and service life.

[0105] Specifically, as can be seen from the results in Table 1 and Figure 1 , the photoelectric conversion efficiency of the perovskite solar cell based on PFBP-4OEH of the present application exceeds that of the perovskite solar cell based on PCBM, and as can be seen from the results in Figure 2 , the stability of the perovskite solar cell is greatly improved.

[0106] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A polyfullerene macromolecule, characterized by, The structure of the polyfullerene macromolecule is shown as formula (1): Formula (1), wherein in formula (1) R1, R2, R3, R4, R5, R6, R7, R8are each independently selected from the group consisting of H, C4-C 40 aryl, C1-C 40 linear alkyl, C3-C 40 branched alkyl, C3-C 40 cycloalkyl, -X-R x ; R1, R2, R3, R4, R5, R6, R7and R8are not simultaneously H, and R1, R2, R3, R4, R5, R6, R7or R8optionally contain at least one substituent from the group consisting of F, Cl, Br, I, CN; X is -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -C(R0)=C(R 00 )-, -C≡C- at least one; R x is C4-C 40 aryl, C1-C 40 linear alkyl, C3-C 40 branched alkyl or C3-C 40 cycloalkyl; R0and R 00 each independently selected from C1-C 40 linear alkyl, C3-C 40 branched alkyl, C3-C 40 cycloalkyl; n is an integer from 1 to 10000000.

2. The polyfullerene polymer of claim 1, wherein In formula (1), R1, R2, R3, R4, R5, R6, R7, R8are each independently selected from the group consisting of H, C4-C 30 aryl, C1-C 30 linear alkyl, C3-C 30 branched alkyl, C3-C 30 cycloalkyl, -X-R x ; R1, R2, R3, R4, R5, R6, R7and R8are not simultaneously H, and R1, R2, R3, R4, R5, R6, R7or R8optionally contain at least one substituent from the group consisting of F, Cl, Br, I, CN; X is -O-, -S-, -C(O)-, -C(O-)-O-, -OC(O)-, -OC(O)-O-, -C(R0)=C(R 00 )-, -C≡C- at least one; R x is C4-C 30 aryl, C1-C 30 linear alkyl, C3-C 30 branched alkyl or C3-C 30 cycloalkyl; R0and R 00 each independently selected from C1-C 30 linear alkyl, C3-C 30 branched alkyl, C3-C 30 cycloalkyl; n is an integer from 1 to 10000000.

3. The polyfullerene polymer of claim 2, wherein In formula (1), R1, R4, R5, R8 are all H; R2and R3are the same and are -O-R x ; R6and R7are the same and are -O-R x ; R in R2 and R6 x each independently selected from C4-C 30 aryl, C1-C 30 straight-chain alkyl, C3-C 30 branched alkyl and C3-C 30 cycloalkyl; n is an integer from 1 to 10000000.

4. The polyfullerene polymer of claim 3, wherein In formula (1), R1, R4, R5, R8 are each H; R2 and R3 are the same, -O-R x ; R6 and R7 are the same, -O-R x ; R x each independently is selected from any one of the following: ， n is an integer from 1 to 10000000.

5. The polyfullerene polymer of claim 4, wherein The polyfullerene macromolecule is PFBP-4OEH, and the structure is shown as formula (2): Formula (2), n is an integer from 1 to 10000000.

6. A method for preparing the polyfullerene macromolecule PFBP-40EH as defined in claim 5, characterized in that The method comprises: (1) in the presence of a solvent, under alkaline conditions, a first raw material and a second raw material are subjected to a first mixing reaction to obtain an intermediate 1; the first raw material is ortho-methyl-p-hydroquinone, and the second raw material is bromoiso-octane; (2) in the presence of a protective atmosphere, the intermediate 1 and carbon tetrachloride are subjected to a second mixing reaction to obtain an intermediate 2; (3) in the presence of a protective atmosphere, the intermediate 2 and bis-(1,5-cyclooctadiene) nickel are subjected to a third mixing reaction to obtain an intermediate 3; (4) in the presence of a solvent, the intermediate 3 and C60 are subjected to a fourth mixing reaction to obtain the polyfullerene macromolecule.

7. The method of claim 6, wherein, In step (2), the second mixing reaction is carried out in the presence of N-bromosuccinimide and azobisisobutyronitrile.

8. Use of the polyfullerene macromolecule according to any one of claims 1-5 in the preparation of a photoelectric device structure.

9. Use according to claim 8, characterized in that, The polyfullerene macromolecule is prepared into the photoelectric device by at least one process selected from spin coating, blade coating, slot coating, dip coating, and spray coating.

10. Use according to claim 8, characterized in that, The photoelectric device is selected from at least one of a solar cell, a field effect transistor, a photoelectric detector, a radiation detector, and a light emitting diode.

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

12. An organic solar cell, characterized by The organic solar cell comprises an electrode layer, a hole transport layer, an organic light absorption layer, an electron transport layer, and a base layer. The electron transport layer and / or the organic light absorption layer comprises the polyfullerene macromolecule according to any one of claims 1-5.

13. The organic solar cell according to claim 12, characterized in that The organic solar cell comprises the electrode layer, the hole transport layer, the organic light absorption layer, the electron transport layer, and the base layer which are sequentially stacked.

14. The organic solar cell according to claim 12, characterized in that The organic solar cell comprises the electrode layer, the electron transport layer, the organic light absorption layer, the hole transport layer, and the base layer which are sequentially stacked.

15. The organic solar cell according to any one of claims 12 to 14, wherein The material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon, and chromium.

16. The organic solar cell according to any one of claims 12 to 14, wherein 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'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), 2,2',7,7'-tetrakis(N,N-di-p-ethoxyphenylamine)-9,9'-spirobifluorene, poly(3-hexylthiophene), NiO, MoO3, and V2O5.

17. The organic solar cell according to any one of claims 12 to 14, wherein The material forming the electron transport layer is selected from at least one of fullerene, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, [6,6]-phenyl-C61-butyric acid methyl ester, indene-C60 bisadduct, zirconium acetylacetonate, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene, poly(9,9-dioctylfluorene-alt-bipyridine), ZnO, LiF, TiO2, SnO2, Nb2O5.

18. A perovskite solar cell, characterized by, The perovskite solar cell contains an electrode layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer and a base layer which are sequentially stacked; The perovskite light-absorbing layer contains the polyfullerene polymer of any one of claims 1-5.

19. The perovskite solar cell of claim 18, wherein, The material forming the electrode layer is selected from at least one of gold, silver, copper, aluminum, carbon and chromium.

20. The perovskite solar cell of claim 18, wherein, The material forming the perovskite light-absorbing layer includes a metal halide perovskite with a chemical formula of ABX3; A is at least one of methylamine ion, formamidine 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 fluorine ion, chlorine ion, bromine ion and iodine ion.

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