Fullerene composite material and manufacturing method thereof, perovskite solar cell and manufacturing method thereof, and electric device

Abstract

The present application relates to a fullerene composite material and a method for manufacturing the same, a perovskite solar cell and a method for manufacturing the same, and an electrical device. The fullerene composite material includes a host material and a dopant material, the host material including at least one of a first fullerene and a first fullerene derivative, the dopant material being at least one selected from a second fullerene and a second fullerene derivative, and a portion of the molecular structure of the dopant material being inserted into the lattice of the first fullerene and / or the first fullerene derivative.

Description

[Technical Field]

[0001] The present application relates to the technical field of solar cells, and in particular to fullerene composite materials and methods for producing same, perovskite solar cells and methods for producing same, and electrical devices. [Background technology]

[0002] As research into solar cells progresses, perovskite solar cells have attracted widespread attention due to their high photoelectric conversion efficiency and simple manufacturing process.

[0003] In the structure of perovskite solar cells, fullerenes and their derivatives are commonly used as electron acceptors. However, as research into perovskite solar cells has progressed, it has become clear that the photoelectric conversion efficiency of cells obtained by fabricating the electron transport layer of perovskite solar cells using pure fullerenes and their derivatives is still low. Summary of the Invention

[0004] According to each embodiment of the present application, the present application provides a fullerene composite material including a host material and a dopant material, wherein the host material includes at least one of a first fullerene and a first fullerene derivative, the dopant material is at least one selected from a second fullerene and a second fullerene derivative, and a portion of the molecular structure of the dopant material is inserted into the lattice of the first fullerene and / or the first fullerene derivative.

[0005] In the present application, by doping a host material containing a first fullerene and / or a first fullerene derivative with at least one of a second fullerene and a second fullerene derivative, the conductivity of the fullerene composite material can be increased, and the photoelectric conversion efficiency of the perovskite solar cell can be improved.

[0006] In some embodiments, the mass percentage of the dopant material relative to the total mass of the first fullerene and / or the first fullerene derivative and the dopant material is 0.0001% to 1%. If the mass percentage of the dopant material is too small, the doping effect will be poor, while if the mass percentage of the dopant material is too large, the inherent structure of the host material may be excessively affected.

[0007] In some embodiments, the first fullerene comprises at least one of C50, C60, and C70, and the first fullerene derivative comprises at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM. These fullerenes and fullerene derivatives are derived from a variety of sources and are readily available.

[0008] In some embodiments, the second fullerene comprises at least one of C50, C60, and C70, and the second fullerene derivative comprises at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM. These fullerenes and fullerene derivatives are derived from a variety of sources and are readily available.

[0009] This application is The method includes a step of heat-treating a mixture obtained by mixing the first raw material and the second raw material with the first solvent, The present invention further provides a method for producing a fullerene composite material, wherein the first raw material contains a first fullerene and / or a first fullerene derivative and / or a raw material for synthesizing the first fullerene derivative, and the second raw material contains at least one of a second fullerene and a second fullerene derivative used as a dopant material.

[0010] In this manufacturing method, adding the dopant material to the reaction system before the heat treatment allows the dopant material to be dispersed more uniformly in the reaction system, and the dopant material is uniformly doped with the first fullerene derivative in the formed fullerene composite material, which reduces the risk of the dopant material agglomerating and is advantageous for improving the doping uniformity.

[0011] In some embodiments, the raw materials for synthesizing the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and a base, and mixing the first raw material and the second raw material in a solvent includes: The method includes dispersing the methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate and the base in a first sub-solvent, dispersing the second raw material and the third fullerene in a second sub-solvent, and mixing the two solution systems.

[0012] In some embodiments, the molar ratio of the third fullerene, the dopant material, the methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and the base is 1:(10 -5 ~10 -2 ):(1~2):(1~10).

[0013] In some embodiments, the first secondary solvent comprises pyridine.

[0014] In some embodiments, the second co-solvent comprises at least one of toluene, xylene, chlorobenzene, and dichlorobenzene.

[0015] In some embodiments, the base comprises at least one of sodium methoxide, cesium carbonate, sodium hydroxide, and potassium hydroxide.

[0016] In some embodiments, the first solvent comprises at least one of toluene, xylene, chlorobenzene, and dichlorobenzene.

[0017] In some embodiments, the heat treatment temperature is 100°C to 300°C.

[0018] In some embodiments, the heat treatment time is 24 hours to 60 hours.

[0019] In some embodiments, the heat treatment comprises heating to reflux.

[0020] The present application provides a semiconductor device comprising a first electrode, a perovskite layer, an electron transport layer, and a second electrode, which are stacked in this order; the electron transport layer comprises the fullerene composite material, or The present invention further provides a perovskite solar cell, wherein the electron transport layer comprises a fullerene composite material obtained by the above-described manufacturing method.

[0021] In the above-described perovskite solar cell, the electron transport layer contains a fullerene composite material, which can improve the performance of the perovskite solar cell.

[0022] In some embodiments, the electron transport layer has a thickness of 10 nm to 100 nm.

[0023] This application is forming a perovskite layer on the first electrode; forming an electron transport layer on the perovskite layer; forming a second electrode on the electron transport layer; The present invention further provides a method for manufacturing a perovskite solar cell, wherein the electron transport layer comprises a fullerene composite material, the fullerene composite material comprising a host material and a dopant material, the host material comprising at least one of a first fullerene and a first fullerene derivative, the dopant material being at least one selected from a second fullerene and a second fullerene derivative, and the molecular structure of the dopant material being partially inserted into the lattice of the first fullerene and / or the first fullerene derivative.

[0024] The present application further provides an electrical device comprising the perovskite solar cell. [Brief explanation of the drawings]

[0025] In order to more clearly explain the technical solution of the present application, the drawings used in the present application are briefly described below. The drawings described below only show some embodiments of the present application, and it is obvious that those skilled in the art can conceive of other drawings based on these drawings without creative work.

[0026] [Figure 1] FIG. 1 is a structural schematic diagram of an example perovskite solar cell.

[0027] To better describe and explain the embodiments and / or examples of the inventions disclosed herein, reference may be made to one or more drawings, in which additional detail or illustrations for the purposes of illustrating the drawings should not be considered as limiting the scope of any one of the disclosed inventions, the presently described embodiments and / or examples, and the best modes of these inventions as currently understood. DETAILED DESCRIPTION OF THE INVENTION

[0028] The perovskite solar cell, its manufacturing method, and electrical device of the present application will be described in more detail below with reference to specific examples. The present invention is not limited to the embodiments described herein and may be embodied in many different forms. Rather, these embodiments are provided to provide a more thorough and complete understanding of the present disclosure.

[0029] The details of one or more embodiments of the application are set forth in the drawings and description below. Other features, objects, and advantages of the application will become apparent from the description, drawings, and claims.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The terms used in the present specification are for the purpose of describing specific examples only and are not intended to limit the present invention.

[0031] The "ranges" disclosed herein are defined by lower and upper limits. A given range is defined by selecting one lower limit and one upper limit, and the selected lower and upper limits define the boundaries of that particular range. Such defined ranges may or may not include endpoints and may be arbitrarily combined; that is, any lower limit and any upper limit may be combined to form a single range. For example, if ranges of 60 to 120 and 80 to 110 are recited for a particular parameter, the ranges of 60 to 110 and 80 to 120 are also understood to be predictable. Furthermore, if the minimum range values ​​are 1 and 2 and the maximum range values ​​are 3, 4, and 5, the ranges of 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 are all predictable. In this application, unless otherwise specified, a numerical range of "a to b" represents a shorthand notation for any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 and 5" are listed herein, and "0 to 5" is merely shorthand for combinations of these numbers. Note that when a parameter is described as an integer ≧2, this is equivalent to disclosing that the parameter is an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0032] Unless otherwise specified, all embodiments and alternative embodiments in this application can be combined with each other to form new technical solutions.

[0033] Unless otherwise specified, all technical features and alternative technical features in this application can be combined with each other to form a new technical solution.

[0034] Unless otherwise specified, all steps in the present application may be performed in order or randomly, preferably in order. For example, when the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed in order, or may include steps (b) and (a) performed in order. For example, when it is stated above that the method may further include step (c), it means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or may include steps (a), (c), and (b), or may include steps (c), (a), and (b).

[0035] Unless otherwise specified, the terms "comprise" and "comprises" in this application are open-ended but may also be closed-ended. For example, the terms "comprise" and "comprises" may further include or include other components not listed, or may include or include only the listed components.

[0036] Unless otherwise specified, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, any of the following conditions satisfy the condition "A or B": A is true or present and B is false or absent; A is false or absent and B is true or present; or A and B are both true or present.

[0037] Unless otherwise specified, in this application, the term "room temperature" generally refers to a temperature between 4°C and 30°C, preferably 25±5°C.

[0038] The present application provides a fullerene composite material including a host material and a dopant material, wherein the host material includes at least one of a first fullerene and a first fullerene derivative, and the dopant material is at least one selected from a second fullerene and a second fullerene derivative, and a portion of the molecular structure of the dopant material is inserted into the lattice of the first fullerene and / or the first fullerene derivative.

[0039] The fullerene composite material of the present application comprises a host material containing a first fullerene and / or a first fullerene derivative doped with at least one of a second fullerene and a second fullerene derivative, and a part of the molecular structure of the dopant material is inserted into the lattice of the first fullerene and / or the first fullerene derivative, thereby increasing the electrical conductivity of the fullerene composite material and improving the photoelectric conversion efficiency of perovskite solar cells.

[0040] In fullerene derivatives, the presence of branched chains increases the intermolecular distance, making it difficult to extract carriers and limiting the improvement of the conductive performance of the fullerene derivative. By inserting a part of the molecular structure of the dopant material into the lattice of the first fullerene and / or the first fullerene derivative, the intermolecular distance can be shortened, the electron transport capacity can be increased, and the conductivity of the fullerene composite material can be improved.

[0041] It can be understood that the first fullerene and the second fullerene can be the same or different, and the first fullerene derivative and the second fullerene derivative can be the same or different.

[0042] In some embodiments, the first fullerene comprises at least one of C50, C60, and C70. The first fullerene derivative comprises at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM. The second fullerene comprises at least one of C50, C60, and C70. The second fullerene derivative comprises at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM. These fullerenes and fullerene derivatives are derived from a variety of sources and are readily available.

[0043] It can be further understood that fullerene derivatives are typically obtained by modifying fullerenes, and since the lattice of fullerenes is typically spherical, the lattice of the fullerene derivative is also referred to as having a primarily spherical shape. When a portion of the molecular structure of a dopant material is inserted into the lattice of the first fullerene and / or the first fullerene derivative, it can be expressed as a portion of the molecular structure of the dopant material being inserted into the spherical lattice of the first fullerene and / or the first fullerene derivative. Optionally, when the dopant material has a side chain, the side chain of the dopant material is inserted into the lattice of the first fullerene and / or the first fullerene derivative. It can be understood that fullerene derivatives are typically obtained by modifying fullerenes such as C50, C60, and C70.

[0044] It can be further understood that when a portion of the molecular structure of the dopant material is inserted into the lattice of the first fullerene and / or first fullerene derivative, another portion of the molecular structure of the dopant material may protrude from the lattice of the first fullerene and / or first fullerene derivative and may be attached to the outer surface of the lattice of the first fullerene and / or first fullerene derivative.

[0045] In some embodiments, the weight percentage of the dopant material, as a percentage of the total weight of the first fullerene and / or first fullerene derivative and the dopant material, is 0.0001% to 1%. Optionally, the weight percentage of the dopant material, as a percentage of the total weight of the first fullerene and / or first fullerene derivative and the dopant material, is 0.0001%, 0.001%, 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc. If the weight percentage of the dopant material is too small, the doping effect will be poor, while if the weight percentage of the dopant material is too large, the inherent structure of the host material may be excessively affected.

[0046] Alternatively, the type and content of the dopant material can be measured by liquid chromatography, which is optionally performed under the following conditions: the chromatography column is a 15 cm long C18 directional column, the mobile phase is toluene:methanol=1:2, and the detector is a DAD detector.

[0047] In this application, the mass percentage of the dopant material as a percentage of the total mass of the first fullerene and / or first fullerene derivative and the dopant material may be expressed as the doping amount of the dopant material.

[0048] In some embodiments, the fullerene composite material comprises a host material and a dopant material, the host material being at least one selected from a first fullerene and a first fullerene derivative, the dopant material being at least one selected from a fullerene and a second fullerene derivative, and a portion of the molecular structure of the dopant material being inserted into the lattice of the first fullerene and / or the first fullerene derivative. Optionally, the mass percentage of the dopant material, as a percentage of the total mass of the first fullerene and / or the first fullerene derivative and the dopant material, is 0.0001% to 1%. Optionally, the mass percentage of the dopant material as a percentage of the total mass of the first fullerene and / or first fullerene derivative and the dopant material is 0.0001%, 0.001%, 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.

[0049] The present application further provides a method for producing a fullerene composite material, the method comprising the step of heat-treating a mixture of a first raw material and a second raw material in a first solvent, the first raw material containing a first fullerene and / or a first fullerene derivative and / or a raw material for synthesizing the first fullerene derivative, and the second raw material containing at least one of a fullerene and a second fullerene derivative used as a dopant material.

[0050] During the production of a fullerene composite material, aggregation of the dopant material is one of the factors that affect the performance of the composite material. In this production method, adding the dopant material to the reaction system before heat treatment allows the dopant material to be more uniformly dispersed in the reaction system. The dopant material is uniformly doped into the formed fullerene composite material by the first fullerene derivative, which reduces the risk of aggregation of the dopant material and is advantageous for improving doping uniformity.

[0051] In some embodiments, the first raw material contains raw materials for synthesizing a first fullerene derivative, and the raw materials for synthesizing the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and a base; and mixing the first raw material and the second raw material in a solvent includes dispersing methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate and the base in a first secondary solvent, dispersing the second raw material and the third fullerene in a second secondary solvent, and mixing the two solution systems.

[0052] Optionally, the third fullerene comprises at least one of C50, C60, and C70. Optionally, the first fullerene, the second fullerene, and the third fullerene may all be the same, or some or all may be different.

[0053] In some embodiments, the molar ratio of the third fullerene, the dopant material, methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and the base is 1:(10 -5 ~10 -2 ):(1-2):(1-10). Optionally, the molar ratio of the third fullerene, the dopant material, the methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and the base is 1:10. -5 :1:1, 1:10 -5 :1:5, 1:10 -5 :1:8, 1:10 -4 :1:1, 1:10 -4 :1:5, 1:10 -4 :1:8, 1:10 -3 :1:1, 1:10 -3 :1:5, 1:10 -3 :1:8, 1:10 -2 :1:1, 1:10 -2 :1:5, 1:10 -2 :1:8, etc.

[0054] In some embodiments, the first secondary solvent comprises pyridine.

[0055] Optionally, the second co-solvent includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene. Xylene includes at least one of o-xylene, m-xylene, and p-xylene. Dichlorobenzene includes at least one of o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene.

[0056] Optionally, the base comprises at least one of sodium methoxide, cesium carbonate, sodium hydroxide, and potassium hydroxide.

[0057] Alternatively, the raw materials for synthesizing the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and a base, and mixing the first raw material and the second raw material in a solvent includes adding methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate to a first secondary solvent, adding a base, stirring, and degassing the solution system so as to store it under an argon atmosphere; and adding the second raw material and the third fullerene to the second secondary solvent, and adding the resulting solution to a solution system containing the first secondary solvent.

[0058] Optionally, the raw materials for synthesizing the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and a base. The method further includes heat-treating a mixture of the first raw material and the second raw material in a first solvent, and then removing the solvent from the product obtained by the heat treatment to separate the product. Optionally, rotary evaporation may be used to remove the solvent. Optionally, column chromatography may be used to separate the product.

[0059] In some embodiments, the first raw material is a first fullerene derivative. The weight percentage of the dopant material, as a percentage of the total weight of the first fullerene derivative and the dopant material, is 0.0001% to 1%. Optionally, the weight percentage of the dopant material, as a percentage of the total weight of the first fullerene derivative and the dopant material, is 0.0001%, 0.001%, 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.

[0060] Optionally, the first raw material is a first fullerene derivative. The method further includes heat-treating the mixture of the first raw material and the second raw material in the first solvent, concentrating the product obtained by the heat treatment, and adding it to methanol for precipitation. The fullerene composite material is obtained by precipitation.

[0061] In some embodiments, the first solvent includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene. Xylene includes at least one of o-xylene, m-xylene, and p-xylene. Dichlorobenzene includes at least one of o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene.

[0062] In some embodiments, the heat treatment temperature is 100°C to 300°C. The heat treatment time is 24 hours to 60 hours. The heat treatment includes heating under reflux. Optionally, the heat treatment temperature is 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, 280°C, 300°C, etc. The heat treatment time is 24 hours, 30 hours, 36 hours, 48 ​​hours, 60 hours, etc.

[0063] In some embodiments, a method for producing methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate includes mixing methyl 4-benzoylbutyrate, p-toluenesulfonylhydrazide, and methanol, heating to reflux, cooling to room temperature, storing away from light, then transferring to -15°C and storing away from light overnight, suction filtering the product, recrystallizing the product in methanol, and vacuum-filtering the product at 40°C overnight to obtain methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate as a white solid. Optionally, the heating to reflux reaction time is 12 hours, and after cooling to room temperature, the product is stored away from light for 24 hours.

[0064] In some embodiments, a method for producing methyl 4-benzoylbutyrate includes dissolving benzoylbutyric acid in chlorobenzene, adding methanol and stirring until completely dissolved, adding hydrochloric acid dropwise, continuing to stir, heating and refluxing overnight, stopping the stirring, neutralizing with saturated sodium carbonate until no more bubbles remain, and separating the oil and water. Thereafter, extracting the aqueous phase with ethyl acetate, combining the organic phases and removing water with anhydrous calcium chloride, distilling the resulting mixture under reduced pressure to remove the solvent, and eluting and separating the resulting product through a silica gel column (using ethyl acetate and n-hexane as the eluent, with a volume ratio of ethyl acetate to n-hexane of 3:1) to obtain methyl 4-benzoylbutyrate as a pale yellow oily liquid.

[0065] The present application further provides an electron transport film. The electron transport film comprises the fullerene composite material described above or a fullerene composite material obtained by the method for producing a fullerene composite described above. Optionally, the electron transport film has a thickness of 10 nm to 100 nm. More optionally, the electron transport film has a thickness of 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc.

[0066] The present application further provides an electron transport slurry. The electron transport slurry includes a second solvent and further includes the fullerene composite described above or a fullerene composite obtained by the method for producing a fullerene composite described above. Optionally, the second solvent in the electron transport slurry includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene. The xylene includes at least one of o-xylene, m-xylene, and p-xylene. The dichlorobenzene includes at least one of o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene.

[0067] The present application further provides a perovskite solar cell. The perovskite solar cell includes a first electrode layer, a perovskite layer, an electron transport layer, and a second electrode layer, which are stacked in this order. The electron transport layer includes the fullerene composite material described above, or the electron transport layer includes the fullerene composite material obtained by the manufacturing method described above, or the electron transport layer includes the electron transport film described above, or the electron transport layer is manufactured from a material including the electron transport slurry described above. In the perovskite solar cell, the electron transport layer includes the fullerene composite material, thereby improving the performance of the perovskite solar cell.

[0068] Alternatively, an electron transport layer may be fabricated by spin coating and annealing a material comprising the electron transport slurry described above. Additionally, an electron transport layer may be fabricated by spin coating and annealing a material comprising the electron transport slurry described above.

[0069] Optionally, the thickness of the electron transport layer is 10 nm to 100 nm. Optionally, the thickness of the electron transport layer is 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc.

[0070] Alternatively, the electron transport layer can be obtained by spin coating and annealing a material comprising the electron transport slurry described above.

[0071] Optionally, the first electrode is a transparent electrode or a metal electrode. The second electrode is a transparent electrode or a metal electrode. Further optionally, the first electrode and the second electrode are different. Optionally, the transparent electrode is a transparent glass electrode.

[0072] In some embodiments, the first electrode is typically a transparent conductive glass. Optionally, the first electrode is at least one selected from fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), and indium tungsten oxide (IWO). Optionally, the thickness of the first electrode layer is 100 nm to 1000 nm, and optionally 300 nm to 800 nm.

[0073] In some embodiments, the second electrode is typically a metal electrode. Optionally, the second electrode is at least one selected from Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W, and alloys thereof. Optionally, the thickness of the second electrode is 20 nm to 200 nm, optionally 60 nm to 100 nm, and further optionally 70 nm to 90 nm. The perovskite layer is a light absorbing layer, and can be understood to be made of a perovskite material. Optionally, the chemical formula of the material of the perovskite layer is ABX3 or A2CDX6, where: A is an inorganic cation, an organic cation, or an organic-inorganic mixed cation, including at least one of an organic amine cation, a Cs cation, a K cation, a Rb cation, and a Li cation. The organic amine cation is (NR1R2R3R4) + , (R1R2N=CR3R4) + , (R1R2N-C(R5)=NR3R4) + or (R1R2N-C(NR5R6)=R3R4) + wherein R1, R2, R3, R4, R5, and R6 are each independently selected from H, substituted or unsubstituted C1-20 alkyl, or substituted or unsubstituted aryl. A is optionally a methylamino cation (CH3NH3 + )(MA +), carbamimidoyl cation (HC(NH2)2 + )(FA + ), cesium ions (Cs + ) and rubidium ion (Rb + ), and more preferably at least one of the methylamino cation (CH3NH3 + ) or carbamimidoyl cation (HC(NH2)2 + )

[0074] B is an inorganic cation or an organic cation or a mixed organic-inorganic cation including at least one of lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium, and optionally the divalent metal ion Pb 2+ and Sn 2+ At least one of the following is true:

[0075] C is an inorganic cation or an organic cation or a mixed organic-inorganic cation, optionally a monovalent metal ion such as Ag + And so on.

[0076] D is an inorganic or organic or mixed organic-inorganic cation, optionally a trivalent metal ion, such as the bismuth cation Bi 3+ , antimony cation Sb 3+ , indium cation In 3+ And so on.

[0077] X is an inorganic anion or an organic anion or a mixed organic-inorganic anion, and is optionally one or more of a halogen anion and a carboxylate anion, and is further optionally a bromide ion (Br - ) or iodide ion (I - )

[0078] In some embodiments, the bandgap of the perovskite layer is between 1.20 eV and 2.30 eV.

[0079] In some embodiments, the thickness of the perovskite layer is between 200 nm and 800 nm, optionally between 400 nm and 600 nm.

[0080] In some embodiments, the perovskite solar cell further comprises a hole transport layer between the first electrode and the perovskite layer. Optionally, the hole transport layer is selected from the group consisting of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly-3-hexylthiophene (P3HT), triptycene-cored triphenylamine (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamine)carbazole-spirobifluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS), polythiophene, nickel oxide (NiO x ), molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (CuO) and their derivatives, and at least one of the materials by doping or passivating them.

[0081] In some embodiments, the perovskite solar cell further comprises a first passivation layer between the perovskite layer and the hole transport layer. Optionally, the material of the first passivation layer is PTAA.

[0082] In some embodiments, the perovskite solar cell further comprises a second passivation layer and / or a buffer layer between the electron transport layer and the second electrode. Optionally, the material of the second passivation layer or buffer layer is bathocuproine (BCP).

[0083] Perovskite solar cells can be understood to include forward perovskite solar cells and inverted perovskite solar cells. For forward perovskite solar cells, the forward perovskite solar cell includes a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode, which are stacked in this order on the transparent electrode. For inverted perovskite solar cells, the inverted perovskite solar cell includes a transparent electrode, and a hole transport layer, a perovskite layer, an electron transport layer, and a metal electrode, which are stacked in this order on the transparent electrode. In this application, by selecting the materials for the first electrode and the second electrode, corresponding forward perovskite solar cells and inverted perovskite solar cells can be obtained.

[0084] Referring to Figure 1, the structure of a perovskite solar cell in one embodiment of the present application is shown. The first electrode is FTO, and a hole transport layer, a passivation layer, a perovskite layer, an electron transport layer, a passivation layer or buffer layer, and a metal electrode are stacked in this order on the first electrode. A glass substrate is provided on the surface of the FTO away from the perovskite layer.

[0085] The present application further provides a method for manufacturing a perovskite solar cell, the method comprising the steps of: forming a perovskite layer on a first electrode; forming an electron transport layer on the perovskite layer; and forming a second electrode on the electron transport layer, wherein the electron transport layer comprises a fullerene composite material, the fullerene composite material comprising a host material and a dopant material, the host material comprising a first fullerene derivative, the dopant material being at least one selected from fullerenes and second fullerene derivatives, and a portion of the molecular structure of the dopant material being inserted into the lattice of the first fullerene derivative.

[0086] Optionally, the perovskite layer is fabricated by spin coating and annealing. Optionally, the electron transport layer is fabricated by spin coating and annealing. Optionally, the second electrode is fabricated by evaporation.

[0087] Optionally, the electron transport layer is fabricated by spin coating and annealing the electron transport slurry described above.

[0088] The present application further provides an electric device, which includes the perovskite solar cell described above. Optionally, the electric device is an electric device in the fields of communications, transportation, industry and agriculture, lighting, etc. The electric device may include, for example, satellites, communications equipment, traffic lights, lighthouses, radio telephone booths, monitoring equipment in the field of oil drilling, power supply systems, camping lights, electric vehicles, chargers for electronic devices, etc.

[0089] Example The following examples of the present application are described. The examples described below are illustrative and are used only to interpret the present application, and should not be understood as limiting the present application. In the examples, specific techniques or conditions are not specified, and are carried out according to the techniques or conditions described in the literature in this field or the product specifications. Reagents and equipment used without specifying the manufacturer are all common products that are commercially available.

[0090] Example 1 The manufacturing process of the fullerene composite material in this example is as follows.

[0091] S101: Synthesis of methyl 4-benzoylbutyrate: A clean, dry 500 mL two-neck flask was taken, and 19.25 g (0.1 mol) of benzoylbutyric acid was added thereto and dissolved in 300 mL of chlorobenzene. 100 mL of methanol was added and stirred until completely dissolved. 30 mL of hydrochloric acid was added dropwise, and stirring was continued. The mixture was heated under reflux overnight. After confirming that the reaction had progressed completely by thin layer chromatography, stirring was stopped, and the mixture was neutralized with saturated sodium carbonate until no more bubbles remained. The mixture was then separated into oil and water. The aqueous phase was then extracted with ethyl acetate, and the organic phases were combined and water was removed with anhydrous calcium chloride. The solvent was removed by distillation under reduced pressure. The product was eluted and separated on a silica gel column (eluent: ethyl acetate / n-hexane (volume ratio 3:1)) to obtain 18 g of a pale yellow oily liquid, methyl 4-benzoylbutyrate.

[0092] S102: Synthesis of methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate: 10.5 g (0.05 mol) of methyl 4-benzoylbutyrate, 11.5 g (0.06 mol) of p-toluenesulfonylhydrazide, and 200 ml of methanol were heated to reflux in a single-necked round-bottom flask and reacted for 12 hours. The flask was then cooled to room temperature and stored in the dark for 24 hours. The flask was then transferred to -15°C and stored in the dark overnight. The product was filtered with suction and recrystallized in methanol. The product was then placed under vacuum at 40°C overnight to obtain 18.2 g of methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate as a white solid.

[0093] S103: Synthesis of F1-OMe: In a clean, dry 1 L three-neck flask, 11.25 g (0.03 mol) of methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate was dissolved in 250 mL of pyridine, 1.75 g of sodium methoxide was added, and the mixture was stirred. The mixture was degassed and stored under an argon atmosphere. Separately, a clean, dry round-bottom flask was taken, and 10.8 g of C60 was added to it, and the mixture was dissolved in 300 mL of o-dichlorobenzene. The mixture was added dropwise to the above three-neck flask and heated under reflux for 24 hours. The product was rotary evaporated to remove most of the solvent, and the product was separated by column chromatography to obtain 6.83 g of the product F1-OMe.

[0094] S104: Fullerene composite material: 6.83 g of F1-OMe and the dopant material C50 were dissolved in o-dichlorobenzene, and the resulting product was heated under reflux for 48 hours. The product was concentrated and then added to methanol for precipitation to obtain a fullerene composite. In this example, the dopant material was C50 and the host material was PC61BM. The mass percentage of the dopant material C50 in the resulting fullerene composite was 0.1%, i.e., the doping amount was 0.1%.

[0095] The manufacturing process of the perovskite solar cell in this example is as follows.

[0096] S201: 20 sheets of 2.0cm x 2.0cm FTO conductive glass were taken and 0.35cm of FTO was removed from each end by laser etching to expose the glass substrate. The etched FTO conductive glass was then ultrasonically cleaned in water, acetone, and isopropyl alcohol, in that order. The cleaned FTO conductive glass was then sprayed with a nitrogen gun to remove the solvent, and placed in an ultraviolet ozone device for ultraviolet ozone cleaning.

[0097] S202: 10 mg / mL nickel oxide nanoparticles (water as the solvent) were spin-coated at 4000 rpm onto an FTO substrate that had been subjected to UV-ozone cleaning, and then annealed on a hot plate at 100°C for 30 minutes to form a hole transport layer.

[0098] S203:PTAA was dissolved in chlorobenzene at a concentration of 1 mg / mL, stirred, and then filtered through a 0.45 μm filter membrane. 50 μL of the solution was then dropped onto the hole transport layer, spin-coated at 4000 rpm, and annealed on a hot plate at 100°C for 10 minutes to obtain a passivation layer.

[0099] S204: 223 mg of lead iodide (PbI2), 80 mg of formamidinium iodide (FAI), and 15 mg of methylammonium chloride (MACl) were weighed and dissolved in a mixture of 0.8 mL of DMF and 0.2 mL of DMSO. The mixture was stirred for 3 hours and filtered through a 0.22 μm organic filter membrane to obtain a perovskite precursor solution. The perovskite precursor solution was spin-coated onto the passivation layer at 3000 rpm, annealed at 120 °C for 30 minutes, and cooled to room temperature to form a perovskite layer. The active material in the perovskite layer was FA-based, and the thickness was 500 nm.

[0100] S205: The fullerene composite material obtained in S104 was dissolved in chlorobenzene to form a 20 mg / mL electron transport slurry. The electron transport slurry was spin-coated onto the perovskite layer at 1500 rpm and annealed at 100°C for 10 minutes to form a 50 nm thick electron transport layer. Next, a 0.5 mg / mL BCP solution in isopropyl alcohol was spin-coated at 5000 rpm to form a 5 nm thick passivation layer. The resulting layer was then placed in an evaporator to form a metal electrode (Ag) by vapor deposition, yielding a perovskite solar cell.

[0101] Example 2 This example differs from Example 1 in that the dopant material was PC51BM. Here, PC51BM was produced by steps S101 to S103 in Example 1, except that C50 was used instead of C60 in S103.

[0102] When producing the fullerene composite material, PC51BM was used instead of C50 as the dopant material in S104 in Example 1.

[0103] In this example, the dopant material was PC51BM, the host material was PC61BM, and the mass percentage of the dopant material PC51BM in the obtained fullerene composite material was 0.05%, that is, the doping amount was 0.05%.

[0104] Example 3 This example differs from Example 1 in that C50 and C60 were used instead of C60 in S103. Here, the total mass of C50 and C60 was equal to the mass of C60 in S103 in Example 1, and the mass percentage of C50 relative to the total mass of C50 and C60 was 0.1%.

[0105] In this example, the dopant material was PC51BM, the host material was PC61BM, and the mass percentage of the dopant material PC51BM in the obtained fullerene composite material was 0.05%, that is, the doping amount was 0.05%.

[0106] Example 4 This example differs from Example 1 in that C50, C60, and C70 were used instead of C60 in S103. Here, the total mass of C50, C60, and C70 was equal to the mass of C60 in S103 in Example 1, and the mass percentage of C50 relative to the total mass of C50, C60, and C70 was 0.1% and the mass percentage of C70 was 0.03%.

[0107] In this example, the dopant materials were PC51BM and PC71BM, the host material was PC61BM, and the mass percentage of the dopant material PC51BM in the obtained fullerene composite was 0.05%, and the mass percentage of the dopant material PC71BM in the fullerene composite was 0.015%, that is, the doping amount of PC51BM was 0.05%, and the doping amount of PC71BM was 0.03%.

[0108] Example 5 This example differs from Example 1 in that the amount of the dopant material C50 added in S104 was adjusted. Here, the dopant material was C50, the host material was PC61BM, and the mass percentage of the dopant material C50 in the obtained fullerene composite material was 0.0001%.

[0109] Example 6 This example differs from Example 1 in that the amount of the dopant material C50 added in S104 was adjusted. Here, the dopant material was C50, the host material was PC61BM, and the mass percentage of the dopant material C50 in the obtained fullerene composite material was 1%.

[0110] Example 7 This embodiment differs from the first embodiment in that C70 is used instead of C50.

[0111] Example 8 This example differs from Example 1 in that the amount of the dopant material C50 added in S104 was adjusted. Here, the dopant material was C50, the host material was PC61BM, and the mass percentage of the dopant material C50 in the obtained fullerene composite material was 0.00005%.

[0112] Example 9 This example differs from Example 1 in that the amount of the dopant material C50 added in S104 was adjusted. Here, the dopant material was C50, the host material was PC61BM, and the mass percentage of the dopant material C50 in the obtained fullerene composite material was 1.3%.

[0113] Example 10 This example differs from Example 1 in that steps S101 to S103 are not performed, and instead, in S104, C60 and the dopant material C50 are dissolved in o-dichlorobenzene, and the product obtained by heating under reflux for 48 hours is concentrated and then added to methanol for precipitation and deposition to obtain a fullerene composite material. Here, the dopant material is C50, the host material is C60, and the mass percentage of the dopant material C50 in the obtained fullerene composite material is 0.1%.

[0114] Comparative Example 1 This comparative example differs from Example 1 in that C50 was not added in S104, that is, doping to PC61BM was not performed.

[0115] Comparative Example 2 This comparative example differs from Example 1 in that the fullerene composite material was obtained by directly mixing PC61BM and C50. Here, the mass percentage of C50 in the fullerene composite material was 0.1%.

[0116] Comparative Example 3 Compared with Example 1, in this comparative example, no fullerene composite material was prepared, and an electron transport layer was prepared in the perovskite solar cell by vapor deposition of C60.

[0117] Test example: Standard simulated sunlight (AM1.5G, 100mW / cm 2 The performance of the battery was tested under irradiation of 1000 kJ / cm and the IV curve was obtained. The IV curve and the data fed back from the test equipment were used to calculate the short circuit current Jsc (unit: mA / cm ). 2 The cell's fill factor FF (unit: %) was calculated using the formula FF = Jsc × Voc / (Jmpp × Vmpp). The cell's photoelectric conversion efficiency PCE (unit: %) was calculated using the formula PCE = Jsc × Voc × FF / Pw. Pw represents the input power, measured in mW.

[0118] The doping amounts of the dopant materials and the test results of the batteries in the examples and comparative examples are shown in Table 1.

[0119] [Table 1]

[0120] As can be seen from Table 1, the perovskite solar cells in the Examples achieved higher photoelectric conversion efficiencies than the Comparative Examples. For example, as can be seen from the Examples, Comparative Examples 1, and 3, perovskite solar cells in which the electron transport layer contained a dopant material had higher photoelectric conversion efficiencies. As can be seen from Example 1 and Comparative Example 2, perovskite solar cells obtained by applying the fullerene composite material obtained by the manufacturing method in Example 1 to the electron transport layer had higher photoelectric conversion efficiencies than those obtained by directly mixing PC61BM and C50. Furthermore, when the mass percentage of the dopant material in the fullerene composite material is 0.0001% to 1%, perovskite solar cells can achieve higher photoelectric conversion efficiencies.

[0121] It should be noted that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and all embodiments that have substantially the same technical ideas and provide the same functions and effects within the scope of the technical solution of the present application are included in the technical scope of the present application. Furthermore, various modifications that can be conceived by a person skilled in the art to the embodiments and other forms formed by combining some of the components of the embodiments are also included in the scope of the present application, as long as they do not deviate from the gist of the present application.

Claims

1. A fullerene composite material comprising a host material and a dopant material, wherein the host material comprises at least one of a first fullerene and a first fullerene derivative, the dopant material is at least one selected from a second fullerene and a second fullerene derivative, and a portion of the molecular structure of the dopant material is inserted into the lattice of the first fullerene and / or the first fullerene derivative.

2. 2. The fullerene composite material according to claim 1, wherein the mass percentage of the dopant material in terms of the total mass of the first fullerene and / or the first fullerene derivative and the dopant material is 0.0001% to 1%.

3. 3. The fullerene composite material according to claim 1, wherein the first fullerene comprises at least one of C50, C60, and C70, and the first fullerene derivative comprises at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM.

4. 4. The fullerene composite material according to claim 1, wherein the second fullerene comprises at least one of C50, C60, and C70, and the second fullerene derivative comprises at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM.

5. The method includes a step of heat-treating a mixture obtained by mixing the first raw material and the second raw material with the first solvent, A method for producing a fullerene composite material, characterized in that the first raw material contains a first fullerene and / or a first fullerene derivative and / or a raw material for synthesizing the first fullerene derivative, and the second raw material contains at least one of a second fullerene and a second fullerene derivative used as a dopant material.

6. The raw materials for synthesizing the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and a base, and mixing the first raw material and the second raw material in a solvent includes:

6. The method for producing a fullerene composite material according to claim 5, comprising dispersing the methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate and the base in a first sub-solvent, dispersing the second raw material and the third fullerene in a second sub-solvent, and mixing the two solution systems.

7. The molar ratio of the third fullerene, the dopant material, the methyl 5-phenyl-5-(p-toluenesulfonylhydrazino)pentanoate, and the base is 1:(10 －５ ~10 －２ 7. The method for producing a fullerene composite material according to claim 6, wherein the fullerenes are in the range of 1 to 10.

8. the first secondary solvent comprises pyridine; and / or the second co-solvent comprises at least one of toluene, xylene, chlorobenzene, and dichlorobenzene; and / or 8. The method for producing a fullerene composite material according to claim 6, wherein the base includes at least one of sodium methoxide, cesium carbonate, sodium hydroxide, and potassium hydroxide.

9. 9. The method for producing a fullerene composite material according to claim 5, wherein the first solvent includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene.

10. The heat treatment is (1) The temperature of the heat treatment is 100°C to 300°C; (2) The heat treatment time is 24 hours to 60 hours; (3) the heat treatment includes heating under reflux; 9. The method for producing a fullerene composite material according to claim 5, wherein at least one of the following characteristics is satisfied:

11. a first electrode, a perovskite layer, an electron transport layer, and a second electrode, which are stacked in this order; The electron transport layer comprises the fullerene composite material according to any one of claims 1 to 4, or 11. A perovskite solar cell, wherein the electron transport layer contains a fullerene composite material obtained by the manufacturing method according to claim 5.

12. The perovskite solar cell according to claim 11, wherein the electron transport layer has a thickness of 10 nm to 100 nm.

13. Producing a perovskite layer on the first electrode; forming an electron transport layer on the perovskite layer; forming a second electrode on the electron transport layer; a first fullerene derivative; a second fullerene derivative; and a second fullerene derivative. The electron transport layer includes a fullerene composite material, the fullerene composite material including a host material and a dopant material, the host material including at least one of a first fullerene and a first fullerene derivative, the dopant material being at least one selected from a second fullerene and a second fullerene derivative, and a part of a molecular structure of the dopant material being inserted into a lattice of the first fullerene and / or the first fullerene derivative.

14. 13. An electrical device comprising the perovskite solar cell of any one of claims 11 to 12.

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