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

Abstract

This application relates to a fullerene composite material and its preparation method, a perovskite solar cell and its preparation method, and an electrical device. The fullerene composite material includes a host material and a dopant material. The host material includes at least one of a first fullerene and a first fullerene derivative. The dopant material is selected from at least one of a second fullerene and a second fullerene derivative. The molecular structure of the dopant material has a portion of its structure embedded in the lattice of the first fullerene and / or the first fullerene derivative.

Description

Technical Field

[0001] This application relates to the field of solar cell technology, and in particular to a fullerene composite material and its preparation method, a perovskite solar cell and its preparation method, and an electrical device thereof. Background Technology

[0002] With the continuous development of solar cell research, perovskite solar cells have attracted widespread attention due to their high photoelectric conversion efficiency and relatively simple fabrication process.

[0003] In the structure of perovskite solar cells, fullerenes and their derivatives are commonly used electron acceptors. However, with the continuous advancement of research on perovskite solar cells, the photoelectric conversion efficiency of cells prepared using pure fullerenes and their derivatives to fabricate the electron transport layer remains relatively low. Summary of the Invention

[0004] According to various embodiments of this application, this application provides a fullerene composite material, including a host material and a dopant material. The host material includes at least one of a first fullerene and a first fullerene derivative. The dopant material is selected from at least one of a second fullerene and a second fullerene derivative. The molecular structure of the dopant material has a portion of its structure embedded in the lattice of the first fullerene and / or the first fullerene derivative.

[0005] In this application, doping a host material including a first fullerene and / or a first fullerene derivative with at least one of a second fullerene and a second fullerene derivative can improve the conductivity of the fullerene composite material and improve the photoelectric conversion efficiency of the perovskite solar cell.

[0006] In some embodiments, the mass percentage of the dopant material is 0.0001% to 1%, representing a percentage of the total mass of the first fullerene and / or the first fullerene derivative, and the dopant material. If the mass percentage of the dopant material is too small, the doping effect is poor; if the mass percentage of the dopant material is too large, it may have an excessive impact on the intrinsic structure of the host material.

[0007] In some embodiments, the first fullerene includes at least one of C50, C60, and C70, and the first fullerene derivative includes at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM. These fullerenes and fullerene derivatives are widely available and easy to obtain.

[0008] In some embodiments, the second fullerene includes at least one of C50, C60, and C70, and the second fullerene derivative includes at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM. These fullerenes and fullerene derivatives are widely available and easily obtained.

[0009] This application also provides a method for preparing a fullerene composite material, comprising the following steps:

[0010] The first raw material and the second raw material are mixed in the first solvent, and the resulting mixture is subjected to heat treatment.

[0011] 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.

[0012] In this preparation method, adding the dopant to the reaction system before heat treatment allows for more uniform dispersion of the dopant within the system. In the resulting fullerene composite material, the more uniform doping of the dopant into the first fullerene derivative reduces the risk of dopant aggregation and improves doping uniformity.

[0013] In some embodiments, the raw materials used to synthesize the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazyl)valerate, and a base; mixing the first and second raw materials in a solvent includes:

[0014] The methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and the base are dispersed in a first sub-solvent, the second raw material and the third fullerene are dispersed in a second sub-solvent, and the two solution systems are mixed.

[0015] In some embodiments, the molar ratio of the third fullerene, the doped material, the methyl 5-phenyl-5-(p-toluenesulfonylhydrazyl)valerate, and the base is 1:(10) -5 ~10 -2 ):(1~2):(1~10).

[0016] In some embodiments, the first sub-solvent includes pyridine.

[0017] In some embodiments, the second sub-solvent includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene.

[0018] In some embodiments, the alkali includes at least one selected from sodium methoxide, cesium carbonate, sodium hydroxide, and potassium hydroxide.

[0019] In some embodiments, the first solvent includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene.

[0020] In some embodiments, the temperature of the heat treatment is 100°C to 300°C.

[0021] In some embodiments, the heat treatment time is 24h to 60h.

[0022] In some embodiments, the heat treatment includes heating and reflux.

[0023] This application also provides a perovskite solar cell, comprising a first electrode, a perovskite layer, an electron transport layer and a second electrode stacked sequentially.

[0024] The electron transport layer comprises the fullerene composite material, or,

[0025] The electron transport layer comprises the fullerene composite material obtained by the preparation method.

[0026] In the aforementioned perovskite solar cells, the electron transport layer includes a fullerene composite material, which can improve the performance of the perovskite solar cells.

[0027] In some embodiments, the thickness of the electron transport layer is 10 nm to 100 nm.

[0028] This application also provides a method for fabricating a perovskite solar cell, comprising the following steps:

[0029] A perovskite layer is prepared on the first electrode;

[0030] An electron transport layer is fabricated on the perovskite layer;

[0031] A second electrode is fabricated on the electron transport layer;

[0032] The electron transport layer includes a fullerene composite material, which includes a host material and a dopant material. The host material includes at least one of a first fullerene and a first fullerene derivative. The dopant material is selected from at least one of a second fullerene and a second fullerene derivative. The molecular structure of the dopant material has a portion of its structure embedded in the lattice of the first fullerene and / or the first fullerene derivative.

[0033] This application also provides an electrical device including the perovskite solar cell. Attached Figure Description

[0034] To more clearly illustrate the technical solution of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application; those skilled in the art can obtain other drawings based on the drawings without any creative effort.

[0035] Figure 1 This is a schematic diagram of an example perovskite solar cell.

[0036] To better describe and illustrate embodiments and / or examples of the inventions disclosed herein, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed inventions, the currently described embodiments and / or examples, or the best mode of these inventions as currently understood. Detailed Implementation

[0037] The perovskite solar cell, its fabrication method, and its electrical device according to this application are further described in detail below with reference to specific embodiments. This invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this invention.

[0038] Details of one or more embodiments of this application are set forth in the following drawings and description. Other features, objects, and advantages of this application will become apparent from the specification, drawings, and claims.

[0039] 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 this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0040] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0041] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0042] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0043] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0044] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0045] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0046] Unless otherwise specified, in this application, the term "room temperature" generally refers to 4°C to 30°C, and preferably 25±5°C.

[0047] This application provides a fullerene composite material, including a host material and a dopant material. The host material includes at least one of a first fullerene and a first fullerene derivative. The dopant material is selected from at least one of a second fullerene and a second fullerene derivative. The molecular structure of the dopant material has a portion of its structure embedded in the lattice of the first fullerene and / or the first fullerene derivative.

[0048] In the fullerene composite material of this application, the host material including the first fullerene and / or the first fullerene derivative is doped with at least one of the second fullerene and the second fullerene derivative. In the composite material, a portion of the molecular structure of the doped material is embedded in the lattice of the first fullerene and / or the first fullerene derivative, which can improve the conductivity of the fullerene composite material and improve the photoelectric conversion efficiency of the perovskite solar cell.

[0049] In fullerene derivatives, the presence of branched chains may increase the intermolecular distance, making carrier extraction difficult and limiting the improvement of the conductivity of fullerene derivatives. The doped material has a portion of its molecular structure embedded within the lattice of the first fullerene and / or its derivative, which can reduce the intermolecular distance, improve electron transport capability, and enhance the conductivity of the fullerene composite material.

[0050] It is understandable that the first fullerene and the second fullerene can be the same or different. Similarly, the first fullerene derivative and the second fullerene derivative can be the same or different.

[0051] In some embodiments, the first fullerene includes at least one of C50, C60, and C70. The first fullerene derivative includes at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM. The second fullerene includes at least one of C50, C60, and C70. The second fullerene derivative includes at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM. These fullerenes and fullerene derivatives are widely available and easily obtained.

[0052] It is also understandable that fullerene derivatives are typically obtained by modifying fullerenes, where the crystal lattice of fullerenes is usually spherical, so the crystal lattice of fullerene derivatives also primarily exhibits a spherical shape. When a portion of the molecular structure of the dopant material is embedded within the crystal lattice of the first fullerene and / or the first fullerene derivative, it can be interpreted as a partial embedding of the molecular structure of the dopant material within the spherical crystal lattice of the first fullerene and / or the first fullerene derivative. Optionally, when the dopant material has side chains, the side chains of the dopant material are embedded within the crystal lattice of the first fullerene and / or the first fullerene derivative. It is understood that fullerene derivatives are typically obtained by modifying fullerenes such as C50, C60, and C70.

[0053] It is also understandable that when a portion of the molecular structure of the doped material is embedded within the lattice of the first fullerene and / or the first fullerene derivative, other structures of the molecular structure of the doped material may extend out from the lattice of the first fullerene and / or the first fullerene derivative, or may be attached to the outer surface of the lattice of the first fullerene and / or the first fullerene derivative.

[0054] In some embodiments, the mass percentage of the dopant material is 0.0001% to 1%, representing a percentage of the total mass of the first fullerene and / or the first fullerene derivative, and the dopant material. Optionally, the mass percentage of the dopant material, representing a percentage of the total mass of the first fullerene and / or 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. If the mass percentage of the dopant material is too small, the doping effect is poor; if the mass percentage of the dopant material is too large, it may have an excessive impact on the intrinsic structure of the host material.

[0055] Optionally, the type and content of the dopant material can be determined by liquid chromatography. Optionally, the liquid chromatography conditions are as follows: a 15 cm long C18 column, a mobile phase of toluene:methanol = 1:2, and a DAD detector.

[0056] In this application, the mass percentage of the dopant material can be expressed as a percentage of the total mass of the first fullerene and / or the first fullerene derivative, and the dopant material.

[0057] In some embodiments, the fullerene composite material comprises a host material and a dopant material. The host material is selected from at least one of a first fullerene and a first fullerene derivative, and the dopant material is selected from at least one of a fullerene and a second fullerene derivative. The molecular structure of the dopant material has a portion embedded within the crystal lattice of the first fullerene and / or the first fullerene derivative. Optionally, the mass percentage of the dopant material is 0.0001% to 1%, representing a percentage of the total mass of the first fullerene and / or the first fullerene derivative and the dopant material. Optionally, the mass percentage of the dopant material, expressed as a percentage of the total mass of the first fullerene and / or 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.

[0058] This application also provides a method for preparing a fullerene composite material. The method includes the following steps: mixing a first raw material and a second raw material in a first solvent, and subjecting the resulting mixture to heat treatment; 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 fullerene and a second fullerene derivative used as a dopant material.

[0059] In the preparation of fullerene composites, the agglomeration of dopant is a significant factor affecting the composite's performance. In this preparation method, adding the dopant to the reaction system before heat treatment allows for a more uniform dispersion of the dopant within the system. In the resulting fullerene composite, the more uniform doping of the dopant into the first fullerene derivative reduces the risk of dopant agglomeration and improves doping uniformity.

[0060] In some embodiments, the first raw material contains a raw material for synthesizing a first fullerene derivative, the raw material for synthesizing the first fullerene derivative including a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazine)valerate, and a base; mixing the first raw material and the second raw material in a solvent includes: dispersing methyl 5-phenyl-5-(p-toluenesulfonylhydrazine)valerate 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.

[0061] Optionally, the third fullerene includes at least one of C50, C60, and C70. Optionally, the first fullerene, the second fullerene, and the third fullerene may not be completely identical, or they may be completely identical.

[0062] In some embodiments, the molar ratio of the third fullerene, the dopant material, methyl 5-phenyl-5-(p-toluenesulfonylhydrazyl)valerate, and the base is 1:(10) -5 ~10 -2 ):(1~2):(1~10). Optionally, the molar ratio of the third fullerene, the dopant material, methyl 5-phenyl-5-(p-toluenesulfonylhydrazyl)valerate, 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.

[0063] In some embodiments, the first sub-solvent includes pyridine.

[0064] Optionally, the second sub-solvent includes at least one selected from toluene, xylene, chlorobenzene, and dichlorobenzene. Xylene includes at least one selected from o-xylene, m-xylene, and p-xylene. Dichlorobenzene includes at least one selected from o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene.

[0065] Optionally, the alkali includes at least one of sodium methoxide, cesium carbonate, sodium hydroxide, and potassium hydroxide.

[0066] Optionally, the raw materials used to synthesize the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazyl)valerate, and a base; mixing the first and second raw materials in a solvent includes: adding methyl 5-phenyl-5-(p-toluenesulfonylhydrazyl)valerate to the first sub-solvent, then adding the base, stirring, and evacuating the gas to place the solution system under an argon atmosphere; adding the second raw material and the third fullerene to the second sub-solvent, and then adding the resulting solution to a solution system containing the first sub-solvent.

[0067] Optionally, the raw materials used to synthesize the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate, and a base. The process further includes mixing the first and second raw materials in a first solvent, heat-treating the resulting mixture, removing the solvent from the heat-treated product, and then separating the product. Optionally, the solvent can be removed by rotary evaporation. Optionally, the product can be separated by column chromatography.

[0068] In some embodiments, the first raw material is a first fullerene derivative. The mass percentage of the dopant material, based on the total mass of the first fullerene derivative and the dopant material, is 0.0001% to 1%. Optionally, the mass percentage of the dopant material, based on the total mass 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.

[0069] Optionally, the first raw material is a first fullerene derivative. The process further includes mixing the first and second raw materials in a first solvent, heat-treating the resulting mixture, concentrating the heat-treated product, adding methanol, and precipitating the product. The precipitate yields a fullerene composite material.

[0070] In some embodiments, the first solvent includes at least one selected from toluene, xylene, chlorobenzene, and dichlorobenzene. Xylene includes at least one selected from o-xylene, m-xylene, and p-xylene. Dichlorobenzene includes at least one selected from o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene.

[0071] 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 reflow heating. 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.

[0072] In some embodiments, the preparation method of methyl 5-phenyl-5-(p-toluenesulfonylhydrazine)valerate includes: mixing methyl 4-benzoylbutyrate, p-toluenesulfonylhydrazine, and methanol, heating and refluxing, cooling to room temperature, storing in the dark, then transferring to -15°C and storing in the dark overnight, filtering, recrystallizing the product in methanol, and storing the product under vacuum at 40°C overnight to obtain a white solid methyl 5-phenyl-5-(p-toluenesulfonylhydrazine)valerate. Optionally, the heating and refluxing time is 12 h, and after cooling to room temperature, it is stored in the dark for 24 h.

[0073] In some embodiments, the preparation method of methyl 4-benzoylbutyrate includes: dissolving benzoylbutyric acid in chlorobenzene, adding methanol, stirring until completely dissolved, adding hydrochloric acid dropwise, continuing stirring, heating under reflux overnight, stopping stirring, neutralizing with saturated sodium carbonate until no bubbles are present, separating the oil and water, then extracting the aqueous phase with ethyl acetate, combining the organic phases together, removing water with anhydrous calcium chloride, removing the solvent by vacuum distillation, and eluting the product in a silica gel column with ethyl acetate and n-hexane as the eluent, wherein the volume ratio of ethyl acetate to n-hexane is 3:1, to obtain a pale yellow oily liquid, methyl 4-benzoylbutyrate.

[0074] This application also provides an electron transport thin film. The electron transport thin film comprises the above-described fullerene composite material or a fullerene composite material obtained by the above-described method for preparing the fullerene composite material. Optionally, the thickness of the electron transport thin film is 10 nm to 100 nm. More preferably, the thickness of the electron transport thin film is 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc.

[0075] This application also provides an electron transport slurry. The electron transport slurry includes a second solvent and further includes the fullerene composite material described above or the fullerene composite material obtained by the preparation method of the fullerene composite material described above. Optionally, the second solvent in the electron transport slurry 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.

[0076] This application also 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 sequentially stacked. The electron transport layer comprises the aforementioned fullerene composite material, or the electron transport layer comprises a fullerene composite material obtained by the aforementioned preparation method, or the electron transport layer comprises the aforementioned electron transport thin film, or the electron transport layer is prepared from a material comprising the aforementioned electron transport paste. In the perovskite solar cell, the electron transport layer comprising a fullerene composite material can improve the performance of the perovskite solar cell.

[0077] Optionally, the electron transport layer is prepared by spin coating and annealing of a material comprising the aforementioned electron transport paste. Further, the electron transport layer is prepared by spin coating and annealing of the aforementioned electron transport paste.

[0078] Optionally, the thickness of the electron transport layer is 10nm to 100nm. Optionally, the thickness of the electron transport layer is 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc.

[0079] Optionally, the electron transport layer is obtained by spin coating and annealing a material comprising the aforementioned electron transport slurry.

[0080] 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.

[0081] In some embodiments, the first electrode is typically a transparent conductive glass. Optionally, the first electrode is selected from at least one of 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.

[0082] In some embodiments, the second electrode is typically a metal electrode. Optionally, the second electrode is selected from at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W, and their alloys. Optionally, the thickness of the second electrode is 20 nm to 200 nm, optionally 60 nm to 100 nm, and more preferably 70 nm to 90 nm. It is understood that the perovskite layer is a light-absorbing layer composed of perovskite material. Optionally, the chemical formula of the perovskite layer material is ABX3 or A2CDX6, wherein:

[0083] A is an inorganic, organic, or mixed organic-inorganic cation, comprising at least one of organic amine cations, Cs cations, K cations, Rb cations, and Li cations; wherein the organic amine cation is selected from (NR1R2R3R4). + (R1R2N=CR3R4) + (R1R2N-C(R5)=NR3R4) + Or (R1R2N-C(NR5R6)=R3R4) + R1, R2, R3, R4, R5, and R6 are each independently selected from H, substituted or unsubstituted C1-20 alkyl groups, or substituted or unsubstituted aryl groups; A is optionally methylamino (CH3NH3) + (MA) + ), formamidinyl (HC(NH2)2 + (FA) + ), cesium ion (Cs +) and rubidium (Rb + At least one of the following, further optionally methylamino (CH3NH3) + ) or formamidinyl (HC(NH2)2 + ).

[0084] B is an inorganic, organic, or 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 a divalent metal ion Pb. 2+ and Sn 2+ At least one of them.

[0085] C is an inorganic, organic, or mixed organic-inorganic cation, optionally a monovalent metal ion Ag. + wait.

[0086] D is an inorganic, organic, or mixed organic-inorganic cation, optionally a trivalent metal ion bismuth cation Bi. 3+ Antimony cation Sb 3+ Indium cations In 3+ wait.

[0087] X is an inorganic, organic, or mixed organic-inorganic anion, optionally one or more of a halide anion and a carboxyl anion, and further optionally a bromide ion (Br). - ) or iodide ions (I - ).

[0088] In some implementations, the band gap of the perovskite layer is 1.20 eV-2.30 eV.

[0089] In some embodiments, the thickness of the perovskite layer is 200 nm to 800 nm, and optionally 400 nm to 600 nm.

[0090] In some embodiments, the perovskite solar cell further includes a hole transport layer located between the first electrode and the perovskite layer. Optionally, the hole transport layer may be at least one of the following materials and their derivatives, or materials obtained by doping or passivation: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly-3-hexylthiophene (P3HT), triphenylamine with a triphenylene core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-aniline)carbazole-spirobisfluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), polythiophene, nickel oxide (NiO x Molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (CuO), etc.

[0091] In some embodiments, the perovskite solar cell further includes a first passivation layer located between the perovskite layer and the hole transport layer. Optionally, the first passivation layer is made of PTAA.

[0092] In some embodiments, the perovskite solar cell further includes a second passivation layer and / or a buffer layer, which are located between the electron transport layer and the second electrode. Optionally, the material of the second passivation layer and the buffer layer is copper bath (BCP).

[0093] Understandably, perovskite solar cells include conventional perovskite solar cells and inverted perovskite solar cells. For a conventional perovskite solar cell, it includes a transparent electrode and, sequentially stacked on the transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode. For an inverted perovskite solar cell, it includes a transparent electrode and, sequentially stacked on the transparent electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a metal electrode. In this application, the corresponding conventional and inverted perovskite solar cells can be obtained by selecting the materials of the first and second electrodes.

[0094] Please see Figure 1 The diagram illustrates the structure of a perovskite solar cell in one embodiment of this application. 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 sequentially stacked on the first electrode. A glass substrate is disposed on the surface of the FTO away from the perovskite layer.

[0095] This application also provides a method for fabricating a perovskite solar cell. The method includes the following steps: fabricating a perovskite layer on a first electrode; fabricating an electron transport layer on the perovskite layer; fabricating a second electrode on the electron transport layer; the electron transport layer comprises a fullerene composite material, which includes a host material and a dopant material. The host material includes a first fullerene derivative, and the dopant material is selected from at least one of fullerene and a second fullerene derivative, wherein a portion of the molecular structure of the dopant material is embedded within the lattice of the first fullerene derivative.

[0096] Optionally, the perovskite layer is prepared by spin coating and annealing. Optionally, the electron transport layer is prepared by spin coating and annealing. Optionally, the second electrode is prepared by vapor deposition.

[0097] Optionally, the electron transport layer can be prepared by spin-coating the above-mentioned electron transport paste and then annealing.

[0098] This application also provides an electrical device. The electrical device includes the aforementioned perovskite solar cell. Optionally, the electrical device can be used in fields such as communications, transportation, industry and agriculture, and lighting. Examples of electrical devices include satellites, communication equipment, traffic lights, lighthouses, wireless telephone booths, monitoring equipment in oil drilling, power systems, camping lights, electric vehicles, and electronic device chargers.

[0099] Example

[0100] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0101] Example 1

[0102] The preparation steps of the fullerene composite material in this embodiment are as follows:

[0103] S101: Synthesis of methyl 4-benzoylbutyrate:

[0104] Take a clean and dry 500mL double-necked flask, add 19.25g (0.1mol) of benzoylbutyric acid, dissolve it in 300mL of chlorobenzene, add 100mL of methanol, stir until completely dissolved, add 30mL of hydrochloric acid dropwise, continue stirring, heat under reflux overnight, and check the reaction on TLC to confirm that the reaction has proceeded to completion. Then stop stirring, neutralize with saturated sodium carbonate until no bubbles are present, separate the oil and water, extract the aqueous phase with ethyl acetate, combine the organic phases together, remove water with anhydrous calcium chloride, remove the solvent by vacuum distillation, and elute the product in a silica gel column with ethyl acetate / n-hexane (volume ratio 3:1) to obtain 18g of pale yellow oily liquid methyl 4-benzoylbutyrate.

[0105] Synthesis of S102: Methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate:

[0106] 10.5 g (0.05 mol) of methyl 4-benzoylbutyrate, 11.5 g (0.06 mol) of p-toluenesulfonylhydrazine, and 200 mL of methanol were heated to reflux in a single-necked round-bottom flask and reacted for 12 h. The mixture was then cooled to room temperature and stored in the dark for 24 h. After that, it was transferred to -15 °C and stored in the dark overnight. The mixture was filtered, and the product was recrystallized in methanol. The product was then incubated under vacuum at 40 °C overnight to give 18.2 g of white solid methyl 5-phenyl-5-(p-toluenesulfonylhydrazine)pentanoate.

[0107] S103: Synthesis of F1-OMe:

[0108] Take a clean and dry 1L three-necked flask, dissolve 11.25g (0.03mol) of methyl 5-phenyl-5-(p-toluenesulfonylhydrazinoyl)valerate in 250mL of pyridine, add 1.75g ​​of sodium methoxide, stir, evacuate the gas, and preserve it under an argon atmosphere. Take another clean and dry round-bottom flask, add 10.8g of C60, dissolve it in 300mL of o-dichlorobenzene, and add it dropwise to the above three-necked flask. Heat under reflux for 24h, remove most of the solvent by rotary evaporation, and separate the product by column chromatography to obtain product F1-OMe 6.83g.

[0109] S104: Fullerene composite material:

[0110] 6.83 g of F1-OMe and the dopant C50 were dissolved in o-dichlorobenzene and refluxed for 48 h. After the product was concentrated, it was added to methanol, and precipitation occurred to obtain the fullerene composite material. In this example, the dopant was C50, the host material was PC61BM, and the mass percentage of the dopant C50 in the obtained fullerene composite material was 0.1%, i.e., the doping amount was 0.1%.

[0111] The perovskite solar cell in this embodiment is fabricated using the following steps:

[0112] S201: Take 20 pieces of FTO conductive glass with a specification of 2.0cm*2.0cm, remove 0.35cm of FTO from each end by laser etching to expose the glass substrate; use water, acetone and isopropanol to ultrasonically clean the etched FTO conductive glass in sequence; blow the solvent off the cleaned FTO conductive glass under a nitrogen gun and put it into an ultraviolet ozone generator for ultraviolet ozone cleaning treatment.

[0113] S202: 10 mg / mL nickel oxide nanoparticles (water as solvent) were spin-coated onto an FTO substrate after UV ozone cleaning at a rate of 4000 rpm and annealed on a hot plate at 100°C for 30 minutes to form a hole transport layer.

[0114] S203: Dissolve PTAA in chlorobenzene at a concentration of 1 mg / mL, stir, filter through a 0.45 μm filter membrane, take 50 μL and drop it onto the hole transport layer, spin coat at a rate of 4000 rpm, and anneal on a hot plate at 100℃ for 10 minutes to obtain a passivation layer.

[0115] S204: Weigh 223 mg lead iodide (PbI2), 80 mg formamidine (FAI), and 15 mg methyl chloroamine (MACl) and dissolve them in a mixed solution of 0.8 mL LDMF and 0.2 mL DMSO. Stir for 3 h, filter through a 0.22 μm organic filter membrane to obtain a perovskite precursor solution. Spin-coat the perovskite precursor solution onto the passivation layer at 3000 rpm, anneal at 120 °C for 30 min, and cool to room temperature to form a perovskite layer. The active material in the perovskite layer is the FA system, and the thickness is 500 nm.

[0116] S205: The fullerene composite material obtained in S104 was dissolved in chlorobenzene to form an electron transport paste with a concentration of 20 mg / mL. This paste was spin-coated onto the perovskite layer at 1500 rpm and annealed at 100°C for 10 min to form an electron transport layer with a thickness of 50 nm. Immediately afterwards, a passivation material solution (BCP solution, made by dissolving BCP in isopropanol at a concentration of 0.5 mg / mL) was spin-coated at 5000 rpm to form a passivation layer with a thickness of 5 nm. Then, the perovskite solar cell was obtained by vapor deposition of a metal electrode (Ag) using a vapor deposition machine.

[0117] Example 2

[0118] Compared with Example 1, the difference in this example is that the doping material is PC51BM. PC51BM is prepared by steps S101 to S103 in Example 1, except that C60 in S103 is replaced with C50.

[0119] In the preparation of fullerene composite materials, the dopant C50 in S104 of Example 1 was replaced with PC51BM.

[0120] In this embodiment, the dopant material is PC51BM and the host material is PC61BM. In the obtained fullerene composite material, the dopant material PC51BM accounts for 0.05% of the mass of the fullerene composite material, that is, the doping amount is 0.05%.

[0121] Example 3

[0122] Compared with Example 1, the difference in this example is that C60 in S103 is replaced with C50 and C60, wherein the sum of the masses of C50 and C60 is equal to the mass of C60 in S103 in Example 1, and the mass percentage of C50 is 0.1% of the total mass of C50 and C60.

[0123] In this embodiment, the dopant material is PC51BM and the main material is PC61BM. In the obtained fullerene composite material, the dopant material PC51BM accounts for 0.05% of the mass of the fullerene composite material, that is, the doping amount is 0.05%.

[0124] Example 4

[0125] Compared with Example 1, the difference in this example is that C60 in S103 is replaced with C50, C60 and C70, wherein the sum of the masses of C50, C60 and C70 is equal to the mass of C60 in S103 in Example 1, and the mass percentage of C50 is 0.1% and the mass percentage of C70 is 0.03% of the total mass of C50, C60 and C70.

[0126] In this embodiment, the doping materials are PC51BM and PC71BM, and the host material is PC61BM. In the obtained fullerene composite material, the mass percentage of doping material PC51BM in the fullerene composite material is 0.05%, and the mass percentage of doping material PC71BM in the fullerene composite material is 0.015%. That is, the doping amount of PC51BM is 0.05%, and the doping amount of PC71BM is 0.03%.

[0127] Example 5

[0128] Compared to Example 1, the difference in this example is that the amount of dopant C50 added in S104 is adjusted. The dopant is C50, the host material is PC61BM, and the resulting fullerene composite material has a C50 dopant content of 0.0001% by mass.

[0129] Example 6

[0130] Compared to Example 1, the difference in this example is that the amount of dopant C50 added in S104 is adjusted. The dopant is C50, the host material is PC61BM, and the resulting fullerene composite material has C50 accounting for 1% of its mass.

[0131] Example 7

[0132] Compared with Example 1, the difference in this example is that C50 is replaced with C70.

[0133] Example 8

[0134] Compared to Example 1, the difference in this example is the adjustment of the amount of dopant C50 added in S104. The dopant is C50, the host material is PC61BM, and the resulting fullerene composite material has a C50 dopant content of 0.00005% by mass.

[0135] Example 9

[0136] Compared to Example 1, the difference in this example is the adjustment of the amount of dopant C50 added in S104. The dopant is C50, the host material is PC61BM, and the resulting fullerene composite material has C50 accounting for 1.3% of its mass.

[0137] Example 10

[0138] Compared to Example 1, the difference in this example is that S101-S103 are omitted. In S104, C60 and the dopant C50 are dissolved in o-dichlorobenzene and heated under reflux for 48 hours. After the product is concentrated, it is added to methanol, and precipitation occurs to obtain the fullerene composite material. The dopant is C50, and the main material is C60. In the obtained fullerene composite material, the dopant C50 accounts for 0.1% of the total mass of the fullerene composite material.

[0139] Comparative Example 1

[0140] Compared with Example 1, the difference in this comparative example is that C50 is not added in S104, that is, PC61BM is not doped.

[0141] Comparative Example 2

[0142] Compared to Example 1, this comparative example differs in that PC61BM and C50 are directly mixed to obtain a fullerene composite material. The C50 constitutes 0.1% of the fullerene composite material by mass.

[0143] Comparative Example 3

[0144] Compared to Example 1, instead of preparing fullerene composite materials, an electron transport layer was prepared in the perovskite solar cell by evaporating C60.

[0145] Test example:

[0146] Under standard simulated sunlight (AM 1.5G, 100mW / cm²) 2 Under irradiation, battery performance is tested to obtain the IV curve. Based on the IV curve and data from the testing equipment, the short-circuit current Jsc (unit: mA / cm²) can be calculated. 2 The open-circuit voltage Voc (in V), maximum light output current Jmpp (in mA), and maximum light output voltage Vmpp (in V) are given. The fill factor FF (in %) is calculated using the formula FF = Jsc × Voc / (Jmpp × Vmpp). The photoelectric conversion efficiency PCE (in %) is calculated using the formula PCE = Jsc × Voc × FF / Pw; Pw represents the input power (in mW).

[0147] The doping amount of the doped material and the test results of the battery in the examples and comparative examples are shown in Table 1.

[0148] Table 1

[0149]

[0150] As shown in Table 1, the perovskite solar cells in the examples achieved higher photoelectric conversion efficiencies compared to the comparative examples. For instance, examples 1 and 3 show that perovskite solar cells with doped materials in the electron transport layer exhibit higher photoelectric conversion efficiencies. Examples 1 and 2 show that, compared to directly mixing PC61BM and C50, the perovskite solar cell obtained by the preparation method in Example 1, when used in the electron transport layer, has a higher photoelectric conversion efficiency. Furthermore, when the doped material accounts for 0.0001% to 1% of the mass percentage of the fullerene composite material, the perovskite solar cell can achieve even higher photoelectric conversion efficiencies.

[0151] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A perovskite solar cell, characterized in that, The device includes a first electrode, a perovskite layer, an electron transport layer, and a second electrode stacked sequentially. The electron transport layer comprises a fullerene composite material, which includes a host material and a dopant material. The host material includes at least one of a first fullerene and a first fullerene derivative. The dopant material is selected from at least one of a second fullerene and a second fullerene derivative. A portion of the molecular structure of the dopant material is embedded within the lattice of the first fullerene and / or the first fullerene derivative.

2. The perovskite solar cell according to claim 1, characterized in that, The thickness of the electron transport layer is 10nm~100nm.

3. The perovskite solar cell according to claim 1, characterized in that, The mass percentage of the doped material is 0.0001% to 1%, which is a percentage of the total mass of the first fullerene and / or the first fullerene derivative and the doped material.

4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that, The first fullerene includes at least one of C50, C60, and C70, and the first fullerene derivative includes at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM.

5. The perovskite solar cell according to any one of claims 1 to 3, characterized in that, The second fullerene includes at least one of C50, C60, and C70, and the second fullerene derivative includes at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM.

6. A method for fabricating a perovskite solar cell, characterized in that, Includes the following steps: A perovskite layer is prepared on the first electrode; An electron transport layer is fabricated on the perovskite layer; A second electrode is fabricated on the electron transport layer; The electron transport layer includes a fullerene composite material, which includes a host material and a dopant material. The host material includes at least one of a first fullerene and a first fullerene derivative. The dopant material is selected from at least one of a second fullerene and a second fullerene derivative. The molecular structure of the dopant material has a portion of its structure embedded in the lattice of the first fullerene and / or the first fullerene derivative.

7. A fullerene composite material, characterized in that, The material comprises a host material and a dopant material. The host material includes at least one of a first fullerene and a first fullerene derivative. The dopant material is selected from at least one of a second fullerene and a second fullerene derivative. The molecular structure of the dopant material has a portion of its structure embedded within the crystal lattice of the first fullerene and / or the first fullerene derivative. The mass percentage of the dopant material is 0.0001% to 1% of the total mass of the first fullerene and / or the first fullerene derivative and the dopant material.

8. The fullerene composite material according to claim 7, characterized in that, The first fullerene includes at least one of C50, C60, and C70, and the first fullerene derivative includes at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM.

9. The fullerene composite material according to any one of claims 7 to 8, characterized in that, The second fullerene includes at least one of C50, C60, and C70, and the second fullerene derivative includes at least one of PC51BM, PC52BM, PC61BM, PC62BM, PC71BM, and PC72BM.

10. A method for preparing a fullerene composite material, characterized in that, Includes the following steps: The first raw material and the second raw material are mixed in the first solvent, and the resulting mixture is subjected to heat treatment. 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; the second raw material contains at least one of a second fullerene and a second fullerene derivative used as a dopant material; the molecular structure of the dopant material has a portion of its structure embedded in the crystal lattice of the first fullerene and / or the first fullerene derivative; the mass percentage of the dopant material is 0.0001% to 1% of the total mass of the first fullerene and / or the first fullerene derivative and the dopant material.

11. The method for preparing the fullerene composite material according to claim 10, characterized in that, The raw materials used to synthesize the first fullerene derivative include a third fullerene, methyl 5-phenyl-5-(p-toluenesulfonylhydrazyl)valerate, and a base; mixing the first and second raw materials in a solvent includes: The methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)valerate and the base are dispersed in a first sub-solvent, the second raw material and the third fullerene are dispersed in a second sub-solvent, and the two solution systems are mixed.

12. The method for preparing the fullerene composite material according to claim 11, characterized in that, The molar ratio of the third fullerene, the doped material, the methyl 5-phenyl-5-(p-toluenesulfonylhydrazido)valerate, and the base is 1:(10) -5 ~10 -2 ): (1~2): (1~10).

13. The method for preparing the fullerene composite material according to claim 11, characterized in that, The first sub-solvent includes pyridine; and / or, The second sub-solvent includes at least one selected from toluene, xylene, chlorobenzene, and dichlorobenzene; and / or, The alkali includes at least one of sodium methoxide, cesium carbonate, sodium hydroxide, and potassium hydroxide.

14. The method for preparing the fullerene composite material according to any one of claims 10 to 13, characterized in that, The first solvent includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene.

15. The method for preparing the fullerene composite material according to any one of claims 10 to 13, characterized in that, The heat treatment satisfies at least one of the following characteristics: (1) The temperature of the heat treatment is 100℃~300℃; (2) The heat treatment time is 24h~60h; (3) The heat treatment includes heating and reflux.

16. An electrical appliance, characterized in that, The perovskite solar cell includes any one of claims 1 to 5.

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