WO2024178679A1 - 富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置 - Google Patents

富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置 Download PDF

Info

Publication number
WO2024178679A1
WO2024178679A1 PCT/CN2023/079072 CN2023079072W WO2024178679A1 WO 2024178679 A1 WO2024178679 A1 WO 2024178679A1 CN 2023079072 W CN2023079072 W CN 2023079072W WO 2024178679 A1 WO2024178679 A1 WO 2024178679A1
Authority
WO
WIPO (PCT)
Prior art keywords
fullerene
composite material
doping
electron transport
derivative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2023/079072
Other languages
English (en)
French (fr)
Inventor
梁伟风
苏硕剑
陈长松
涂保
栾博
郭永胜
陈国栋
陈俊超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Contemporary Amperex Technology Co Ltd
Original Assignee
Contemporary Amperex Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Contemporary Amperex Technology Co Ltd filed Critical Contemporary Amperex Technology Co Ltd
Priority to EP23924649.9A priority Critical patent/EP4586792A4/en
Priority to PCT/CN2023/079072 priority patent/WO2024178679A1/zh
Priority to JP2025521152A priority patent/JP2025535120A/ja
Priority to CN202380054279.9A priority patent/CN119631604B/zh
Priority to KR1020257011734A priority patent/KR20250068692A/ko
Publication of WO2024178679A1 publication Critical patent/WO2024178679A1/zh
Priority to US19/192,360 priority patent/US20250261554A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
    • C07C35/44—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed ring system having more than three rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/351—Thickness
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application relates to the technical field of solar cells, and in particular to a fullerene composite material and a preparation method thereof, a perovskite solar cell and a preparation method thereof, and an electrical device.
  • perovskite solar cells have attracted widespread attention due to their high photoelectric conversion efficiency and relatively simple preparation process.
  • fullerene and its derivatives are commonly used electron acceptors.
  • the photoelectric conversion efficiency of the cells obtained by preparing the electron transport layer of perovskite solar cells with pure fullerene and its derivatives is still relatively low.
  • the present application provides a fullerene composite material, including a main material and a doping material, wherein the main material includes at least one of a first fullerene and a first fullerene derivative, the doping material is selected from at least one of a second fullerene and a second fullerene derivative, and a molecular structure of the doping material has a partial structure embedded in the lattice of the first fullerene and/or the first fullerene derivative.
  • the conductivity of the fullerene composite material can be improved, and the photoelectric conversion efficiency of the perovskite solar cell can be improved.
  • the mass percentage of the doping material is 0.0001% to 1% based on the total mass of the first fullerene and/or the first fullerene derivative and the doping material. If the mass percentage of the doping material is too small, the doping effect is poor, and if the mass percentage of the doping material is too large, it may have a great impact on the intrinsic structure of the main material.
  • 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.
  • the present application also provides a method for preparing a fullerene composite material, comprising the following steps:
  • 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 doping material.
  • the doping material is added to the reaction system before the heat treatment, so that the doping material can be more evenly dispersed in the reaction system.
  • the doping material is more evenly doped into the first fullerene derivative, which can reduce the risk of agglomeration of the doping material and is conducive to improving the doping uniformity.
  • the raw material for synthesizing the first fullerene derivative includes a third fullerene, 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate and a base; mixing the first raw material and the second raw material in a solvent includes:
  • the 5-phenyl-5-(p-toluenesulfonylhydrazide)pentanoic acid methyl ester 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.
  • the molar ratio of the third fullerene, the doping material, the methyl 5-phenyl-5-(p-toluenesulfonylhydrazide)pentanoate and the base is 1:(10 -5 ⁇ 10 -2 ):(1 ⁇ 2):(1 ⁇ 10).
  • the first sub-solvent includes pyridine.
  • the second sub-solvent includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene.
  • the base includes at least one of sodium methoxide, cesium carbonate, sodium hydroxide, and potassium hydroxide.
  • the first solvent includes at least one of toluene, xylene, chlorobenzene, and dichlorobenzene.
  • the heat treatment is performed at a temperature of 100°C to 300°C.
  • the heat treatment time is 24 hours to 60 hours.
  • the thermal treatment comprises heating to reflux.
  • the present application also provides a perovskite solar cell, comprising a first electrode, a perovskite layer, an electron transport layer and a second electrode stacked in sequence;
  • the electron transport layer includes the fullerene composite material, or,
  • the electron transport layer comprises the fullerene composite material obtained by the preparation method.
  • the electron transport layer includes a fullerene composite material, which can improve the perovskite solar cell Battery performance.
  • the thickness of the electron transport layer is 10 nm to 100 nm.
  • the present application also provides a method for preparing a perovskite solar cell, comprising the following steps:
  • the electron transport layer includes a fullerene composite material, which includes a main material and a doping material.
  • the main material includes at least one of a first fullerene and a first fullerene derivative
  • the doping material is selected from at least one of a second fullerene and a second fullerene derivative.
  • the molecular structure of the doping material has a partial structure embedded in the lattice of the first fullerene and/or the first fullerene derivative.
  • the present application also provides an electrical device, comprising the perovskite solar cell.
  • FIG. 1 is a schematic diagram of the structure of an exemplary perovskite solar cell.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the numerical range "a-b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order.
  • 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), etc.
  • the “include” and “comprising” mentioned in this application represent open-ended or closed-ended expressions.
  • the “include” and “comprising” may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: 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).
  • room temperature generally refers to 4°C to 30°C, preferably 25 ⁇ 5°C.
  • the present application provides a fullerene composite material, including a main material and a doping material, wherein the main material includes a first fullerene and at least one of the first fullerene derivatives, the doping material is selected from at least one of the second fullerene and the second fullerene derivative, and the molecular structure of the doping material has a partial structure embedded in the lattice of the first fullerene and/or the first fullerene derivative.
  • the main material including the first fullerene and/or the first fullerene derivative is doped by at least one of the second fullerene and the second fullerene derivative.
  • the molecular structure of the doping material is partially 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.
  • the presence of side chains may increase the distance between molecules, making it difficult to extract carriers, and restricting the improvement of the conductivity of fullerene derivatives.
  • the molecular structure of the doping material is partially embedded in the lattice of the first fullerene and/or the first fullerene derivative, which can reduce the distance between molecules, improve the transmission capacity of electrons, and improve the conductivity of the fullerene composite material.
  • first fullerene and the second fullerene may be the same or different.
  • the first fullerene derivative and the second fullerene derivative may be the same or different.
  • 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.
  • the fullerene derivative is usually obtained by modifying fullerene, wherein the lattice of fullerene is usually spherical, so that the lattice of the fullerene derivative is mainly spherical.
  • the molecular structure of the doping material has a part of its structure embedded in the lattice of the first fullerene and/or the first fullerene derivative, it can be shown that the molecular structure of the doping material has a part of its structure embedded in the spherical lattice of the first fullerene and/or the first fullerene derivative.
  • the side chain of the doping material is embedded in the lattice of the first fullerene and/or the first fullerene derivative.
  • the fullerene derivative is usually obtained by modifying fullerenes such as C50, C60 and C70.
  • the other structure of the molecular structure of the doping material can extend from the crystal lattice of the first fullerene and/or the first fullerene derivative, or can be attached to the outer surface of the crystal lattice of the first fullerene and/or the first fullerene derivative.
  • the mass percentage of the doping material is 0.0001% to 1% based on the total mass of the first fullerene and/or the first fullerene derivative and the doping material.
  • the mass percentage of the doping material is 0.0001%, 0.001%, or 1%. 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 doping material is too small, the doping effect is poor, and if the mass percentage of the doping material is too large, it may have a great impact on the intrinsic structure of the main material.
  • the type and content of the doping material can be measured by liquid chromatography.
  • the mass percentage of the doping material based on the total mass of the first fullerene and/or the first fullerene derivative and the doping material may be recorded as the doping amount of the doping material.
  • the fullerene composite material is composed of a main material and a doping material
  • the main material is selected from at least one of the first fullerene and the first fullerene derivative
  • the doping material is selected from at least one of the fullerene and the second fullerene derivative
  • the molecular structure of the doping material has a partial structure embedded in the lattice of the first fullerene and/or the first fullerene derivative.
  • the mass percentage of the doping material is 0.0001% to 1% in terms of the total mass of the first fullerene and/or the first fullerene derivative and the doping material.
  • the mass percentage of the doping material measured as a percentage of the total mass of the first fullerene and/or the first fullerene derivative, and the doping 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.
  • the present application also provides a method for preparing a fullerene composite material.
  • the method for preparing the fullerene composite material comprises the following steps: mixing a first raw material and a second raw material in a first solvent, and heat treating the obtained mixed system; 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 doping material.
  • the agglomeration of the doping material is an important factor affecting the performance of the composite material.
  • the doping material is added to the reaction system before the heat treatment, so that the doping material can be more evenly dispersed in the reaction system.
  • the doping material is more evenly doped into the first fullerene derivative, which can reduce the risk of agglomeration of the doping material and is conducive to improving the doping uniformity.
  • the first raw material contains a raw material for synthesizing a first fullerene derivative
  • the raw material for synthesizing the first fullerene derivative includes a third fullerene, 5-phenyl-5-(p-toluenesulfonylhydrazide)pentanoic acid methyl ester and a base
  • mixing the first raw material with the second raw material in a solvent includes: dispersing 5-phenyl-5-(p-toluenesulfonylhydrazide)pentanoic acid methyl ester 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.
  • the third fullerene includes at least one of C50, C60 and C70.
  • the first fullerene, the second fullerene and the third fullerene may be different from each other or may be completely the same.
  • the molar ratio of the third fullerene, the doping material, 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl 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.
  • the first sub-solvent includes pyridine.
  • the second sub-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.
  • the base includes at least one of sodium methoxide, cesium carbonate, sodium hydroxide and potassium hydroxide.
  • the raw materials for synthesizing the first fullerene derivative include the third fullerene, 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate and a base; mixing the first raw material with the second raw material in a solvent includes: adding 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate to a first sub-solvent, then adding a base, stirring, and evacuating gas to place the solution system under an argon atmosphere; adding the second raw material and the third fullerene to a second sub-solvent, and then adding the resulting solution to a solution system containing the first sub-solvent.
  • the raw materials for synthesizing the first fullerene derivative include the third fullerene, 5-phenyl-5-(p-toluenesulfonylhydrazide) methyl pentanoate and a base.
  • the first raw material and the second raw material are mixed in a first solvent, and the obtained mixed system is subjected to heat treatment, and the method further includes: removing the solvent from the product obtained after the heat treatment, and then separating the product.
  • the method for removing the solvent can be a rotary evaporation method.
  • the method for separating the product can be a column chromatography method.
  • the first raw material is a first fullerene derivative.
  • the mass percentage of the doping material is 0.0001% to 1% based on the total mass of the first fullerene derivative and the doping material.
  • the mass percentage of the doping 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. based on the total mass of the first fullerene derivative and the doping material.
  • the first raw material is a first fullerene derivative.
  • the first raw material and the second raw material are mixed in a first solvent, and the obtained mixed system is subjected to heat treatment, and the method further comprises: concentrating the product obtained after the heat treatment, and then adding methanol to precipitate. The precipitation obtains a fullerene composite material.
  • the first solvent 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.
  • the temperature of the heat treatment is 100°C to 300°C.
  • the time of the heat treatment is 24h to 60h.
  • the heat treatment includes heating under reflux.
  • the temperature of the heat treatment is 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, 280°C, 300°C, etc.
  • the time of the heat treatment is 24h, 30h, 36h, 48h, 60h, etc.
  • the preparation method of 5-phenyl-5-(toluenesulfonylhydrazide) methyl pentanoate comprises: mixing 4-benzoylbutyric acid methyl ester, toluenesulfonylhydrazide and methanol, heating and refluxing reaction, cooling to room temperature, shielding from light, and then transferring to -15°C and shielding overnight, filtering, and recrystallizing the product in methanol, and the product is vacuumed at 40°C overnight to obtain white solid 5-phenyl-5-(toluenesulfonylhydrazide) methyl pentanoate.
  • the heating reflux reaction time is 12 hours, and after cooling to room temperature, shielding from light is stored for 24 hours.
  • 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 to reflux and reacting overnight, stopping stirring, neutralizing with saturated sodium carbonate until there are no bubbles, separating oil and water, and then extracting the aqueous phase with ethyl acetate, combining the organic phases, removing water with anhydrous calcium chloride, distilling under reduced pressure to remove the solvent, eluting and separating the product in a silica gel column, the eluent is ethyl acetate and n-hexane, wherein the volume ratio of ethyl acetate to n-hexane is 3:1, and a light yellow oily liquid methyl 4-benzoylbutyrate is obtained.
  • the present application also provides an electron transport film.
  • the electron transport film comprises the fullerene composite material or the fullerene composite material obtained by the preparation method of the fullerene composite material.
  • the thickness of the electron transport film is 10nm to 100nm.
  • the thickness of the electron transport film is 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc.
  • the present application also provides an electron transport slurry.
  • the electron transport slurry includes a second solvent and also includes the fullerene composite material or the fullerene composite material obtained by the preparation method of the fullerene composite material.
  • 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.
  • the present application also provides a perovskite solar cell.
  • the perovskite solar cell comprises a first electrode layer, a perovskite layer, an electron transport layer and a second electrode layer stacked in sequence, the electron transport layer comprises the above-mentioned fullerene composite material, or the electron transport layer comprises the fullerene composite material obtained by the above-mentioned preparation method, or the electron transport layer comprises the above-mentioned electron transport film, or the electron transport layer is prepared from a material including the above-mentioned electron transport slurry.
  • the electron transport layer comprises the fullerene composite material, which can improve the performance of the perovskite solar cell.
  • the electron transport layer is prepared by spin coating and annealing the material including the electron transport slurry. Further, the electron transport layer is prepared by spin coating and annealing the material including the electron transport slurry.
  • the thickness of the electron transport layer is 10 nm to 100 nm.
  • 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.
  • the electron transport layer is obtained by spin coating and annealing a material including the above-mentioned electron transport slurry.
  • 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.
  • the transparent electrode is a transparent glass electrode.
  • the first electrode is generally a transparent conductive glass.
  • 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).
  • FTO fluorine-doped tin oxide
  • ITO indium tin oxide
  • AZO aluminum-doped zinc oxide
  • BZO boron-doped zinc oxide
  • IZO indium zinc oxide
  • IWO indium tungsten oxide
  • the thickness of the first electrode layer is 100nm to 1000nm, and can be 300nm to 800nm.
  • the second electrode is generally a metal electrode.
  • the second electrode is selected from at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W and alloys thereof.
  • the thickness of the second electrode is 20nm to 200nm, optionally 60nm to 100nm, and further optionally 70nm to 90nm.
  • the perovskite layer is a light absorbing layer composed of a perovskite material.
  • the chemical formula of the material of the perovskite layer is ABX 3 or A 2 CDX 6 , wherein:
  • B is an inorganic or organic or organic-inorganic mixed 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 at least one of the divalent metal ions Pb2+ and Sn2+ .
  • C is an inorganic or organic or organic-inorganic mixed cation, and may be a monovalent metal ion such as Ag + .
  • D is an inorganic or organic or organic-inorganic mixed cation, and can be optionally a trivalent metal ion such as bismuth cation Bi 3+ , antimony cation Sb 3+ , indium cation In 3+ , or the like.
  • X is an inorganic or organic or organic-inorganic mixed anion, optionally one or more of a halogen anion and a carboxylate anion, and further optionally a bromide ion (Br ⁇ ) or an iodide ion (I ⁇ ).
  • the perovskite layer has a band gap of 1.20 eV to 2.30 eV.
  • the thickness of the perovskite layer is 200 nm to 800 nm, and optionally 400 nm to 600 nm.
  • the perovskite solar cell further comprises a hole transport layer, and the hole transport layer is located between the first electrode and the perovskite layer.
  • the hole transport layer can be at least one of the following materials and their derivatives and materials obtained by doping or passivation: poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), poly-3 hexylthiophene (P3HT), triphenylamine (H101) with triptycene as the core, 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N- (4-aniline) carbazole-spirobifluorene (CzPAF-SBF), poly (3,4-ethylenedioxythiophene): poly (styrene sulfone) (PEDOT:PSS), polythiophene, nickel oxide (NiO x ), molybdenum oxide (MoO 3 ),
  • the perovskite solar cell further comprises a first passivation layer, wherein the first passivation layer is located between the perovskite layer and the hole transport layer.
  • the material of the first passivation layer is PTAA.
  • the perovskite solar cell further comprises a second passivation layer and/or a buffer layer, and the second passivation layer and/or the buffer layer is located between the electron transport layer and the second electrode.
  • the material of the second passivation layer and the buffer layer is bathocuproine (BCP).
  • perovskite solar cells include formal perovskite solar cells and inverted perovskite solar cells.
  • formal perovskite solar cells the formal perovskite solar cell includes a transparent electrode and an electron transport layer, a perovskite layer, a hole transport layer and a metal electrode stacked sequentially on the transparent electrode.
  • 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 stacked sequentially on the transparent electrode.
  • the corresponding formal perovskite solar cell and inverted perovskite solar cell can be obtained by selecting the first electrode and the second electrode materials.
  • FIG. 1 shows the structure of a perovskite solar cell in an embodiment of the present 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 a buffer layer, and a metal electrode are sequentially stacked on the first electrode.
  • a glass substrate is provided on the surface of the FTO away from the perovskite layer.
  • the present application also provides a method for preparing a perovskite solar cell.
  • the method for preparing a perovskite solar cell comprises the following steps: preparing a perovskite layer on a first electrode; preparing an electron transport layer on the perovskite layer; preparing a second electrode on the electron transport layer; the electron transport layer comprises a fullerene composite material, the fullerene composite material comprises a main material and a doping material, the main material comprises a first fullerene derivative, the doping material is selected from at least one of a fullerene and a second fullerene derivative, and a molecular structure of the doping material has a partial structure embedded in the lattice of the first fullerene derivative.
  • the perovskite layer is prepared by spin coating and annealing.
  • the electron transport layer is prepared by spin coating and annealing.
  • the second electrode is prepared by evaporation.
  • the electron transport layer is prepared by spin coating the electron transport slurry and annealing.
  • the present application also provides an electrical device.
  • the electrical device includes the above-mentioned perovskite solar cell.
  • the electrical device is an electrical device in the fields of communications, transportation, industry and agriculture, lighting, etc.
  • the electrical device may include, for example, These include satellites, communication equipment, traffic lights, lighthouses, wireless telephone booths, monitoring equipment in the oil drilling field, power supply systems, camping lights, electric vehicles, and electronic equipment chargers.
  • S201 Take 20 pieces of FTO conductive glass with a specification of 2.0cm*2.0cm, remove 0.35cm of FTO at both ends by laser etching, and expose the glass substrate; ultrasonically clean the etched FTO conductive glass with water, acetone, and isopropanol in turn; blow dry the solvent of the cleaned FTO conductive glass under a nitrogen gun, and put it into a UV ozone machine for UV ozone cleaning treatment.
  • S205 The fullerene composite material obtained in S104 is dissolved in chlorobenzene to form an electron transport slurry with a concentration of 20 mg/mL, and the electron transport slurry is spin-coated on the perovskite layer at 1500 rpm, and annealed at 100°C for 10 minutes to form an electron transport layer with a thickness of 50 nm. Then, the passivation material BCP solution is spin-coated at 5000 rpm, wherein the BCP solution is BCP dissolved in isopropanol with a concentration of 0.5 mg/mL to form a passivation layer with a thickness of 5 nm. Then, it is placed in an evaporator to evaporate the metal electrode Ag to obtain a perovskite solar cell.
  • the doping material is PC51BM.
  • PC51BM is prepared by S101 to S103 in Example 1, and replacing C60 in S103 with C50.
  • the doping material C50 in S104 in Example 1 is replaced with PC51BM.
  • the doping material is PC51BM
  • the main material is PC61BM
  • the mass percentage of the doping material PC51BM in the fullerene composite material is 0.05%, that is, the doping amount is 0.05%.
  • Example 1 Compared with Example 1, the difference of this embodiment is that C60 in S103 is replaced by 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% as a percentage of the total mass of C50 and C60.
  • the doping material is PC51BM
  • the main material is PC61BM
  • the mass percentage of the doping material PC51BM in the fullerene composite material is 0.05%, that is, the doping amount is 0.05%.
  • Example 1 Compared with Example 1, the difference of this embodiment is that C60 in S103 is replaced by 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% as a percentage of the total mass of C50, C60 and C70.
  • the doping materials are PC51BM and PC71BM
  • the main material is PC61BM
  • the mass percentage of the doping material PC51BM in the fullerene composite material is 0.05%
  • the mass percentage of the 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%.
  • Example 2 Compared with Example 1, the difference of this example is that the amount of doping material C50 added in S104 is adjusted.
  • the doping material is C50
  • the main material is PC61BM
  • the mass percentage of doping material C50 in the obtained fullerene composite material is 0.0001%.
  • Example 2 Compared with Example 1, the difference of this example is that the amount of doping material C50 added in S104 is adjusted.
  • the doping material is C50
  • the main material is PC61BM
  • the mass percentage of doping material C50 in the obtained fullerene composite material is 1%.
  • Example 1 Compared with Example 1, the difference of this embodiment is that C50 is replaced by C70.
  • Example 1 Compared with Example 1, the difference of this example is that the amount of doping material C50 added in S104 is adjusted.
  • the doping material is C50
  • the main material is PC61BM
  • the mass percentage of doping material C50 in the obtained fullerene composite material is 0.00005%.
  • Example 1 Compared with Example 1, the difference of this example is that the amount of doping material C50 added in S104 is adjusted.
  • the doping material is C50
  • the main material is PC61BM
  • the mass percentage of doping material C50 in the obtained fullerene composite material is 1.3%.
  • Example 1 Compared with Example 1, the difference of this example is that S101 to S103 are not performed.
  • S104 C60 and doping material C50 are dissolved in o-dichlorobenzene, heated under reflux for reaction for 48 hours, and the product is concentrated and added to methanol for precipitation to obtain a fullerene composite material.
  • the doping material is C50
  • the main material is C60
  • the mass percentage of doping material C50 in the fullerene composite material is 0.1%.
  • Example 1 Compared with Example 1, the difference of this comparative example is that C50 is not added to S104, that is, PC61BM is not doped.
  • Example 1 Compared with Example 1, the difference of this comparative example is that PC61BM and C50 are directly mixed to obtain a fullerene composite material, wherein the mass percentage of C50 in the fullerene composite material is 0.1%.
  • Example 2 Compared with Example 1, the fullerene composite material was not prepared, and the electron transport layer was prepared by evaporating C60 in the perovskite solar cell.
  • the battery performance is tested to obtain the IV curve.
  • the short-circuit current Jsc (unit mA/cm 2 ), open-circuit voltage Voc (unit V), maximum light output current Jmpp (unit mA) and maximum light output voltage Vmpp (unit V)
  • the perovskite solar cell in the embodiment has a higher photoelectric conversion efficiency than the comparative example.
  • the perovskite solar cell in which the electron transport layer includes a doping material has a higher photoelectric conversion efficiency.
  • Example 1 and comparative example 2 that compared with the method of directly mixing PC61BM and C50, the fullerene composite material obtained by the preparation method in Example 1 is applied to the electron transport layer, and the obtained perovskite solar cell has a higher photoelectric conversion efficiency.
  • the doping material accounts for % of the fullerene composite material
  • the mass percentage is 0.0001% to 1%
  • the perovskite solar cell can achieve a higher photoelectric conversion efficiency.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本申请涉及一种富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置。富勒烯复合材料包括主体材料和掺杂材料，主体材料包括第一富勒烯和第一富勒烯衍生物中的至少一种，掺杂材料选自第二富勒烯及第二富勒烯衍生物中的至少一种，掺杂材料的分子结构有部分结构嵌入第一富勒烯和/或第一富勒烯衍生物的晶格内。

Description

富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置 技术领域
本申请涉及太阳能电池技术领域，特别是涉及一种富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置。
背景技术
随着太阳能电池研究的不断发展，钙钛矿太阳能电池因具有光电转换效率较高、制备工艺较为简单而受到广泛关注。
在钙钛矿太阳能电池的结构中，富勒烯及其衍生物是较为常用的电子受体。然而，随着钙钛矿太阳能电池研究的不断深入，以纯的富勒烯及其衍生物来制备钙钛矿太阳能电池的电子传输层得到的电池的光电转换效率还是较低。
发明内容
根据本申请的各实施例，本申请提供一种富勒烯复合材料，包括主体材料和掺杂材料，所述主体材料包括第一富勒烯和第一富勒烯衍生物中的至少一种，所述掺杂材料选自第二富勒烯及第二富勒烯衍生物中的至少一种，所述掺杂材料的分子结构有部分结构嵌入所述第一富勒烯和/或所述第一富勒烯衍生物的晶格内。
本申请中通过第二富勒烯及第二富勒烯衍生物中的至少一种对包括第一富勒烯和/或第一富勒烯衍生物的主体材料进行掺杂，可以提高富勒烯复合材料的导电性，改善钙钛矿太阳能电池的光电转换效率。
在一些实施方式中，以占所述第一富勒烯和/或所述第一富勒烯衍生物，以及所述掺杂材料的总质量的百分数计，所述掺杂材料的质量百分数为0.0001％～1％。掺杂材料的质量百分数过小，掺杂效果较差，掺杂材料的质量百分数过大则可能对主体材料的本征结构造成过大的影响。
在一些实施方式中，所述第一富勒烯包括C50、C60以及C70中的至少一种，所述第一富勒烯衍生物包括PC51BM、PC52BM、PC61BM、PC62BM、PC71BM以及PC72BM中的至少一种。这些富勒烯和富勒烯衍生物来源较为广泛，便于获取。
在一些实施方式中，所述第二富勒烯包括C50、C60以及C70中的至少一种，所述第二富勒烯衍生物包括PC51BM、PC52BM、PC61BM、PC62BM、PC71BM以及PC72BM中的至少一种。这些富勒烯和富勒烯衍生物来源较为广泛，便于获取。
本申请还提供一种富勒烯复合材料的制备方法，包括如下步骤：
将第一原料与第二原料在第一溶剂中混合，对得到的混合体系进行热处理；
所述第一原料含有第一富勒烯和/或第一富勒烯衍生物和/或用于合成所述第一富勒烯衍生物的原料，所述第二原料含有用于作为掺杂材料的第二富勒烯和第二富勒烯衍生物中的至少一种。
在该制备方法中，将掺杂材料在热处理之前加入到反应体系，可以使掺杂材料更加均匀地分散在反应体系中。在形成的富勒烯复合材料中，掺杂材料更加均匀地掺杂到第一富勒烯衍生物中，可以降低掺杂材料出现团聚的风险，有利于提高掺杂均匀性。
在一些实施方式中，所述用于合成所述第一富勒烯衍生物的原料包括第三富勒烯、5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以及碱；将第一原料与第二原料在溶剂中混合包括：
将所述5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯和所述碱分散在第一子溶剂中，将所述第二原料和所述第三富勒烯分散在第二子溶剂中，将两个溶液体系混合。
在一些实施方式中，所述第三富勒烯、所述掺杂材料、所述5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以及所述碱的摩尔比为1：(10-5～10-2)：(1～2)：(1～10)。
在一些实施方式中，所述第一子溶剂包括吡啶。
在一些实施方式中，所述第二子溶剂包括甲苯、二甲苯、氯苯以及二氯苯中的至少一种。
在一些实施方式中，所述碱包括甲醇钠、碳酸铯、氢氧化钠以及氢氧化钾中的至少一种。
在一些实施方式中，所述第一溶剂包括甲苯、二甲苯、氯苯以及二氯苯中的至少一种。
在一些实施方式中，所述热处理的温度为100℃～300℃。
在一些实施方式中，所述热处理的时间为24h～60h。
在一些实施方式中，所述热处理包括加热回流。
本申请还提供一种钙钛矿太阳能电池，包括依次层叠设置的第一电极、钙钛矿层、电子传输层以及第二电极；
所述电子传输层包括所述富勒烯复合材料，或者，
所述电子传输层包括所述制备方法得到的富勒烯复合材料。
在上述钙钛矿太阳能电池中，电子传输层包括富勒烯复合材料，可以改善钙钛矿太阳能 电池的性能。
在一些实施方式中，所述电子传输层的厚度为10nm～100nm。
本申请还提供一种钙钛矿太阳能电池的制备方法，包括如下步骤：
在第一电极上制备钙钛矿层；
在所述钙钛矿层上制备电子传输层；
在所述电子传输层上制备第二电极；
所述电子传输层包括富勒烯复合材料，所述富勒烯复合材料包括主体材料和掺杂材料，所述主体材料包括第一富勒烯和第一富勒烯衍生物中的至少一种，所述掺杂材料选自第二富勒烯及第二富勒烯衍生物中的至少一种，所述掺杂材料的分子结构有部分结构嵌入所述第一富勒烯和/或所述第一富勒烯衍生物的晶格内。
本申请还提供一种用电装置，包括所述钙钛矿太阳能电池。
附图说明
为了更清楚地说明本申请的技术方案，下面将对本申请中所使用的附图作简单介绍。显而易见地，下面所描述的附图仅仅是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。
图1为一示例的钙钛矿太阳能电池的结构示意图。
为了更好地描述和说明这里公开的那些发明的实施例和/或示例，可以参考一副或多副附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的任何一者的范围的限制。
具体实施方式
以下结合具体实施例对本申请的钙钛矿太阳能电池及其制备方法、用电装置作进一步详细的说明。本发明可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本发明公开内容理解更加透彻全面。
本申请的一个或多个实施例的细节在下面的附图和描述中提出。本申请的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施 例的目的，不是旨在于限制本发明。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
如果没有特别的说明，在本申请中，术语“室温”一般指4℃～30℃，较佳地指25±5℃。
本申请提供一种富勒烯复合材料，包括主体材料和掺杂材料，主体材料包括第一富勒烯 和第一富勒烯衍生物中的至少一种，掺杂材料选自第二富勒烯及第二富勒烯衍生物中的至少一种，掺杂材料的分子结构有部分结构嵌入第一富勒烯和/或第一富勒烯衍生物的晶格内。
在本申请的富勒烯复合材料中，通过第二富勒烯及第二富勒烯衍生物中的至少一种对包括第一富勒烯和/或第一富勒烯衍生物的主体材料进行掺杂，在复合材料中，掺杂材料的分子结构有部分结构嵌入第一富勒烯和/或第一富勒烯衍生物的晶格内，可以提高富勒烯复合材料的导电性，改善钙钛矿太阳能电池的光电转换效率。
在富勒烯衍生物中，由于支链的存在，可能会导致分子间距离增大，使得载流子提取困难，制约富勒烯衍生物导电性能的提升。掺杂材料的分子结构有部分结构嵌入第一富勒烯和/或第一富勒烯衍生物的晶格内，可以缩小分子间的距离，提高电子的传输能力，改善富勒烯复合材料的导电性。
可以理解的是，第一富勒烯和第二富勒烯可以相同，也可以不同。第一富勒烯衍生物和第二富勒烯衍生物可以相同，也可以不同。
在一些实施方式中，第一富勒烯包括C50、C60以及C70中的至少一种。第一富勒烯衍生物包括PC51BM、PC52BM、PC61BM、PC62BM、PC71BM以及PC72BM中的至少一种。第二富勒烯包括C50、C60以及C70中的至少一种。第二富勒烯衍生物包括PC51BM、PC52BM、PC61BM、PC62BM、PC71BM以及PC72BM中的至少一种。这些富勒烯和富勒烯衍生物来源较为广泛，便于获取。
还可以理解的是，富勒烯衍生物通常是由富勒烯通过改性得到，其中富勒烯的晶格通常为球形，使得富勒烯衍生物的晶格主要也表现为具有球形形状。当掺杂材料的分子结构有部分结构嵌入第一富勒烯和/或第一富勒烯衍生物的晶格内时，可以表现为掺杂材料的分子结构有部分结构嵌入第一富勒烯和/或第一富勒烯衍生物的球形晶格内。可选地，当掺杂材料具有侧链时，掺杂材料的侧链嵌入第一富勒烯和/或第一富勒烯衍生物的晶格内。可理解，富勒烯衍生物通常是由C50、C60以及C70等富勒烯通过改性得到。
还可以理解的是，当掺杂材料的分子结构有部分结构嵌入第一富勒烯和/或第一富勒烯衍生物的晶格内时，掺杂材料的分子结构的另外的结构可以自第一富勒烯和/或第一富勒烯衍生物的晶格伸出，也可以附着在第一富勒烯和/或第一富勒烯衍生物的晶格的外表面。
在一些实施方式中，以占第一富勒烯和/或第一富勒烯衍生物，以及掺杂材料的总质量的百分数计，掺杂材料的质量百分数为0.0001％～1％。可选地，以占第一富勒烯和/或第一富勒烯衍生物，以及掺杂材料的总质量的百分数计，掺杂材料的质量百分数为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％等。掺杂材料的质量百分数过小，掺杂效果较差，掺杂材料的质量百分数过大则可能对主体材料的本征结构造成过大的影响。
可选地，掺杂材料的种类和含量可以通过液相色谱测得。可选地，液相色谱的条件为：色谱柱为长度为15cm的C18方向柱，流动相为甲苯:甲醇＝1:2，检测器为DAD检测器。
在本申请中，可以将以占第一富勒烯和/或第一富勒烯衍生物，以及掺杂材料的总质量的百分数计，掺杂材料的质量百分数记为掺杂材料的掺杂量。
在一些实施方式中，富勒烯复合材料由主体材料和掺杂材料组成，主体材料选自第一富勒烯和第一富勒烯衍生物中的至少一种，掺杂材料选自富勒烯及第二富勒烯衍生物中的至少一种，掺杂材料的分子结构有部分结构嵌入第一富勒烯和/或第一富勒烯衍生物的晶格内。可选地，以占第一富勒烯和/或第一富勒烯衍生物，以及掺杂材料的总质量的百分数计，掺杂材料的质量百分数为0.0001％～1％。可选地，以占第一富勒烯和/或第一富勒烯衍生物，以及掺杂材料的总质量的百分数计，掺杂材料的质量百分数为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％等。
本申请还提供了一种富勒烯复合材料的制备方法。该富勒烯复合材料的制备方法包括如下步骤：将第一原料与第二原料在第一溶剂中混合，对得到的混合体系进行热处理；其中，第一原料含有第一富勒烯和/或第一富勒烯衍生物和/或用于合成所述第一富勒烯衍生物的原料，第二原料含有用于作为掺杂材料的富勒烯和第二富勒烯衍生物中的至少一种。
在制备富勒烯复合材料时，掺杂材料的团聚是影响复合材料性能的一个重要因素，在该制备方法中，将掺杂材料在热处理之前加入到反应体系，可以使掺杂材料更加均匀地分散在反应体系中。在形成的富勒烯复合材料中，掺杂材料更加均匀地掺杂到第一富勒烯衍生物中，可以降低掺杂材料出现团聚的风险，有利于提高掺杂均匀性。
在一些实施方式中，第一原料含有用于合成第一富勒烯衍生物的原料，用于合成第一富勒烯衍生物的原料包括第三富勒烯、5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以及碱；将第一原料与第二原料在溶剂中混合包括：将5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯和碱分散在第一子溶剂中，将第二原料和第三富勒烯分散在第二子溶剂中，将两个溶液体系混合。
可选地，第三富勒烯包括C50、C60以及C70中的至少一种。可选地，第一富勒烯、第二富勒烯以及第三富勒烯可以不完全相同，也可以完全相同。
在一些实施方式中，第三富勒烯、掺杂材料、5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以 及碱的摩尔比为1：(10-5～10-2)：(1～2)：(1～10)。可选地，第三富勒烯、掺杂材料、5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以及碱的摩尔比为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等。
在一些实施方式中，第一子溶剂包括吡啶。
可选地，第二子溶剂包括甲苯、二甲苯、氯苯以及二氯苯中的至少一种。其中，二甲苯包括邻二甲苯、间二甲苯和对二甲苯中的至少一种。二氯苯包括邻二氯苯、间二氯苯和对二氯苯中的至少一种。
可选地，碱包括甲醇钠、碳酸铯、氢氧化钠以及氢氧化钾中的至少一种。
可选地，用于合成第一富勒烯衍生物的原料包括第三富勒烯、5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以及碱；将第一原料与第二原料在溶剂中混合包括：将5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯加入第一子溶剂中，然后加入碱，搅拌，抽放气，使溶液体系处于氩气氛围下；将第二原料和第三富勒烯加入第二子溶剂中，然后将得到的溶液加入包含第一子溶剂的溶液体系中。
可选地，用于合成第一富勒烯衍生物的原料包括第三富勒烯、5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以及碱。将第一原料与第二原料在第一溶剂中混合，对得到的混合体系进行热处理之后还包括：将经过热处理之后得到的产物除去溶剂，再将产物进行分离。可选地，除去溶剂的方式可以采用旋蒸的方式。可选地，将产物进行分离的方式可以采用柱层析的方式。
在一些实施方式中，第一原料为第一富勒烯衍生物。以占第一富勒烯衍生物和掺杂材料的总质量的百分数计，掺杂材料的质量百分数为0.0001％～1％。可选地，以占第一富勒烯衍生物和掺杂材料的总质量的百分数计，掺杂材料的质量百分数为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％等。
可选地，第一原料为第一富勒烯衍生物。将第一原料与第二原料在第一溶剂中混合，对得到的混合体系进行热处理之后还包括：将经过热处理之后得到的产物浓缩，然后加入甲醇，沉淀析出。沉淀析出得到富勒烯复合材料。
在一些实施方式中，第一溶剂包括甲苯、二甲苯、氯苯以及二氯苯中的至少一种。其中，二甲苯包括邻二甲苯、间二甲苯和对二甲苯中的至少一种。二氯苯包括邻二氯苯、间二氯苯和对二氯苯中的至少一种。
在一些实施方式中，热处理的温度为100℃～300℃。热处理的时间为24h～60h。热处理包括加热回流。可选地，热处理的温度为100℃、120℃、150℃、180℃、200℃、220℃、250℃、280℃、300℃等。热处理的时间为24h、30h、36h、48h、60h等。
在一些实施方式中，5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯的制备方法包括：将4-苯甲酰基丁酸甲酯、对甲苯磺酰肼和甲醇混合加热回流反应，冷却至室温，遮光保存，后转移至-15℃遮光过夜，抽滤，产物在甲醇中进行重结晶，产物于40℃真空过夜，得到白色固体5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯。可选地，加热回流反应的时间为12h，冷却至室温后遮光保存24h。
在一些实施方式中，4-苯甲酰基丁酸甲酯的制备方法包括：将苯甲酰基丁酸溶于氯苯中，加入甲醇，搅拌至完全溶解，滴加盐酸，继续搅拌，加热回流反应过夜，停止搅拌，用饱和碳酸钠中和至没有气泡，油水分离，然后用乙酸乙酯萃取水相，将有机相合并在一起，用无水氯化钙除水，减压蒸馏除去溶剂，在硅胶柱中将产物洗脱分离，洗脱剂为乙酸乙酯和正己烷，其中乙酸乙酯和正己烷的体积比3:1，得到淡黄色油状液体4-苯甲酰基丁酸甲酯。
本申请还提供一种电子传输薄膜。该电子传输薄膜包括上述富勒烯复合材料或者上述富勒烯复合材料的制备方法得到的富勒烯复合材料。可选地，电子传输薄膜的厚度为10nm～100nm。进一步可选地，电子传输薄膜的厚度为10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm等。
本申请还提供一种电子传输浆料。该电子传输浆料包括第二溶剂，还包括上述富勒烯复合材料或者上述富勒烯复合材料的制备方法得到的富勒烯复合材料。可选地，电子传输浆料中第二溶剂包括甲苯、二甲苯、氯苯以及二氯苯中的至少一种。其中，二甲苯包括邻二甲苯、间二甲苯和对二甲苯中的至少一种。二氯苯包括邻二氯苯、间二氯苯和对二氯苯中的至少一种。
本申请还提供一种钙钛矿太阳能电池。该钙钛矿太阳能电池包括依次层叠设置的第一电极层、钙钛矿层、电子传输层以及第二电极层，电子传输层包括上述富勒烯复合材料，或者，电子传输层包括上述制备方法得到的富勒烯复合材料，或者，电子传输层包括上述电子传输薄膜，或者，电子传输层由包括上述电子传输浆料的材料制备而成。在钙钛矿太阳能电池中，电子传输层包括富勒烯复合材料，可以改善钙钛矿太阳能电池的性能。
可选地，电子传输层由包括上述电子传输浆料的材料经过旋涂、退火制备而成。进一步地，电子传输层由上述电子传输浆料经过旋涂、退火制备而成。
可选地，电子传输层的厚度为10nm～100nm。可选地，电子传输层的厚度为10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm等。
可选地，电子传输层由包括上述电子传输浆料的材料经过旋涂、退火得到。
可选地，第一电极为透明电极或金属电极。第二电极为透明电极或金属电极。进一步可选地，第一电极和第二电极不同。可选地，透明电极为透明玻璃电极。
在一些实施方式中，第一电极通常为透明导电玻璃。可选地，第一电极选自氟掺杂的氧化锡(FTO)、氧化铟锡(ITO)、掺铝氧化锌(AZO)、掺硼氧化锌(BZO)、氧化铟锌(IZO)和氧化铟钨(IWO)中的至少一种。可选地，第一电极层的厚度为100nm～1000nm，可选为300nm～800nm。
在一些实施方式中，第二电极通常为金属电极。可选地，第二电极选自Au、Ag、Cu、Al、Ni、Cr、Bi、Pt、Mg、Mo、W及其合金中的至少一种。可选地，第二电极的厚度为20nm～200nm，可选地为60nm～100nm，进一步可选地为70nm～90nm。可以理解的是，钙钛矿层为光吸收层，由钙钛矿材料组成。可选地，钙钛矿层的材料的化学式为ABX3或A2CDX6，其中：
A为无机或有机或有机-无机混合阳离子，包含有机胺阳离子、Cs阳离子、K阳离子、Rb阳离子和Li阳离子中的至少一种；所述有机胺阳离子选自(NR1R2R3R4)+、(R1R2N＝CR3R4)+、(R1R2N-C(R5)＝NR3R4)+或(R1R2N-C(NR5R6)＝R3R4)+，其中，R1、R2、R3、R4、R5和R6各自独立地选自H、取代或非取代的C1-20烷基或取代或非取代的芳基；A可选地为甲胺基(CH3NH3 +)(MA+)，甲脒基(HC(NH2)2 +)(FA+)，铯离子(Cs+)和铷(Rb+)中的至少一种，进一步可选地为甲胺基(CH3NH3 +)或甲脒基(HC(NH2)2 +)。
B为无机或有机或有机-无机混合阳离子，包括铅、锡、锌、钛、锑、铋、镍、铁、钴、银、铜、镓、锗、镁、钙、铟、铝、锰、铬、钼和铕中的至少一种，可选地为二价金属离子Pb2+和Sn2+中的至少一种。
C为无机或有机或有机-无机混合阳离子，可选地为一价金属离子Ag+等。
D为无机或有机或有机-无机混合阳离子，可选地为三价金属离子铋阳离子Bi3+、锑阳离子Sb3+、铟阳离子In3+等。
X为无机或有机或有机-无机混合阴离子，可选地为卤素阴离子和羧酸根阴离子中的一种或多种，进一步可选地为溴离子(Br-)或碘离子(I-)。
在一些实施方式中，钙钛矿层的带隙为1.20eV-2.30eV。
在一些实施方式中，钙钛矿层的厚度为200nm～800nm，可选为400nm～600nm。
在一些实施方式中，钙钛矿太阳能电池还包括空穴传输层，空穴传输层位于第一电极和钙钛矿层之间。可选地，空穴传输层可以为以下材料及其衍生物及其经掺杂或钝化所得的材料中的至少一种：聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚-3已基噻吩(P3HT)、三蝶烯为核的三苯胺(H101)、3,4-乙烯二氧噻吩-甲氧基三苯胺(EDOT-OMeTPA)、N-(4-苯胺)咔唑-螺双芴(CzPAF-SBF)、聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺)(PEDOT:PSS)、聚噻吩，氧化镍(NiOx)、氧化钼(MoO3)、碘化亚铜(CuI)、氧化亚铜(CuO)等。
在一些实施方式中，钙钛矿太阳能电池还包括第一钝化层，第一钝化层位于钙钛矿层和空穴传输层之间。可选地，第一钝化层的材料为PTAA。
在一些实施方式中，钙钛矿太阳能电池还包括第二钝化层和/或缓冲层，第二钝化层和/或缓冲层位于电子传输层和第二电极之间。可选地，第二钝化层、缓冲层的材料为浴铜灵(BCP)。
可以理解地，钙钛矿太阳能电池包括正式钙钛矿太阳能电池和反式钙钛矿太阳能电池。对于正式钙钛矿太阳能电池，正式钙钛矿太阳能电池包括透明电极以及依次层叠于透明电极之上的电子传输层、钙钛矿层、空穴传输层和金属电极。对于反式钙钛矿太阳能电池，反式钙钛矿太阳能电池包括透明电极以及依次层叠于透明电极之上的空穴传输层、钙钛矿层、电子传输层和金属电极。在本申请中，可以通过对第一电极和第二电极材料的选择，得到相应的正式钙钛矿太阳能电池和反式钙钛矿太阳能电池。
请参阅图1，其中示出了本申请一实施例中钙钛矿太阳能电池的结构。其中，第一电极为FTO，在第一电极上依次层叠设置空穴传输层、钝化层、钙钛矿层、电子传输层、钝化层或缓冲层以及金属电极。在FTO远离钙钛矿层的表面设有玻璃基底。
本申请还提供了一种钙钛矿太阳能电池的制备方法。该钙钛矿太阳能电池的制备方法包括如下步骤：在第一电极上制备钙钛矿层；在钙钛矿层上制备电子传输层；在电子传输层上制备第二电极；电子传输层包括富勒烯复合材料，富勒烯复合材料包括主体材料和掺杂材料，主体材料包括第一富勒烯衍生物，掺杂材料选自富勒烯及第二富勒烯衍生物中的至少一种，掺杂材料的分子结构有部分结构嵌入第一富勒烯衍生物的晶格内。
可选地，通过旋涂、退火的方式制备钙钛矿层。可选地，通过旋涂、退火的方式制备电子传输层。可选地，通过蒸镀的方式制备第二电极。
可选地，通过旋涂上述电子传输浆料，并退火的方式制备电子传输层。
本申请还提供了一种用电装置。该用电装置包括上述钙钛矿太阳能电池。可选地，用电装置为例如通信领域、交通领域、工农业领域、照明领域等的用电装置。用电装置例如可包 括卫星、通讯设备、交通信号灯、灯塔、无线电话亭、石油钻探领域的监测设备、电源系统、野营灯、电动汽车、电子设备充电器等。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
本实施例中富勒烯复合材料的制备步骤如下：
S101：4-苯甲酰基丁酸甲酯的合成：
取一500mL洁净干燥的双口烧瓶，加入苯甲酰基丁酸19.25g(0.1mol)，溶于300mL氯苯中，加入100mL甲醇，搅拌至完全溶解，滴加盐酸30mL，继续搅拌，加热回流反应过夜，点板确定反应完全进行，之后停止搅拌，用饱和碳酸钠中和至没有气泡，油水分离，然后用乙酸乙酯萃取水相，将有机相合并在一起，用无水氯化钙除水，减压蒸馏除去溶剂，在硅胶柱中将产物洗脱分离，洗脱剂为乙酸乙酯/正己烷(体积比3:1)，得到淡黄色油状液体4-苯甲酰基丁酸甲酯18g。
S102：5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯的合成：
将4-苯甲酰基丁酸甲酯10.5g(0.05mol)、对甲苯磺酰肼11.5g(0.06mol)和200ml甲醇在单口圆底烧瓶中加热回流，反应12h，冷却至室温，遮光保存24h，后转移至-15℃遮光过夜，抽滤，产物在甲醇中进行重结晶，产物于40℃真空过夜，得到白色固体5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯18.2g。
S103：F1-OMe的合成：
取一洁净干燥的1L的三口烧瓶，将5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯11.25g(0.03mol)溶于250mL吡啶中，加入1.75g甲醇钠，搅拌，抽放气，使其保存在氩气氛围下，另取一洁净干燥的圆底烧瓶，加入10.8gC60，溶于300mL邻二氯苯中，将其滴加至上述三口烧瓶中，加热回流24h，将产物旋蒸除去大部分溶剂，通过柱层析将产物分离，得到产物F1-OMe 6.83g。
S104：富勒烯复合材料：
将6.83g F1-OMe和掺杂材料C50溶于邻二氯苯中，加热回流反应48h，产物浓缩后，加入甲醇中，沉淀析出，得到富勒烯复合材料。在本实施例中，掺杂材料为C50，主体材料为 PC61BM，得到的富勒烯复合材料中，掺杂材料C50占富勒烯复合材料的质量百分数为0.1％，即掺杂量为0.1％。
本实施例中钙钛矿太阳能电池，制备步骤如下：
S201：取20片规格为2.0cm*2.0cm的FTO导电玻璃，两端通过激光刻蚀各去掉0.35cm的FTO，裸露出玻璃基底；用水、丙酮、异丙醇依次超声清洗刻蚀后的FTO导电玻璃；将清洗后的FTO导电玻璃在氮气枪下吹干溶剂，放入紫外臭氧机中进行紫外臭氧清洗处理。
S202：在紫外臭氧清洗处理后的FTO基片上以4000rpm的速率旋涂10mg/mL的氧化镍纳米颗粒(水为溶剂)在100℃热台上退火处理30分钟，形成空穴传输层。
S203：将PTAA按照1mg/mL的浓度溶于氯苯中，搅拌后用0.45μm的滤膜进行过滤，取50μL滴加在空穴传输层上，以4000rpm的速率旋涂，在100℃热台上退火处理10分钟，得到钝化层。
S204：称取223mg碘化铅PbI2、80mg碘甲脒FAI、15mg氯甲胺(MACl)溶解在0.8mL DMF与0.2mL DMSO的混合溶液中，搅拌3h，用0.22μm有机滤膜过滤，得到钙钛矿前驱体溶液，在钝化层上以3000rpm旋涂钙钛矿前驱液，120℃下退火30min，冷却至室温，形成钙钛矿层，其中钙钛矿层中的活性物质为FA体系，厚度为500nm。
S205：将S104中得到的富勒烯复合材料溶于氯苯，形成浓度为20mg/mL的电子传输浆料，在钙钛矿层上以1500rpm旋涂电子传输浆料，于100℃下退火10min，形成电子传输层，厚度为50nm。紧接着以5000rpm旋涂其钝化材料BCP溶液，其中BCP溶液是将BCP溶于异丙醇，浓度0.5mg/mL，形成钝化层，厚度为5nm。然后放入蒸镀机，蒸镀金属电极Ag，获得钙钛矿太阳能电池。
实施例2
与实施例1相比，本实施例的不同之处在于，掺杂材料为PC51BM。其中，PC51BM通过实施例1中S101～S103，并将S103中C60替换成C50，制备得到。
在制备富勒烯复合材料时，将实施例1中S104中的掺杂材料C50替换成PC51BM。
在本实施例中，掺杂材料为PC51BM，主体材料为PC61BM，得到的富勒烯复合材料中，掺杂材料PC51BM占富勒烯复合材料的质量百分数为0.05％，即掺杂量为0.05％。
实施例3
与实施例1相比，本实施例的不同之处在于，将S103中C60替换成C50和C60，其中C50和C60的质量之和与实施例1中S103中C60的质量相等，且以占C50和C60的总质量百分比计，C50的质量百分数为0.1％。
本实施例中，掺杂材料为PC51BM，主体材料为PC61BM，得到的富勒烯复合材料中，掺杂材料PC51BM占富勒烯复合材料的质量百分数为0.05％，即掺杂量为0.05％。
实施例4
与实施例1相比，本实施例的不同之处在于，将S103中C60替换成C50、C60和C70，其中C50、C60和C70的质量之和与实施例1中S103中C60的质量相等，且以占C50、C60和C70的总质量百分比计，C50的质量百分数为0.1％，C70的质量百分数为0.03％。
本实施例中，掺杂材料为PC51BM和PC71BM，主体材料为PC61BM，得到的富勒烯复合材料中，掺杂材料PC51BM占富勒烯复合材料的质量百分数为0.05％，掺杂材料PC71BM占富勒烯复合材料的质量百分数为0.015％。，即PC51BM的掺杂量为0.05％，PC71BM的掺杂量为0.03％。
实施例5
与实施例1相比，本实施例的不同之处在于，调整S104中掺杂材料C50的加入量。其中，掺杂材料为C50，主体材料为PC61BM，得到的富勒烯复合材料中，掺杂材料C50占富勒烯复合材料的质量百分数为0.0001％。
实施例6
与实施例1相比，本实施例的不同之处在于，调整S104中掺杂材料C50的加入量。其中，掺杂材料为C50，主体材料为PC61BM，得到的富勒烯复合材料中，掺杂材料C50占富勒烯复合材料的质量百分数为1％。
实施例7
与实施例1相比，本实施例的不同之处在于，将C50替换成C70。
实施例8
与实施例1相比，本实施例的不同之处，调整S104中掺杂材料C50的加入量。其中，掺杂材料为C50，主体材料为PC61BM，得到的富勒烯复合材料中，掺杂材料C50占富勒烯复合材料的质量百分数为0.00005％。
实施例9
与实施例1相比，本实施例的不同之处，调整S104中掺杂材料C50的加入量。其中，掺杂材料为C50，主体材料为PC61BM，得到的富勒烯复合材料中，掺杂材料C50占富勒烯复合材料的质量百分数为1.3％。
实施例10
与实施例1相比，本实施例的不同之处，不进行S101～S103，在S104中，将C60和掺杂材料C50溶于邻二氯苯中，加热回流反应48h，产物浓缩后，加入甲醇中，沉淀析出，得到富勒烯复合材料。其中，掺杂材料为C50，主体材料为C60，得到的富勒烯复合材料中，掺杂材料C50占富勒烯复合材料的质量百分数为0.1％。
对比例1
与实施例1相比，本对比例的不同之处在于，S104中不加入C50，即对PC61BM不进行掺杂。
对比例2
与实施例1相比，本对比例的不同之处在于，将PC61BM和C50直接混合，得到富勒烯复合材料。其中，C50占富勒烯复合材料的质量百分数为0.1％。
对比例3
与实施例1相比，不进行富勒烯复合材料的制备，在钙钛矿太阳能电池中，通过蒸镀C60的方式制备电子传输层。
测试例：
在标准模拟太阳光(AM 1.5G，100mW/cm2)照射下，对电池性能进行测试，获取I-V曲线。根据I-V曲线以及测试设备反馈的数据可以得到短路电流Jsc(单位mA/cm2)、开路电压Voc(单位V)、最大光输出电流Jmpp(单位mA)和最大光输出电压Vmpp(单位V)。通过公式FF＝Jsc×Voc/(Jmpp×Vmpp)计算出电池的填充因子FF，单位％。通过公式PCE＝Jsc×Voc×FF/Pw计算出电池的光电转换效率PCE，单位％；Pw表示输入功率，单位mW。
实施例和对比例中掺杂材料的掺杂量、电池的测试结果如表1所示。
表1
由表1可以看出，实施例中的钙钛矿太阳能电池相对于对比例获得了更高的光电转换效率。比如，由实施例、对比例1、对比例3可以看出，电子传输层包括掺杂材料的钙钛矿太阳能电池具有更高的光电转换效率。由实施例1、对比例2可以看出，与将PC61BM和C50直接混合的方式相比，实施例1中的制备方法得到的富勒烯复合材料中应用到电子传输层中，得到的钙钛矿太阳能电池具有更高的光电转换效率。同时，当掺杂材料占富勒烯复合材料的 质量百分数为0.0001％～1％时，能够使钙钛矿太阳能电池获得更高的光电转换效率。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (14)

  1. 一种富勒烯复合材料，其特征在于，包括主体材料和掺杂材料，所述主体材料包括第一富勒烯和第一富勒烯衍生物中的至少一种，所述掺杂材料选自第二富勒烯及第二富勒烯衍生物中的至少一种，所述掺杂材料的分子结构有部分结构嵌入所述第一富勒烯和/或所述第一富勒烯衍生物的晶格内。
  2. 根据权利要求1所述的富勒烯复合材料，其特征在于，以占所述第一富勒烯和/或所述第一富勒烯衍生物，以及所述掺杂材料的总质量的百分数计，所述掺杂材料的质量百分数为0.0001％～1％。
  3. 根据权利要求1～2中任一项所述的富勒烯复合材料，其特征在于，所述第一富勒烯包括C50、C60以及C70中的至少一种，所述第一富勒烯衍生物包括PC51BM、PC52BM、PC61BM、PC62BM、PC71BM以及PC72BM中的至少一种。
  4. 根据权利要求1～3中任一项所述的富勒烯复合材料，其特征在于，所述第二富勒烯包括C50、C60以及C70中的至少一种，所述第二富勒烯衍生物包括PC51BM、PC52BM、PC61BM、PC62BM、PC71BM以及PC72BM中的至少一种。
  5. 一种富勒烯复合材料的制备方法，其特征在于，包括如下步骤：
    将第一原料与第二原料在第一溶剂中混合，对得到的混合体系进行热处理；
    所述第一原料含有第一富勒烯和/或第一富勒烯衍生物和/或用于合成所述第一富勒烯衍生物的原料，所述第二原料含有用于作为掺杂材料的第二富勒烯和第二富勒烯衍生物中的至少一种。
  6. 根据权利要求5所述的富勒烯复合材料的制备方法，其特征在于，所述用于合成所述第一富勒烯衍生物的原料包括第三富勒烯、5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以及碱；将第一原料与第二原料在溶剂中混合包括：
    将所述5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯和所述碱分散在第一子溶剂中，将所述第二原料和所述第三富勒烯分散在第二子溶剂中，将两个溶液体系混合。
  7. 根据权利要求6所述的富勒烯复合材料的制备方法，其特征在于，所述第三富勒烯、所述掺杂材料、所述5-苯基-5-(对甲苯磺酰肼基)戊酸甲酯以及所述 碱的摩尔比为1：(10-5～10-2)：(1～2)：(1～10)。
  8. 根据权利要求6～7中任一项所述的富勒烯复合材料的制备方法，其特征在于，所述第一子溶剂包括吡啶；和/或，
    所述第二子溶剂包括甲苯、二甲苯、氯苯以及二氯苯中的至少一种；和/或，
    所述碱包括甲醇钠、碳酸铯、氢氧化钠以及氢氧化钾中的至少一种。
  9. 根据权利要求5～8中任一项所述的富勒烯复合材料的制备方法，其特征在于，所述第一溶剂包括甲苯、二甲苯、氯苯以及二氯苯中的至少一种。
  10. 根据权利要求5～8中任一项所述的富勒烯复合材料的制备方法，其特征在于，所述热处理满足以下特征中的至少一个：
    (1)所述热处理的温度为100℃～300℃；
    (2)所述热处理的时间为24h～60h；
    (3)所述热处理包括加热回流。
  11. 一种钙钛矿太阳能电池，其特征在于，包括依次层叠设置的第一电极、钙钛矿层、电子传输层以及第二电极；
    所述电子传输层包括权利要求1～4中任一项所述的富勒烯复合材料，或者，
    所述电子传输层包括权利要求5～10中任一项所述的制备方法得到的富勒烯复合材料。
  12. 根据权利要求11所述的钙钛矿太阳能电池，其特征在于，所述电子传输层的厚度为10nm～100nm。
  13. 一种钙钛矿太阳能电池的制备方法，其特征在于，包括如下步骤：
    在第一电极上制备钙钛矿层；
    在所述钙钛矿层上制备电子传输层；
    在所述电子传输层上制备第二电极；
    所述电子传输层包括富勒烯复合材料，所述富勒烯复合材料包括主体材料和掺杂材料，所述主体材料包括第一富勒烯和第一富勒烯衍生物中的至少一种，所述掺杂材料选自第二富勒烯及第二富勒烯衍生物中的至少一种，所述掺杂材料的分子结构有部分结构嵌入所述第一富勒烯和/或所述第一富勒烯衍生物的晶格内。
  14. 一种用电装置，其特征在于，包括权利要求11～12中任一项所述的钙钛矿太阳能电池。
PCT/CN2023/079072 2023-03-01 2023-03-01 富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置 Ceased WO2024178679A1 (zh)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP23924649.9A EP4586792A4 (en) 2023-03-01 2023-03-01 FULLEREN COMPOSITE MATERIAL AND ITS PREPARATION PROCESS, PEROVSKITE PHOTOVOLTAIC CELL AND ITS PREPARATION PROCESS, AND ELECTRICAL DEVICE
PCT/CN2023/079072 WO2024178679A1 (zh) 2023-03-01 2023-03-01 富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置
JP2025521152A JP2025535120A (ja) 2023-03-01 2023-03-01 フラーレン複合材料及びその製造方法、ペロブスカイト太陽電池及びその製造方法、並びに電気装置
CN202380054279.9A CN119631604B (zh) 2023-03-01 2023-03-01 富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置
KR1020257011734A KR20250068692A (ko) 2023-03-01 2023-03-01 풀러렌 복합재료 및 그 제조 방법, 페로브스카이트 태양전지 및 그 제조 방법, 및 전기 장치
US19/192,360 US20250261554A1 (en) 2023-03-01 2025-04-29 Fullerene composite material and preparation method therefor, perovskite solar cell and preparation method therefor, and electrical device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/079072 WO2024178679A1 (zh) 2023-03-01 2023-03-01 富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US19/192,360 Continuation US20250261554A1 (en) 2023-03-01 2025-04-29 Fullerene composite material and preparation method therefor, perovskite solar cell and preparation method therefor, and electrical device

Publications (1)

Publication Number Publication Date
WO2024178679A1 true WO2024178679A1 (zh) 2024-09-06

Family

ID=92589399

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/079072 Ceased WO2024178679A1 (zh) 2023-03-01 2023-03-01 富勒烯复合材料及其制备方法、钙钛矿太阳能电池及其制备方法，以及用电装置

Country Status (6)

Country Link
US (1) US20250261554A1 (zh)
EP (1) EP4586792A4 (zh)
JP (1) JP2025535120A (zh)
KR (1) KR20250068692A (zh)
CN (1) CN119631604B (zh)
WO (1) WO2024178679A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120456798A (zh) * 2025-07-11 2025-08-08 昆山协鑫光电材料有限公司 一种钙钛矿太阳能电池、电子传输层的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120463596B (zh) * 2025-07-11 2025-10-21 昆山协鑫光电材料有限公司 一种pcbm及其制备方法和应用以及用于制备pcbm的装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08175813A (ja) * 1994-12-26 1996-07-09 Nec Corp フラーレン系インターカレーション化合物薄膜およびその作製方法
US20140116510A1 (en) * 2012-10-26 2014-05-01 Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan Structure for improving thermal stability of bulk heterojunction solar cells and related photovoltaic apparatus and method for making the same
CN105646561A (zh) * 2014-08-08 2016-06-08 纳米及先进材料研发院有限公司 富勒烯衍生物以及它们在有机光伏中的应用
CN105967966A (zh) * 2016-05-23 2016-09-28 合肥市激子能源技术有限公司 一种纯异构富勒烯双加成衍生物及其制备方法
CN107074678A (zh) * 2014-09-08 2017-08-18 昭和电工株式会社 富勒烯衍生物的制造方法
CN107112420A (zh) * 2015-01-29 2017-08-29 积水化学工业株式会社 太阳能电池及太阳能电池的制造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106519307B (zh) * 2016-10-20 2019-05-14 华南理工大学 一种细菌纤维素/富勒烯复合材料及其制备方法
CN107394047B (zh) * 2017-07-31 2020-04-03 苏州大学 醇溶性富勒烯衍生物在钙钛矿太阳能电池中的应用
CN109698280B (zh) * 2018-12-26 2022-10-04 苏州大学 富勒烯亚甲基衍生物ⅰ在钙钛矿太阳能电池中的应用、钙钛矿太阳能电池及其制备方法
CN109742245B (zh) * 2019-01-10 2022-12-16 苏州大学 苯酚取代的富勒烯衍生物在钙钛矿太阳能电池中的应用、钙钛矿太阳能电池及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08175813A (ja) * 1994-12-26 1996-07-09 Nec Corp フラーレン系インターカレーション化合物薄膜およびその作製方法
US20140116510A1 (en) * 2012-10-26 2014-05-01 Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan Structure for improving thermal stability of bulk heterojunction solar cells and related photovoltaic apparatus and method for making the same
CN105646561A (zh) * 2014-08-08 2016-06-08 纳米及先进材料研发院有限公司 富勒烯衍生物以及它们在有机光伏中的应用
CN107074678A (zh) * 2014-09-08 2017-08-18 昭和电工株式会社 富勒烯衍生物的制造方法
CN107112420A (zh) * 2015-01-29 2017-08-29 积水化学工业株式会社 太阳能电池及太阳能电池的制造方法
CN105967966A (zh) * 2016-05-23 2016-09-28 合肥市激子能源技术有限公司 一种纯异构富勒烯双加成衍生物及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4586792A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120456798A (zh) * 2025-07-11 2025-08-08 昆山协鑫光电材料有限公司 一种钙钛矿太阳能电池、电子传输层的制备方法

Also Published As

Publication number Publication date
CN119631604A (zh) 2025-03-14
KR20250068692A (ko) 2025-05-16
EP4586792A4 (en) 2026-02-25
CN119631604B (zh) 2026-03-03
EP4586792A1 (en) 2025-07-16
JP2025535120A (ja) 2025-10-22
US20250261554A1 (en) 2025-08-14

Similar Documents

Publication Publication Date Title
Jiang et al. On the interface reactions and stability of nonfullerene organic solar cells
Liao et al. In-situ growing CdS single-crystal nanorods via P3HT polymer as a soft template for enhancing photovoltaic performance
Chang et al. A solution-processed n-doped fullerene cathode interfacial layer for efficient and stable large-area perovskite solar cells
Kim et al. High‐performance and environmentally stable planar heterojunction perovskite solar cells based on a solution‐processed copper‐doped nickel oxide hole‐transporting layer
Zhou et al. Dual optimization of bulk and interface via the synergistic effect of ligand anchoring and hole transport dopant enables 23.28% efficiency inverted perovskite solar cells
CN104788649B (zh) 一种电子传输层材料及钙钛矿太阳电池
US20250261554A1 (en) Fullerene composite material and preparation method therefor, perovskite solar cell and preparation method therefor, and electrical device
Yin et al. Dual-interface modification with BMIMPF6 for high-efficiency and stable carbon-based CsPbI2Br perovskite solar cells
CN108976392B (zh) 含喹喔啉酰亚胺稠环的共轭聚合物光电材料及其应用
CN107286157B (zh) 一种苝二酰亚胺类化合物及其制备方法、应用
Yoon et al. Semi‐transparent metal electrode‐free all‐inorganic perovskite solar cells using floating‐catalyst‐synthesized carbon nanotubes
Ma et al. Non-fullerene electron acceptors with benzotrithiophene with π-extension terminal groups for the development of high-efficiency organic solar cells
Chen et al. Dominant Face‐On Oriented Perylene‐Diimide Interlayers for High‐Performance Organic Solar Cells
CN108832000A (zh) 一种三元聚合物太阳能电池
Makenali et al. Charge transfer balancing of planar perovskite solar cell based on a low cost and facile solution-processed CuOx as an efficient hole transporting layer
Chang et al. High-performance printable hybrid perovskite solar cells with an easily accessible n-doped fullerene as a cathode interfacial layer
Guo et al. Sn‐Pb binary perovskite films with high crystalline quality for high performance solar cells
Guo et al. High-κ La2O3 as an anode modifier to reduce leakage current for efficient perovskite solar cells
Yan et al. Incorporation of quaternary ammonium salts containing different counterions to improve the performance of inverted perovskite solar cells
KR20170000422A (ko) 1,8 디아이오도옥탄이 도핑된 페로브스카이트 태양전지 제조방법
CN119300617A (zh) 一种体相钝化钙钛矿吸光层、太阳能电池及制备方法
CN118201377A (zh) 太阳能电池及其制备方法
KR20250133989A (ko) 페로브스카이트 전지, 제조 방법 및 이에 상응하는 전기기기
CN112358430B (zh) 席夫碱金属配合物及其制备方法、钙钛矿太阳能电池及其制备方法
Gao et al. Symmetrical Oxalate Derivative for Dual Interface-Grain Boundary Chelation Enabling High-Efficiency and Stable Perovskite Solar Cells

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23924649

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202380054279.9

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 202380054279.9

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 20257011734

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020257011734

Country of ref document: KR

Ref document number: 2023924649

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2025521152

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025521152

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 2023924649

Country of ref document: EP

Effective date: 20250410

WWP Wipo information: published in national office

Ref document number: 1020257011734

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2023924649

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE