WO2025242003A1 - 钙钛矿太阳能电池及其制备方法、光伏组件、发电装置和用电装置 - Google Patents

钙钛矿太阳能电池及其制备方法、光伏组件、发电装置和用电装置

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Publication number
WO2025242003A1
WO2025242003A1 PCT/CN2025/095460 CN2025095460W WO2025242003A1 WO 2025242003 A1 WO2025242003 A1 WO 2025242003A1 CN 2025095460 W CN2025095460 W CN 2025095460W WO 2025242003 A1 WO2025242003 A1 WO 2025242003A1
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Prior art keywords
perovskite
electron transport
layer
transport layer
solar cell
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English (en)
French (fr)
Inventor
刘泽政
李文佳
梁江湖
汪旭先
涂保
林维乐
陈国栋
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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    • 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
    • H10K30/50—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
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • 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
    • 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
    • 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
    • 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

  • This disclosure relates to the field of battery technology, and in particular to a perovskite solar cell and its preparation method, photovoltaic module, power generation device and power consumption device.
  • Solar cells also known as photovoltaic cells, are devices that directly convert light energy into electrical energy through the photoelectric effect or photochemical effect.
  • Perovskite solar cells are a widely studied new type of solar cell, gradually becoming a hot topic in next-generation solar cell research due to their advantages such as high photoelectric conversion efficiency, simple fabrication process, and low production and material costs.
  • advantages such as high photoelectric conversion efficiency, simple fabrication process, and low production and material costs.
  • current perovskite solar cells still need further improvement in photoelectric conversion efficiency.
  • This disclosure is made in view of the above-mentioned issues, and its purpose is to provide a perovskite solar cell, photovoltaic module, power generation device, and power consumption device with good photoelectric conversion efficiency.
  • the first aspect of this disclosure provides a perovskite solar cell, comprising: a first electrode and a second electrode; a perovskite layer and an electron transport layer sequentially arranged between the first electrode and the second electrode along a first direction, wherein the electron transport layer partially covers the perovskite layer; the first direction is the light incident direction.
  • the electron transport layer partially covering the perovskite layer enables point contact between the perovskite layer and the electron transport layer, reducing the contact area between the interface and decreasing non-radiative recombination caused by interface contact. Furthermore, it reduces the thickness of the electron transport layer, helping to improve the electron transport efficiency, thereby increasing the photoelectric conversion efficiency of the perovskite solar cell and saving costs.
  • the electron transport layer covers 30%-90% of the perovskite layer. In other embodiments, the electron transport layer covers 42%-62% of the perovskite layer. Therefore, an electron transport layer coverage within the above range is beneficial for achieving sufficient point contact at the interface between the perovskite layer and the electron transport layer, further improving the electron transport efficiency of the electron transport layer, and thus enhancing the photoelectric conversion efficiency of the perovskite solar cell.
  • the root mean square roughness of the perovskite layer is 8 nm to 40 nm. This facilitates the formation of a partially covered electron transport layer on the perovskite layer, thereby improving electron transport efficiency.
  • the electron transport layer includes an electron transport material, which includes at least one of fullerenes and their derivatives, metal oxides, and metal fluorides.
  • fullerenes and their derivatives include one or more of fullerene C60 , fullerene C70 , methyl [6,6]-phenyl C61 butyrate, methyl [6,6]-phenyl C71 butyrate, and indene-C60 diadducts; or, the metal oxides include one or two of tin dioxide and zinc oxide; or, the metal fluorides include one or two of lithium fluoride and calcium fluoride.
  • the second aspect of this disclosure provides a method for fabricating a perovskite solar cell, comprising the following steps: forming a perovskite layer on a first electrode; forming an electron transport layer on the perovskite layer, wherein the electron transport layer partially covers the perovskite layer; and forming a second electrode on the electron transport layer.
  • This disclosure improves the point contact between the electron transport layer and the perovskite by forming an electron transport layer that partially covers the perovskite layer, thereby reducing nonradiative recombination caused by interface contact, improving electron transport efficiency, and saving costs.
  • the electron transport layer covers 30%-90% of the perovskite layer. This facilitates full contact between the perovskite layer and the electron transport layer, and further improves electron transport efficiency.
  • forming an electron transport layer on the perovskite layer includes: simultaneously applying an electron transport layer ink onto the perovskite layer to form a wet film via slot coating, and then performing air knife treatment.
  • the combined use of slot coating and air knife treatment allows the electron transport layer to be uniformly distributed on and partially cover the perovskite layer.
  • the thickness of the wet film is less than 6 ⁇ m.
  • the thickness of the wet film is less than 6 ⁇ m.
  • the airflow rate of the air knife treatment is 60-200 ⁇ L/s.
  • the airflow rate of the air knife treatment it is helpful to control the coverage of the electron transport layer on the perovskite, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.
  • the concentration of the electron transport layer ink is 5-30 mg/ml
  • the injection rate of the slit coating is 70-300 ⁇ L/s
  • the moving speed of the slit coating is 10-100 mm/s.
  • This disclosure provides a photovoltaic module in a third aspect, the photovoltaic module including the perovskite solar cell provided in the first aspect or the perovskite solar cell prepared according to the preparation method provided in the second aspect.
  • photovoltaic modules disclosed herein include the perovskite solar cells described above, they have at least the same advantages as perovskite solar cells.
  • the fourth aspect of this disclosure provides a power generation device, which includes a perovskite solar cell provided in the first aspect or a perovskite solar cell prepared according to the preparation method provided in the second aspect.
  • the power generation device of this disclosure includes the perovskite solar cell of the present disclosure, it has at least the same advantages as the perovskite solar cell.
  • the fifth aspect of this disclosure provides an electrical device comprising a perovskite solar cell provided in the first aspect or a perovskite solar cell prepared according to the preparation method provided in the second aspect.
  • the power supply device of this disclosure includes the perovskite solar cell of this disclosure, it has at least the same advantages as the perovskite solar cell.
  • Figure 1 is a schematic diagram of the structure of a perovskite solar cell according to an embodiment of the present disclosure.
  • Figure 2 is a SEM color block analysis diagram of the perovskite solar cell of Embodiment 1 of this disclosure after the formation of the electron transport layer.
  • Figure 3 shows the surface potential diagram of the perovskite solar cell of Embodiment 1 of this disclosure obtained by KPFM characterization.
  • Figure 4 is a SEM color block analysis diagram of the perovskite solar cell of Comparative Example 1 of this disclosure after the formation of the electron transport layer.
  • FIG. 10 Perovskite solar cell; 11 First electrode; 12 Second electrode; 13 Perovskite layer; 14 Electron transport layer.
  • ranges disclosed in this disclosure is defined by a lower limit and an upper limit, whereby a given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the 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 expected. Furthermore, if minimum range values 1 and 2 are listed, and if maximum range values 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.
  • the numerical range "a-b” represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers.
  • 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.
  • 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.
  • steps of this disclosure may be performed sequentially or randomly, preferably sequentially.
  • a method includes steps (a) and (b)
  • the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially.
  • the method may also include step (c)
  • step (c) it means that step (c) may be added to the method in any order.
  • 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.
  • the term "layer” refers to any substantially layered structure.
  • a layer may have a thickness that varies over its length. Typically, the thickness of a layer is approximately constant.
  • thickness of a layer refers to the average thickness of the layer. The thickness of a layer can be readily measured using conventional methods.
  • references in this disclosure to a layer being on/located on another layer include the case where the first layer is directly on the second layer, i.e., the two layers are in direct contact, and the case where there are other intercalated layers (such as a third layer) between the first and second layers.
  • perovskite refers to a material having a three-dimensional crystal structure associated with the three-dimensional crystal structure of CaTiO3 , or a layered material comprising a structure associated with the structure of CaTiO3 .
  • Materials having a three-dimensional crystal structure associated with CaTiO3 are well known and may be referred to as perovskites having a "3D perovskite structure,” or simply “3D perovskites.”
  • perovskite When exposed to sunlight, electrons in a perovskite are excited, transitioning from the valence band to the conduction band, creating electron-hole pairs.
  • perovskite in this disclosure refers to 3D perovskite materials.
  • the general chemical formula for perovskite can be represented as ABX3 , where A is typically a cation with a large radius.
  • A includes at least one of: CH( NH2 ) 2+ , CH3NH3 + , K + , Rb + , and Cs + .
  • B is a cation with a small radius, including but not limited to at least one of Pb2+ , Sn2+ , Mg2+ , Ca2+ , Ba2+ , Zn2+ , Ge2+ , and Co2+ .
  • X is an anion, for example, X includes at least one of Cl ⁇ , Br ⁇ , I ⁇ , SCN ⁇ , CNO ⁇ , OCN ⁇ , OSCN ⁇ , SH ⁇ , OH ⁇ , CP ⁇ , CN ⁇ , and SeCN ⁇ .
  • a cation different A cations can be distributed in an ordered or disordered manner at the A sites.
  • B cation different B cations can be distributed in an ordered or disordered manner at the B sites.
  • the perovskite includes more than one X anion different X anions can be distributed in an ordered or disordered manner at the X sites.
  • Solar cells also known as photovoltaic cells, are devices that directly convert light energy into electrical energy through the photoelectric effect or photochemical effect.
  • Perovskite solar cells in particular, possess numerous advantages such as excellent optical absorption coefficient, high luminous quantum efficiency, and low-cost manufacturing processes, giving them significant application potential.
  • the photoelectric conversion efficiency of perovskite solar cells still needs improvement.
  • the present disclosure provides a perovskite solar cell and a method for preparing the same, as well as a photovoltaic module, a power generation device and a power consumption device including the perovskite solar cell.
  • the perovskite solar cell disclosed herein includes: a first electrode and a second electrode, wherein a perovskite layer and an electron transport layer are arranged sequentially between the first electrode and the second electrode along a first direction, wherein the electron transport layer partially covers the perovskite layer; the first direction is the light incident direction.
  • FIG. 1 is a schematic diagram of the structure of a perovskite solar cell according to an embodiment of the present disclosure.
  • the perovskite solar cell 10 includes a first electrode 11 and a second electrode 12, and a perovskite layer 13 and an electron transport layer 14 are arranged sequentially between the first electrode 11 and the second electrode 12 along the light incident direction (i.e., the first direction), wherein the electron transport layer 14 partially covers the perovskite layer 13.
  • the electron transport layer covers 30%-90% of the perovskite layer.
  • the electron transport layer's coverage of the perovskite layer is within this range, it sufficiently covers the grain boundaries of the perovskite layer, providing adequate electron transport channels and improving the electron transport efficiency.
  • the electron transport layer's coverage of the perovskite layer can be 30%, 40%, 42%, 46%, 50%, 54%, 55%, 60%, 62%, 65%, 70%, 72%, 75%, 80%, 90%, or any value within a range of any two of these values.
  • the electron transport layer's coverage of the perovskite layer is 42%-62%.
  • the coverage of the electron transport layer is measured using scanning electron microscopy (SEM) image colorimetric analysis.
  • SEM scanning electron microscopy
  • the electron transport layer of the perovskite solar cell is analyzed using SEM, and SEM images are obtained.
  • Image analysis software such as Colorpix, is used to perform colorimetric analysis on the SEM images to identify the RGB values of each pixel, distinguishing between covered and uncovered areas. Multiple samples are taken and averaged to calculate the coverage.
  • Figure 2 is an SEM image taken after an electron transport layer is formed on a perovskite layer according to an embodiment of this disclosure.
  • Black represents grain boundaries
  • dark gray represents well-covered areas
  • light gray represents poorly covered areas.
  • RGB three primary colors for identification, defining black and dark gray as the first type of color (covered areas) and light gray as the second type of color (uncovered areas). By comparing RGB colors, it is found that the chromaticity values of the R, G, and B channels of the SEM image are relatively close under black and white display.
  • RGB average value (R channel chromaticity value + B channel chromaticity value + G channel chromaticity value) / 3.
  • Figure 2 defines RGB average values of 80-120 as the first type of color and RGB average values of 140-180 as the second type of color.
  • the coverage of the electron transport layer on the perovskite layer is the percentage of the area of the first-class color patch to the total area of the color patch.
  • the surface potential of the region of the perovskite layer covered by the electron transport layer is 100mV-200mV higher than the surface potential of the region not covered by the electron transport layer.
  • the surface potential of the electron transport layer is 100mV, 120mV, 140mV, 160mV, 180mV, 200mV, or any two of these values that are higher than the surface potential of the surface not covered by the electron transport layer.
  • surface potential refers to the potential difference at the interface between two phases caused by the difference in the mobility of ions or electrons.
  • Surface potential can be measured using Kelvin probe force microscopy (KPFM). The presence of a potential difference indicates that the electron transport layer does not completely cover the perovskite layer.
  • the electron transport layer comprises an electron transport material.
  • the electron transport material there are no particular limitations on the electron transport material; for example, at least one of fullerenes and their derivatives, metal oxides, and metal fluorides may be used.
  • fullerenes and their derivatives include one or more of fullerene C60 , fullerene C70 , methyl [6,6]-phenyl C61 butyrate (PC61BM), methyl [6,6]-phenyl C71 butyrate (PC71BM), indene-C60 diadduct (ICBA), or other fullerene derivatives
  • metal oxides include one or more of tin dioxide ( SnO2 ), zinc oxide (ZnO), etc.
  • metal fluorides include one or more of lithium fluoride (LiF), calcium fluoride ( CaF2 ), etc.
  • the perovskite layer described above serves as a light-absorbing layer and includes a perovskite material.
  • This disclosure does not impose any particular limitation on the perovskite material included in the perovskite layer, and the material can be selected according to actual needs.
  • the molecular formula of the perovskite material may be ABX3 or A2CDX6 , where A represents an inorganic cation, an organic cation , or a mixed organic-inorganic cation.
  • methylamino CH3NH3+
  • formamidinyl HC( NH2 ) 2+
  • dimethylamine cation ethylamine cation
  • propylamine cation propylamine cation
  • butylamine cation pentamine cation, hexamine cation
  • imidazole cation cesium ion (Cs + ), lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), silver ion (Ag + ), and rubidium ion (Rb + ), etc.
  • B represents divalent metal cations, including but not limited to the following materials: lead ion (Pb2 + ), divalent tin ion (Sn2 + ), beryllium ion (Be2 + ), magnesium ion (Mg2 + ), calcium ion (Ca2 + ), strontium ion
  • the cations include, but are not limited to, one or more of the following: cobalt ions ( Co2+ ), copper ions ( Cu2+ ), and nickel ions ( Ni2+ ); more preferably, ions B include one or two of lead ions ( Pb2+ ) and tin ions ( Sn2+ ); C represents one or two of monovalent metal cations, such as sodium ions ( Na+ ), potassium ions ( K+ ), silver ions ( Ag+ ), and rubidium ions ( Rb+ ); D represents trivalent metal cations, including but not limited to: bismuth ions ( Bi3+ ), antimony ions ( Sb3+ ), chromium ions ( Cr3+ ), iron ions ( Fe3+ ), cobalt ions ( Co3+ ), gallium ions ( Ga3+ ), arsenic ions ( As3+ ), ruthenium ions ( Ru3+ ), and rhodium ions ( Rh3+ ).
  • the symbol X represents a monovalent anion, such as a halide ion or a halide-like ion, including but not limited to the following materials: chloride ion ( Cl- ), bromide ion ( Br- ), iodide ion ( I- ) , SCN- , BF4- , HCO2- , SeCN- , CN- , etc.
  • perovskite materials include at least one of inorganic halide materials, organic halide materials, and organic-inorganic halide perovskite materials.
  • the perovskite material includes at least one of: CH3NH3PbI3 ( abbreviated as MAPbI3 ), CH( NH2 ) 2PbI3 (abbreviated as FAPbI3 ), Cs0.05 ( FA0.83MA0.17 ) 0.95Pb ( I0.83Br0.17 ) 3 (abbreviated as CsFAMA), CsPbI3 , CsPbI2Br , and CsPbIBr2 .
  • CH3NH3PbI3 abbreviated as MAPbI3
  • CH( NH2 ) 2PbI3 abbreviated as FAPbI3
  • Cs0.05 FA0.83MA0.17
  • I0.83Br0.17 I0.83Br0.17
  • CsFAMA CsPbI3
  • CsPbI2Br CsPbIBr2 .
  • the perovskite layer can be prepared by the following steps: dissolving the perovskite material precursor in a solvent to prepare a perovskite precursor solution, then coating it onto the sample to be coated by a coating method, and drying and annealing to obtain the perovskite layer.
  • the perovskite material precursor raw materials include compounds containing AX and BX2 , where A, B, and X are defined as described above, such as AX-type compounds like CsI, FAI, MAI, and MACl (FA represents CH( NH2 ) 2+ , MA represents CH3NH3 + ), and BX2 -type compounds like PbI2 and SnI2 .
  • the solvent used to prepare the perovskite precursor solution may include one or more of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and chlorobenzene.
  • DMF N,N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • chlorobenzene chlorobenzene
  • the annealing temperature is 90°C to 150°C.
  • the annealing temperature can be 90°C, 92°C, 95°C, 98°C, 100°C, 102°C, 105°C, 108°C, 110°C, 120°C, 128°C, 130°C, 140°C, or any value within the range of any two of the above values.
  • the annealing time is 5 min to 30 min.
  • the annealing time can be 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 20 min, 25 min, 30 min, or any value within the range of any two of the above values.
  • Coating methods include slot coating, scraping coating, etc., and are not limited here.
  • drying can be achieved by vacuum drying.
  • the perovskite layer can be prepared by a gas-phase method or a gas-liquid method, and there is no limitation here.
  • the roughness of the perovskite layer can be expressed, for example, by root mean square (RMS) roughness.
  • the surface height can be measured using instruments such as laser interferometers or atomic force microscopes.
  • the root mean square roughness of the perovskite layer is 8 nm to 40 nm.
  • a root mean square roughness within this range is beneficial for forming a partially covering electron transport layer on the perovskite layer, ensuring the electron transport layer fully covers the grain boundaries of the perovskite layer and provides sufficient electron transport channels, thereby improving electron transport efficiency.
  • the root mean square roughness of the perovskite layer can be 8 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, or a value within a range of any two of these values.
  • the root mean square roughness of the perovskite layer can be adjusted by changing the solvent of the perovskite precursor solution, adjusting the vacuum drying time, annealing temperature, and time, etc.
  • increasing the boiling point of the solvent in the perovskite precursor solution can reduce the root mean square roughness of the perovskite layer.
  • the thickness of the perovskite layer may be 400-1500 nm, such as 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1200 nm, 1500 nm, or a value within a range of any two of these values.
  • other functional layers such as a passivation layer, may be disposed between the perovskite layer and the electron transport layer. It is understood that these other functional layers do not completely cover the perovskite layer. In embodiments where other functional layers are disposed between the perovskite layer and the electron transport layer, the coverage of the electron transport layer over the perovskite layer can be understood as the coverage of the perovskite layer and the surface formed by the other functional layers disposed thereon.
  • the material of the passivation layer may include at least one of piperazine, N-methyl-1,3-propanediammonium diiodide, 3-aminopyridine, ferrocene, or their homologues or derivatives; the thickness of the passivation layer is generally 0.5 nm to 2.5 nm.
  • the first electrode described above may also be referred to as the bottom electrode, which is the electrode that first receives incident light and is used to collect electrons/holes.
  • the material used for the first electrode includes a transparent conductive material. This disclosure does not impose any particular limitation on the transparent conductive material used in the first electrode.
  • Exemplary transparent conductive materials include at least one of: tin oxide, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), indium-doped zinc oxide (IZO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), antimony-doped tin oxide, and indium-doped tungsten oxide.
  • the second electrode may also be referred to as the top electrode, which is the electrode that last receives the incident light and is used to collect electrons/holes.
  • the material used for the second electrode includes conductive materials. This disclosure does not impose any particular limitation on the conductive materials used in the second electrode.
  • the conductive material includes at least one of organic conductive materials and inorganic conductive materials, wherein the inorganic conductive material includes at least one of the above-mentioned transparent conductive materials, metals and their alloys, and elemental carbon materials.
  • metals and their alloys include at least one of gold, silver, copper, aluminum, nickel, chromium, bismuth, platinum, magnesium, molybdenum, and tungsten.
  • elemental carbon materials include at least one of graphite, graphene, and carbon nanotubes.
  • organic conductive materials include at least one of poly(3,4-ethylenedioxythiophene), polythiophene, and polyacetylene.
  • the perovskite solar cell described above may further include a hole transport layer, which comprises a hole transport material.
  • a hole transport layer which comprises a hole transport material.
  • exemplary examples include, but are not limited to, nickel oxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), polyethylenedioxythiophene-polystyrene sulfonate (PEDOT:PSS), 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid, poly3-hexylthiophene, triphenylamine with a triphenylene core, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4
  • the perovskite solar cell described above may further include a lower passivation layer.
  • the lower passivation layer is disposed on the lower surface of the perovskite layer.
  • This disclosure does not impose any particular limitation on the material of the lower passivation layer; materials commonly used in the art can be used.
  • the lower passivation layer may include ⁇ - ⁇ conjugated self-assembled molecules, with one end anchored to the perovskite layer, such as 3-triethoxysilylpropionitrile, 2-aminothiazolyl-4-acetic acid, and 1-hydroxy-4-carbonylbenzene, but is not limited thereto.
  • the perovskite solar cell described above may further include an upper passivation layer.
  • the upper passivation layer is disposed on the upper surface of the perovskite layer.
  • This disclosure does not impose any particular limitation on the material of the upper passivation layer; materials commonly used in the art can be used.
  • the material of the upper passivation layer may include piperazine, N-methyl-1,3-propanediammonium diiodide, 3-aminopyridine, ferrocene, etc., but is not limited thereto.
  • the perovskite solar cell described above may further include a barrier layer.
  • a barrier layer This disclosure does not impose any particular limitation on the material of the barrier layer; materials commonly used in the art can be used.
  • the material of the barrier layer may include indium tungsten oxide (IWO), indium tin oxide (ITO), copper bath (BCP), tin oxide, zirconium acetylacetonate, but is not limited thereto.
  • the perovskite solar cell disclosed herein can be fabricated by the following method.
  • the fabrication method includes: forming a perovskite layer on a first electrode; forming an electron transport layer on the perovskite layer, wherein the electron transport layer partially covers the perovskite layer; and forming a second electrode on the electron transport layer.
  • the electron transport layer has a coverage of 30%-90% on the perovskite layer.
  • the coverage of the electron transport layer on the perovskite layer is within this range, the electron transport layer sufficiently covers the grain boundaries of the perovskite layer, which is beneficial for providing sufficient electron transport channels and improving the electron transport efficiency of the electron transport layer.
  • the coverage of the electron transport layer on the perovskite layer can be 30%, 40%, 42%, 46%, 50%, 54%, 55%, 60%, 62%, 65%, 70%, 72%, 75%, 80%, 90%, or a value within a range of any two of these values.
  • the coverage of the electron transport layer on the perovskite layer is 42%-62%.
  • forming an electron transport layer on the perovskite layer includes: simultaneously applying electron transport layer ink onto the perovskite layer to form a wet film using slit coating, and performing air knife treatment.
  • Slot coating is a coating technique that uses extremely fine nozzles and a high-precision coating system to apply viscous liquids or pastes to specific locations on a product. This disclosure utilizes slot coating to more precisely distribute electron transport layer ink onto the perovskite layer. Furthermore, slot coating improves the material utilization rate of the electron transport layer ink, thereby enhancing coating quality and efficiency.
  • the air knife driven by a high-pressure blower, delivers uniform and powerful hot air to achieve the drying purpose.
  • This disclosure uses an air knife to rapidly dry the wet film of the electron transport layer ink coated on the perovskite layer, quickly reaching the saturation critical point to precipitate electron transport material crystals and form a dry film at the grain boundaries of the perovskite layer. Since the surface of the perovskite layer has protrusions and depressions, using an air knife prevents the electron transport layer ink from flowing to the depressions, ensuring that the perovskite surface in the depressions is completely covered by the electron transport layer, while the protrusions on the perovskite surface remain uncovered.
  • This disclosure describes the formation of an electron transport layer on a perovskite layer using a slit coating method combined with air knife treatment. This allows the electron transport layer to be uniformly distributed on the perovskite layer and partially cover the perovskite layer, thus covering the grain boundaries of the perovskite layer and providing sufficient electron transport channels to achieve effective electron transport efficiency.
  • the wet film thickness formed by the electron transport layer ink on the perovskite layer is less than or equal to 6 ⁇ m.
  • the wet film thickness formed by the electron transport layer ink on the perovskite layer can be 0.5 ⁇ m, 0.67 ⁇ m, 0.88 ⁇ m, 1 ⁇ m, 1.75 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, or a value within a range of any two of these values.
  • the wet film thickness formed by the electron transport layer ink on the perovskite layer is within the above range, the wet film, after being processed by an air knife, can form an ultra-thin electron transport layer that partially covers the perovskite layer.
  • the airflow rate of the air knife treatment is 60 ⁇ L/s to 200 ⁇ L/s. Controlling the airflow rate within this range helps to ensure a suitable coverage of the electron transport layer on the perovskite layer, thereby improving the transmission efficiency of the electron transport layer and the photoelectric conversion efficiency of the perovskite solar cell.
  • the airflow rate of the air knife treatment can be 60 ⁇ L/s, 80 ⁇ L/s, 90 ⁇ L/s, 100 ⁇ L/s, 120 ⁇ L/s, 150 ⁇ L/s, 160 ⁇ L/s, 200 ⁇ L/s, or a value within a range of any two of these values.
  • the electron transport layer ink comprises an electron transport material and a solvent.
  • the electron transport material is as described above and will not be repeated here.
  • the solvent includes one or more of chlorobenzene and o-dichlorobenzene. The combination of the electron transport material and solvent provides good electrical conductivity, and the resulting electron transport layer ink is suitable for slot coating, easy to process, and easily dried quickly by air knife treatment to form a uniformly distributed electron transport layer dry film.
  • the concentration of the electron transport layer ink is 5-30 mg/ml. A concentration within this range provides the electron transport layer ink with a suitable viscosity, which is beneficial for application in slot coating methods, improving coating accuracy and efficiency.
  • the concentration of the electron transport layer ink can be 5 mg/ml, 10 mg/ml, 15 mg/ml, 20 mg/ml, 25 mg/ml, 30 mg/ml, or a value within a range of any two of these values.
  • the concentration of the electron transport layer ink is 8-20 mg/ml, optionally 10-20 mg/ml.
  • the injection rate of the above-described slot coating method is 70-300 ⁇ L/s.
  • the injection rate of the above-described slot coating method can be 70 ⁇ L/s, 100 ⁇ L/s, 140 ⁇ L/s, 200 ⁇ L/s, 240 ⁇ L/s, 300 ⁇ L/s, or any value within a range of any two of these values.
  • the moving speed of the coating die in the above-described slot coating method is 10-100 mm/s.
  • the moving speed of the slot coating can be 10 mm/s, 30 mm/s, 50 mm/s, 80 mm/s, 90 mm/s, 100 mm/s, or any value within a range of any two of these values.
  • the electron transport layer covers the grain boundaries of the perovskite layer and partially covers the perovskite layer, thereby providing an effective electron transport channel and improving electron transport efficiency.
  • the injection rate of the above-mentioned slit coating method is 100-240 ⁇ L/s, optionally 140-240 ⁇ L/s; the moving speed is 60-100 mm/s, optionally 80-100 mm/s; and the air output of the above-mentioned air knife treatment is 70-200 ⁇ L/s, optionally 90-160 ⁇ L/s.
  • the amount of electron transport layer coated by the above slit coating and air knife treatment is equivalent to coating an electron transport layer with a thickness of 10nm-20nm on an almost completely flat substrate, such as a smooth and flat pure glass substrate.
  • the above treatment can form an electron transport layer that partially covers the perovskite layer, with the resulting electron transport layer covering the grain boundaries of the perovskite layer.
  • the hole transport layer may be prepared using spin coating, vapor deposition (e.g., magnetron sputtering), etc.
  • the perovskite layer can be prepared using liquid-phase methods such as spin coating, slot coating, or blade coating, or gas-phase methods such as vapor deposition, or a combination of gas and liquid methods.
  • the second electrode may be prepared using magnetron sputtering, vapor deposition, or other methods.
  • a photovoltaic module includes the above-described perovskite solar cells, solder strips connecting multiple perovskite solar cells, a junction box for current transmission, and cell encapsulation components.
  • the battery encapsulation component includes photovoltaic glass, which covers the perovskite solar cell and serves to protect it. Simultaneously, the photovoltaic glass possesses excellent light transmittance and high hardness, allowing it to withstand large diurnal temperature variations and harsh weather conditions.
  • the battery encapsulation component includes an ethylene-vinyl acetate copolymer (EVA) film disposed between the photovoltaic glass and the perovskite solar cell for bonding the photovoltaic glass and the solar cell.
  • EVA ethylene-vinyl acetate copolymer
  • the battery encapsulation components include a photovoltaic backsheet, which also serves to protect the perovskite solar cells.
  • the photovoltaic backsheet material can be a polyvinyl fluoride composite film or a thermoplastic elastic material.
  • the photovoltaic backsheet material possesses properties such as insulation, waterproofing, and aging resistance.
  • the battery encapsulation component includes a solar aluminum frame, made of aluminum alloy, which features high strength and good corrosion resistance. It serves to support and protect the solar cells.
  • this disclosure also provides a power generation device, including the perovskite solar cell provided in the above embodiments.
  • this disclosure also provides an electrical device, including the perovskite solar cell provided in the above embodiments.
  • the electrical device may also be a lighting device, an energy storage device, etc., and the embodiments disclosed herein include, but are not limited to, these.
  • the electrical device may be a solar water heater, a solar street light, a solar photovoltaic generator, etc.
  • NiOx with a thickness of about 20 nm was formed on the first electrode by magnetron sputtering and annealed at 300 °C for 60 min to obtain hole transport layer.
  • Perovskite light-absorbing material was prepared using a one-step method. 0.05 mol CsI, 0.95 mol FAI, and 1 mol PbI2 were weighed and placed in 666 ml of DMF. The mixture was stirred at room temperature for 6 h, filtered through a 0.22 ⁇ m filter, and loaded into a coating machine. The perovskite light-absorbing material was then coated using a slit coating method (coating die movement speed of 50 mm/s, liquid injection speed of 200 ⁇ L/s).
  • the material was placed in an oven and annealed at 140 °C for 20 min to obtain a perovskite layer with a thickness of 500 nm (FA0.9Cs0.1PbI3 ) .
  • the root mean square roughness of the obtained perovskite layer was measured to be 35 nm using atomic force microscopy (AFM).
  • Preparation of the second electrode The sheet with the electron transport layer prepared above is placed in a vapor deposition apparatus. When the vapor deposition vacuum is below 5* 10-4 Pa, an 80nm metal back electrode Cu is deposited at a rate of 0.1A/s to obtain a perovskite solar cell.
  • the sheet with the electron transport layer was analyzed using a Zeiss GeminiSEM, and SEM images were captured. The obtained SEM images were then analyzed using Colorpix software to identify the R, G, and B channel chromaticity values of each pixel.
  • KPFM Kelvin probe force microscope
  • the fabricated perovskite solar cell was tested using a Keithley 2400SMU and an AM1.5G solar irradiation system under a 1000W/ m2 light source.
  • the positive electrode of the Keithley 2400SMU was connected to the anode (hole terminal) and the negative electrode to the cathode (electron terminal) of the perovskite solar cell.
  • the starting voltage was set to -0.1V, the ending voltage to 1.2V, and the scan mode was set to reverse scan.
  • the measured output power ( Pout ) and incident light power ( Popt ) of the cell were recorded.
  • Perovskite solar cells were prepared according to the method of Example 1, with the difference being that different coverage rates were obtained by adjusting the process parameters in step 4), and the specific values are shown in Table 1.
  • Perovskite solar cells were prepared according to the method of Example 1, except that the solvent DMF in step 3) was replaced with a mixed solvent of DMSO/DMF in a volume ratio of 1:9, and the root mean square roughness of the resulting perovskite layer was 8 nm.
  • Perovskite solar cells were prepared according to the method of Example 1, except that the annealing temperature in step 3) was replaced with 120°C, and the root mean square roughness of the resulting perovskite layer was 40 nm.
  • Perovskite solar cells were prepared according to the method in Example 1, with the difference that a passivation layer preparation step was added between step 3) and step 4). Specifically,
  • a piperazine iodine isopropanol solution (concentration 0.5 mg/mL) was coated onto the perovskite layer using a slit coating method.
  • the coating die moving speed was 50 mm/s
  • the injection speed was 300 ⁇ L/s
  • the layer was dried with an air knife to obtain an upper passivation layer with a thickness of approximately 2 nm.
  • an electron transport layer ink was coated onto the upper passivation layer using the slit coating method, with the remaining steps the same as in Example 1.
  • Perovskite solar cells were prepared according to the method of Example 1, with the difference that in step 5), the electron transport layer completely covered the perovskite layer, with a coverage rate of 100%.
  • the SEM color patch analysis image of the electron transport layer is shown in Figure 4.
  • the photoelectric conversion efficiency of the perovskite solar cell in this disclosure is improved by partially covering the perovskite layer with the electron transport layer.

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Abstract

本公开提供一种钙钛矿太阳能电池及其制备方法、光伏组件、发电装置和用电装置，钙钛矿太阳能电池包括第一电极和第二电极，在第一电极和第二电极之间，沿第一方向依次排布有钙钛矿层和电子传输层，其中，电子传输层部分覆盖钙钛矿层；第一方向为光入射方向。

Description

钙钛矿太阳能电池及其制备方法、光伏组件、发电装置和用电装置
相关申请的交叉引用
本公开基于申请号为202410643082.5、申请日为2024年05月22日、发明名称为“钙钛矿太阳能电池及其制备方法、光伏组件、发电装置和用电装置”的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本公开作为参考。
技术领域
本公开涉及电池技术领域，尤其涉及一种钙钛矿太阳能电池及其制备方法、光伏组件、发电装置和用电装置。
背景技术
随着现代工业的发展，全球能源短缺和环境污染问题日益突出，太阳能电池作为理想的可再生能源受到越来越多的重视。太阳能电池，又称为光伏电池，是一种通过光电效应或光化学效应将光能直接转化为电能的装置。
钙钛矿电池是目前广泛研究的一类新型太阳能电池，其凭借其高光电转换效率、简单的制作工艺、低的生产成本和材料成本等优势而逐渐成为新一代太阳能电池研究的热点。然而，目前的钙钛矿太阳能电池在光电转换效率方面仍需进一步改善。
发明内容
本公开是鉴于上述课题而进行的，其目的在于，提供一种具有良好的光电转换效率的钙钛矿太阳能电池、光伏组件、发电装置和用电装置。
为了达到上述目的，本公开第一方面提供了一种钙钛矿太阳能电池，钙钛矿太阳能电池包括：第一电极和第二电极，在第一电极和第二电极之间，沿第一方向依次排布有钙钛矿层和电子传输层，其中，电子传输层部分覆盖钙钛矿层；第一方向为光入射方向。通过本公开，电子传输层部分覆盖钙钛矿层，一方面能够使钙钛矿层和电子传输层界面实现点接触，减小钙钛矿层和电子传输层界面间的接触面积，降低由于界面接触而导致的非辐射复合的发生，另一方面，可减小电子传输层的厚度，有助于提升电子传输层的传输效率，从而提高钙钛矿太阳能电池的光电转化效率，而且能够节约成本。
在一些实施方式中，电子传输层对钙钛矿层的覆盖率为30％-90％。在一些实施方式中，电子传输层对钙钛矿层的覆盖率为42％-62％。由此，电子传输层对钙钛矿层的覆盖率在上述范围内，有利于充分实现钙钛矿层和电子传输层间界面的点接触，更有利于提高电子传输层的电子传输效率，进而提高钙钛矿太阳能电池的光电转化效率。
在一些实施方式中，钙钛矿层的均方根粗糙度为8nm-40nm。由此有利于在钙钛矿层上形成部分覆盖的电子传输层，从而改进电子传输效率。
在一些实施方式中，电子传输层包括电子传输材料，电子传输材料包括富勒烯及其衍生物、金属氧化物、金属氟化物中的至少一种。
在一些实施方式中，富勒烯及其衍生物包括富勒烯C60、富勒烯C70、[6,6]-苯基C61丁酸甲酯、[6,6]-苯基C71丁酸甲酯、茚-C 60双加合物中的一种或几种；或，金属氧化物包括二氧化锡、氧化锌的一种或两种；或，金属氟化物包括氟化锂、氟化钙的一种或两种。
本公开第二方面提供一种钙钛矿太阳能电池的制备方法，包括如下步骤：在第一电极上形成钙钛矿层；在钙钛矿层上形成电子传输层，电子传输层部分覆盖钙钛矿层；和在电子传输层上形成第二电极。
本公开通过在钙钛矿层上形成部分覆盖钙钛矿层的电子传输层，由此，有利于提升电子传输层与钙钛矿的点接触，降低由于界面接触而导致的非辐射复合的发生，能够提高电子传输效率并且节约成本。
在一些实施方式中，电子传输层对钙钛矿层的覆盖率为30％-90％。由此，有利于充分实现钙钛矿层和电子传输层间界面的接触，更有利于提高电子传输效率。
在一些实施方式中，在钙钛矿层上形成电子传输层包括：通过狭缝涂布将电子传输层墨水涂布在钙钛矿层上形成湿膜的同时，进行风刀处理。通过狭缝涂布和风刀处理结合使用，使得电子传输层能够均匀地分布在钙钛矿层上且部分覆盖钙钛矿层。
在一些实施方式中，湿膜的厚度为6μm以下。通过设置湿膜的厚度为6μm以下，并结合狭缝涂布和风刀处理的结合使用，有助于控制电子传输层在钙钛矿层上的覆盖率，更有利于提高电子传输层速率。
在一些实施方式中，风刀处理的出风量为60-200ul/s。通过控制风刀处理的出风量，有助于控制电子传输层在钙钛矿的覆盖率，进而提高钙钛矿太阳能电池的光电转换效率。
在一些实施方式中，电子传输层墨水的浓度为5-30mg/ml，狭缝涂布的注液速度为70-300ul/s，狭缝涂布的移动速度为10-100mm/s。
通过控制上述条件，更有利于使电子传输层均匀地分布在钙钛矿层上且控制电子传输层在钙钛矿层的覆盖率。
本公开第三方面提供一种光伏组件，光伏组件包括第一方面提供的钙钛矿太阳能电池或根据第二方面提供的制备方法制备的钙钛矿太阳能电池。
由于本公开的光伏组件包括上述本公开的钙钛矿太阳能电池，因而至少具有与钙钛矿太阳能电池相同的优势。
本公开第四方面提供一种发电装置，发电装置包括第一方面提供的钙钛矿太阳能电池或根据第二方面提供的制备方法制备的钙钛矿太阳能电池。
由于本公开的发电装置包括上述本公开的钙钛矿太阳能电池，因而至少具有与钙钛矿太阳能电池相同的优势。
本公开第五方面提供一种用电装置，用电装置包括第一方面提供的钙钛矿太阳能电池或根据第二方面提供的制备方法制备的钙钛矿太阳能电池。
由于本公开的用电装置包括上述本公开的钙钛矿太阳能电池，因而至少具有与钙钛矿太阳能电池相同的优势。
附图说明
图1为本公开一实施方式的钙钛矿太阳能电池的结构示意图。
图2为本公开实施例1的钙钛矿太阳能电池在形成电子传输层后的SEM色块分析图。
图3为本公开实施例1的钙钛矿太阳能电池在KPFM表征中获得表面电势图。
图4为本公开对比例1的钙钛矿太阳能电池在形成电子传输层后的SEM色块分析图。
附图标记：
10钙钛矿太阳能电池；11第一电极；12第二电极；13钙钛矿层；14
电子传输层。
具体实施方式
以下，适当地参照附图详细说明具体公开了本公开的钙钛矿太阳能电池及其制备方法、光伏组件、发电装置和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本公开而提供的，并不旨在限定权利要求书所记载的主题。
本公开所公开的“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。在本公开中，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，本公开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，本公开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，本公开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，方法包括步骤(a)和(b)，表示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，提到方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到方法，例如，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，本公开中使用的术语具有本领域技术人员通常所理解的公知含义。
如果没有特别的说明，本公开中提到的各参数的数值可以用本领域常用的各种测试方法进行测定，例如，可以按照本公开给出的测试方法进行测定。
本公开中使用的术语“层”是指任何基本上为层状的结构。层可具有在该层延伸的范围内变化的厚度。通常情况下，层具有的厚度是近似恒定的。本公开中使用的层的“厚度”是指层的平均厚度。层的厚度可以很容易地利用常规方法测量。
如果没有特别的说明，本公开中提及一层在/位于另一层上包括第一层直接位于第二层上，即，这两层直接接触的情况，以及在在第一层和第二层之间还具有间插的其他层(如第三层)的情况。
本公开中使用的术语“钙钛矿”是指一种具有与CaTiO3的三维晶体结构相关的三维晶体结构的材料，或包括具有与CaTiO3的结构相关的结构的层材料。具有与CaTiO3的三维晶体结构相关的材料是公知的，可称为具有“3D钙钛矿结构”的钙钛矿，或称为“3D钙钛矿”。当接收太阳光时，钙钛矿中的电子会被激发，电子从价带跃迁至导带，产生电子-空穴对。如果没有特别的说明，本公开中提到“钙钛矿”是指3D钙钛矿材料。钙钛矿化学通式可以表示为ABX3，其中A通常为半径较大的阳离子。例如，A包括：CH(NH2)2 +、CH3NH3 +、K+、Rb+、Cs+中的至少一种。B为半径较小的阳离子，B包括但不限于Pb2+、Sn2+、Mg2+、Ca2+、Ba2+、Zn2+、Ge2+、Co2+、中的至少一种。X为阴离子，例如，X包括：Cl-、Br-、I-、SCN-、CNO-、OCN-、OSCN-、SH-、OH-、CP-、CN-、SeCN-中的至少一种。当钙钛矿包括多于一种A阳离子时，不同的A阳离子可以有序或无序地分布在A位点上。当钙钛矿包括多于一种B阳离子时，不同的B阳离子可以有序或无序地分布在B位点上。当钙钛矿包括多于一种X阴离子时，不同的X阴离子可以有序或无序地分布在X位点上。
太阳能电池又称为光伏电池，是一种通过光电效应或光化学效应将光能直接转换为电能的装置。其中，钙钛矿太阳能电池具有良好的光学吸收系数、发光量子效率、低成本的制造工艺等诸多优点，具有强大的应用潜力。但是，钙钛矿太阳能电池的光电转换效率仍需提高。
针对于此，本公开提供了一种钙钛矿太阳能电池及其制备方法，以及包括该钙钛矿太阳能电池的光伏组件、发电装置和用电装置。
钙钛矿太阳能电池
本公开提供的钙钛矿太阳能电池包括：第一电极和第二电极，在第一电极和第二电极之间，沿第一方向依次排布有钙钛矿层和电子传输层，其中，电子传输层部分覆盖钙钛矿层；第一方向为光入射方向。
目前行业中通常认为电子传输层需要完全覆盖钙钛矿层以提高电子传输效率。但是，经研究发现，电子传输层完全覆盖钙钛矿层意味着需要形成很厚的电子传输层，而膜层太厚对电子传输不利，从而影响钙钛矿太阳能电池的光电转换效率。
通过进一步研究发现，在钙钛矿太阳能电池工作中，钙钛矿层经光照产生电子-空穴对，其中电子的传输主要在钙钛矿层的晶界处实现，基于此，本公开中通过使电子传输层有效地覆盖钙钛矿层的钙钛矿晶界处，尽管在钙钛矿晶体的峰顶处没有实现完全覆盖，但能够使钙钛矿层和电子传输层界面实现点接触，仍然能够为钙钛矿层中产生的电子提供足够的传输通道。而且，由于电子传输层仅需部分覆盖钙钛矿层，最终形成的电子传输层较薄，因此，不仅有助于提升电子传输层的传输效率，从而提高电池的光电转换效率，而且能够节约成本。
图1为本公开一实施方式的钙钛矿太阳能电池的结构示意图。如图1所示，钙钛矿太阳能电池10包括第一电极11和第二电极12，并且，在第一电极11和第二电极12之间沿光入射方向(即第一方向)依次排布有钙钛矿层13和电子传输层14，其中，电子传输层14部分覆盖钙钛矿层13。
在一些实施方式中，上述电子传输层对上述钙钛矿层的覆盖率为30％-90％。电子传输层在钙钛矿层上的覆盖率在上述范围内，电子传输层能够充分覆盖于钙钛矿层的晶界处，有利于提供足够的电子传输通道，提高电子传输层的电子传输效率。示例性的，上述电子传输层在上述钙钛矿层上的覆盖率可以为30％、40％、42％、46％、50％、54％、55％、60％、62％、65％、70％、72％、75％、80％、90％，或它们任意两个数值所组成的范围之间的值。可选地，上述电子传输层在上述钙钛矿层上的覆盖率为42％-62％。
在本公开中，电子传输层的覆盖率采用扫描电镜(SEM)图像色度分析法来进行测量。将钙钛矿太阳能电池的电子传输层进行扫描电镜分析，拍摄得到扫描SEM图像，采用图像分析软件，例如colorpix软件对SEM图像进行色度分析，识别每个像素的RBG值，区分覆盖区域和未覆盖区域，多处取样测平均值，由此计算覆盖率。
示例性地，图2为本公开一实施例在钙钛矿层上形成电子传输层之后拍摄的SEM图像，黑色表示晶界处，深灰色表示覆盖良好处，浅灰色表示覆盖不良处，本公开通过RGB三原色识别的方式，将黑色和深灰色定义为第一类色(被覆盖的区域)，将浅灰色定义为第二类色(未覆盖的区域)。通过对比RGB颜色，发现在黑白显示下SEM图像的R、G、B三色通道的色度值比较接近，因此采用RGB三色的色度平均值来表示颜色，即RGB平均值＝(R通道色度值+B通道色度值+G通道色度值)/3。当第一类色的RGB平均值最大值与第二类色的RGB平均值最小值相差20时，即可区分第一类色和第二类色。图2经图像分析软件处理之后，定义RGB平均值为80-120为第一类色，定义RGB平均值为140-180为第二类色。在本公开中，电子传输层在钙钛矿层上的覆盖率则为第一类色的色块面积占总色块的面积的占比。
在电子传输层的表面与电子传输层未覆盖的钙钛矿层的表面，存在100mV-200mV的电势差。在钙钛矿层上覆盖有上述电子传输层的区域的表面电势比未覆盖上述电子传输层的区域的表面电势高100mV-200mV。示例性地，电子传输层的表面的表面电势比电子传输层未覆盖的表面的表面电势高100mV、120mV、140mV、160mV、180mV、200mV或它们中任意两个数值所组成的范围之间的值。
在本公开中，表面电势是指在两相交界处由于离子或电子的迁移率的不同而引起的电势差。表面电势可以通过开尔文探针力显微镜(KPFM)技术测得。电势差的存在表明电子传输层未完全覆盖钙钛矿层。
在一些实施方式中，上述电子传输层包括电子传输材料。作为电子传输材料，没有特殊的限制，例如富勒烯及其衍生物、金属氧化物、金属氟化物中的至少一种。进一步的，富勒烯及其衍生物包括富勒烯C60、富勒烯C70、[6,6]-苯基C61丁酸甲酯(PC61BM)、[6,6]-苯基C71丁酸甲酯(PC71BM)、茚-C 60双加合物(ICBA)或其它富勒烯衍生物的一种或几种；金属氧化物包括二氧化锡(SnO2)、氧化锌(ZnO)等的一种或几种；金属氟化物包括氟化锂(LiF)、氟化钙(CaF2)等的一种或几种。
在一些实施方式中，上述钙钛矿层作为吸光层，包括钙钛矿材料。本公开对钙钛矿层包括的钙钛矿材料没有特别限制，可以根据实际需求选择。钙钛矿材料的分子式可为ABX3或A2CDX6，其中A表示无机阳离子、有机阳离子、或有机无机混合阳离子，示例性地，有机一价阳离子包括(NR1R2R3R4)+、(R1R2N＝CR3R4)+、(R1R2N-C(R5)＝NR3R4)+和(R1R2N-C(NR5R6)＝NR3R4)+中的一种或多种，其中，R1、R2、R3、R4、R5和R6各自独立地选自H、取代或未取代的C1～C20烷基、或取代或未取代的芳基。可选的，包括但不限于以下材料：甲胺基(CH3NH3 +)、甲脒基(HC(NH2)2 +)、二甲胺阳离子、乙胺阳离子、丙胺阳离子、丁胺阳离子、戊胺阳离子、己胺阳离子、咪唑阳离子、铯离子(Cs+)、锂离子(Li+)、钠离子(Na+)、钾离子(K+)、银离子(Ag+)和铷(Rb+)等；B表示二价金属阳离子，包括但不限于以下材料：铅离子(Pb2+)、二价锡离子(Sn2+)、铍离子(Be2+)、镁离子(Mg2+)、钙离子(Ca2+)、锶离子(Sr2+)、钡离子(Ba2+)、锌离子(Zn2+)、锗离子(Ge2+)、亚铁离子(Fe2+)、二价锰离子(Mn2+)、二价钴离子(Co2+)、二价铜离子(Cu2+)和二价镍离子(Ni2+)等中的一种或多种；更可选地，B离子包括铅离子(Pb2+)、二价锡离子(Sn2+)中的一种或两种；C表示一价金属阳离子，如钠离子(Na+)、钾离子(K+)、银离子(Ag+)和铷(Rb+)等的一种或两种；D表示三价金属阳离子，包括但不限于：三价铋离子(Bi3+)、三价锑离子(Sb3+)、三价铬离子(Cr3+)、三价铁离子(Fe3+)、三价钴离子(Co3+)、三价镓离子(Ga3+)、三价砷离子(As3+)、三价钌离子(Ru3+)、三价铑离子(Rh3+)等；X表示一价阴离子，如卤素离子或类卤素离子等，包括但不限于以下材料：氯离子(Cl-)、溴离子(Br-)、碘离子(I-)、SCN-、BF4 -、HCO2 -、SeCN-、CN-等。示例性地，钙钛矿材料包括无机卤化物材料、有机卤化物材料、有机-无机卤化物钙钛矿材料中的至少一种。在一些实施方式中，钙钛矿材料包括：CH3NH3PbI3(简写为MAPbI3)、CH(NH2)2PbI3(简写为FAPbI3)、Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3(简写为CsFAMA)、CsPbI3、CsPbI2Br、CsPbIBr2中的至少一种。
在一些实施方式中，上述钙钛矿层可以采用以下步骤制备：将钙钛矿材料前体原料溶于溶剂中制备得到钙钛矿前驱体溶液，之后采用涂布法涂布至待涂布样品上，干燥、退火即可制备得到钙钛矿层。
可选的，钙钛矿材料前体原料包括含有AX、BX2，其中A、B、X的定义同上文所述，比如，CsI、FAI、MAI、MACl等AX类化合物(FA表示CH(NH2)2 +，MA表示CH3NH3 +)，PbI2、SnI2等BX2类化合物。
可选地，制备钙钛矿前驱体溶液的溶剂可以包括N,N-二甲基甲酰胺(简称：DMF)、二甲基亚砜(简称：DMSO)、氯苯中的一种或多种。
在一些实施方式中，退火处理的温度为90℃～150℃。比如，退火处理的温度可以是90℃、92℃、95℃、98℃、100℃、102℃、105℃、108℃、110℃、120℃、128℃、130℃、140℃以及由上述任意两个数值构成的范围内的任意值。
在一些实施方式中，退火处理的时间为5min～30min。可选地，退火处理的时间可以是8min、9min、10min、11min、12min、13min、14min、15min、20min、25min、30min以及由上述任意两个数值构成的范围内的任意值。
涂布法包括狭缝涂布法、刮涂法等方法，此处不做限制。
在一些实施例中，干燥可以通过真空干燥法实现。
在另一实施方式中，可通过气相法或者气液法制备钙钛矿层，此处不做限制。
在本公开对钙钛矿层的粗糙度没有特别限制，采用本领域常规使用的粗糙度即可。钙钛矿层的粗糙度可以采用例如均方根粗糙度来表示。均方根粗糙度(RMS)是表示表面不平整程度的物理量的一种，通常表示表面高度的均方根值，其可以采用公式RMS＝(1/N)∑(|hi|)来计算，其中RMS表示均方根粗糙度，N表示测量点的数量，hi表示每个测量点的高度。表面高度可以采用例如激光干涉仪、原子力显微镜等仪器来测量。
在一些实施方式中，上述钙钛矿层的均方根粗糙度为8nm-40nm。钙钛矿层的均方根粗糙度在上述范围内，有利于在钙钛矿层上形成部分覆盖的电子传输层，并且使得电子传输层能够充分覆盖钙钛矿层的晶界，提供足够的电子传输通道，从而改进电子传输效率。示例性地，上述钙钛矿层的均方根粗糙度可以为8nm、10nm、15nm、20nm、25nm、30nm、35nm、40nm，或者它们中任意两个数值所组成的范围之间的值。在一些实施方式中，上述钙钛矿层的均方根粗糙度可以通过改变钙钛矿前驱体溶液的溶剂、调整真空干燥的时间、退火温度和时间等手段来调整。示例性的，增大钙钛矿前驱体溶液的溶剂的沸点可降低钙钛矿层的均方根粗糙度。
本公开对钙钛矿层的厚度没有特别限制，采用本领域常规使用的厚度即可。示例性地，钙钛矿层的厚度可以为400-1500nm，例如400nm、500nm、600nm、700nm、800nm、900nm、1000nm、1200nm、1500nm，或它们中任意两个数值所组成的范围之间的值。
在一些实施方式中，钙钛矿层和电子传输层之间还可以设置其他功能层，如钝化层等。可以理解的是，其他功能层不完全覆盖钙钛矿层。在钙钛矿层和电子传输层之间还设置有其他功能层的实施方式中，电子传输层对钙钛矿层的覆盖率可以理解为电子传输层对钙钛矿层和设在其上的其他功能层形成的表面的覆盖率。示例性的，钝化层的材料可以包括哌嗪、N-甲基-1,3-丙烷二碘化二铵、3-氨基吡啶、二茂铁等同系物或衍生物中的至少一个；钝化层的厚度一般为0.5nm-2.5nm。
在一些实施方式中，上述第一电极也可以称之为底电极指首先接收入射光的电极，用于收集电子/空穴。第一电极采用的材料包括透明导电材料。本公开对第一电极包括的透明导电材料没有特别限制。示例性的，透明导电材料包括：氧化锡、氧化铟锡(ITO)、氟掺杂的氧化锡(FTO)、铟掺杂的氧化锌(IZO)、铝掺杂的氧化锌(AZO)、硼掺杂的氧化锌(BZO)、锑掺杂的氧化锡、铟掺杂的氧化钨中的至少一种。
在一些实施方式中，上述第二电极也可以称之为顶电极指最后接收入射光的电极，用于收集电子/空穴。第二电极采用的材料包括导电材料。本公开对第二电极包括的导电材料没有特别限制。例如，导电材料包括有机导电材料、无机导电材料中的至少一种，其中，无机导电材料包括上述透明导电材料、金属及其合金、碳单质材料中的至少一种。示例性的，金属及其合金包括金、银、铜、铝、镍、铬、铋、铂、镁、钼、钨中的至少一种。示例性的，碳单质材料包括石墨、石墨烯、碳纳米管中的至少一种。示例性的，有机导电材料包括：聚(3,4-乙烯二氧噻吩)、聚噻吩、聚乙炔中的至少一种。
在一些实施方式中，上述钙钛矿太阳能电池还可以包括空穴传输层，空穴传输层包括空穴传输材料。本公开对空穴传输材料没有特别限制。示例性地，空穴传输材料包括但不限于氧化镍、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚乙撑二氧噻吩-聚苯乙烯磺酸盐(PEDOT:PSS)、2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(Spiro-OMeTAD)、聚(3,4-乙烯二氧噻吩)：聚苯乙烯磺酸、聚3-已基噻吩、三蝶烯为核的三苯胺、3,4-乙烯二氧噻吩-甲氧基三苯胺、N-(4-苯胺)咔唑-螺双芴、聚噻吩、磷酸基单分子及其聚合物、咔唑基单分子及其聚合物、磺酸基单分子及其聚合物、三苯胺基单分子及其聚合物、芳香基单分子及其聚合物、碘化亚铜和硫氰酸亚铜中的至少一种。本公开对空穴传输层的厚度没有特别限制，采用本领域惯用的空穴传输层厚度即可。
在一些实施方式中，上述钙钛矿太阳能电池还可以包括下钝化层。下钝化层设置在上述钙钛矿层的下表面。本公开对下钝化层的材料没有特别限制，采用本领域常用的材料即可。示例性地，下钝化层可以包括π-π共轭的自组装分子，且一端可与钙钛矿层锚定的分子，例如3-三乙氧硅基丙腈、2-氨基噻唑-4-乙酸、1-羟基-4-羰基苯，但不限于此。
在一些实施方式中，上述钙钛矿太阳能电池还可以包括上钝化层。上钝化层设置在上述钙钛矿层的上表面。本公开对上钝化层的材料没有特别限制，采用本领域常用的材料即可。示例性地，上钝化层的材料可以包括哌嗪、N-甲基-1,3-丙烷二碘化二铵、3-氨基吡啶、二茂铁等，但不限于此。
在一些实施方式中，上述钙钛矿太阳能电池还可以包括阻挡层。本公开对阻挡层的材料没有特别限制，采用本领域常用的材料即可。示例性地，阻挡层的材料可以包括氧化铟钨(IWO)、氧化铟锡(ITO)、浴铜灵(BCP)、氧化锡、乙酰丙酮锆，但不限于此。
钙钛矿太阳能电池的制备方法
本公开的钙钛矿太阳能电池可以通过如下方法制备。制备方法包括：在第一电极上形成钙钛矿层；在钙钛矿层上形成电子传输层，电子传输层部分覆盖钙钛矿层；和在电子传输层形成第二电极。
在一些实施方式中，上述电子传输层在上述钙钛矿层上的覆盖率为30％-90％。电子传输层在钙钛矿层上的覆盖率在上述范围内，电子传输层充分覆盖于钙钛矿层的晶界处，有利于提供足够的电子传输通道，提高电子传输层的电子传输效率。示例性的，上述电子传输层在上述钙钛矿层上的覆盖率可以为30％、40％、42％、46％、50％、54％、55％、60％、62％、65％、70％、72％、75％、80％、90％，或它们任意两个数值所组成的范围之间的值。在一些实施方式中，上述电子传输层在上述钙钛矿层上的覆盖率为42％-62％。
在钙钛矿层上形成电子传输层的方法没有特殊的限制，只要能够使电子传输层部分覆盖钙钛矿层即可。在一些实施方式中，在上述钙钛矿层上形成电子传输层包括：通过狭缝涂布将电子传输层墨水涂布在钙钛矿层上形成湿膜的同时，进行风刀处理。
狭缝涂布法是采用极细的喷嘴和高精度的涂布系统，将粘性液体或膏状材料涂布在产品的特定位置的一种涂布技术。本公开采用狭缝涂布法能够更加精确地将电子传输层墨水分布在钙钛矿层上，此外，采用狭缝涂布法能够提高电子传输层墨水的材料利用率，提高涂布的质量和效率。
风刀通过高压风机驱动，送出均匀强劲的热风，从而达到干燥的目的。本公开采用风刀将上述涂布在钙钛矿层上的电子传输层墨水湿膜快速风干，快速达到饱和临界点，以析出电子传输材料的晶体以在钙钛矿层的晶界处形成干膜。由于钙钛矿层表面存在凸起和低洼处，采用风刀处理可以避免电子传输层墨水流动到低洼处而使得低洼处的钙钛矿表面被电子传输层完全覆盖而钙钛矿层表面的凸起处完全不被电子传输层覆盖。
本公开通过狭缝涂布法结合风刀处理在钙钛矿层上形成电子传输层，使得电子传输层能够均匀地分布在钙钛矿层上，并且电子传输层部分覆盖钙钛矿层，使得电子传输层覆盖在钙钛矿层晶界处，提供足够的电子传输通道，以实现有效的电子传输效率。
在一些实施方式中，上述电子传输层墨水在上述钙钛矿层上形成的湿膜厚度小于或等于6μm。示例性地，电子传输层墨水在上述钙钛矿层上形成的湿膜厚度可以为0.5μm、0.67μm、0.88μm、1μm、1.75μm、2μm、2.5μm、3μm、4μm、5μm、6μm，或它们中任意两个数值所组成的范围之间的值。电子传输层墨水在钙钛矿层上形成的湿膜厚度在上述范围内时，使得该湿膜经风刀处理后能够形成超薄且部分覆盖钙钛矿层的电子传输层。
在一些实施方式中，上述风刀处理的出风量为60ul/s-200ul/s，风刀处理的出风量控制在上述范围内，有助于控制电子传输层在钙钛矿层上有合适的覆盖率，进而提高电子传输层的传输效率和钙钛矿太阳能电池的光电转换效率。示例性地，上述风刀处理的出风量可以为60ul/s、80ul/s、90ul/s、100ul/s、120ul/s、150ul/s、160ul/s、200ul/s，或它们中任意两个数值所组成的范围之间的值。
在一些实施方式中，上述电子传输层墨水包括电子传输材料和溶剂，其中，作为电子传输材料如上所述，在此不做赘述；作为溶剂，包括氯苯、邻二氯苯中的一种或多种。上述电子传输材料和溶剂的组合能够提供良好的导电性能，并且所形成的电子传输层墨水适用于狭缝涂布法，易于加工，并且易于通过风刀处理快速风干，以形成均匀分布的电子传输层干膜。
在一些实施方式中，上述电子传输层墨水的浓度为5-30mg/ml。电子传输层墨水的浓度在上述范围内，使得电子传输层墨水具有合适的粘度，有利于应用于狭缝涂布法，提高涂布的精度和效率。示例性地，上述电子传输层墨水的浓度可以为5mg/ml、10mg/ml、15mg/ml、20mg/ml、25mg/ml、30mg/ml，或它们中任意两个数值所组成的范围之间的值。在一些实施方式中，上述电子传输层墨水的浓度为8-20mg/ml，可选地10-20mg/ml。
在一些实施方式中，上述狭缝涂布法的注液速度为70-300ul/s。示例性地，上述狭缝涂布法的注液速度可以为70ul/s、100ul/s、140ul/s、200ul/s、240ul/s、300ul/s，或它们中任意两个数值所组成的范围之间的值。在一些实施方式中，上述狭缝涂布法的涂布模头的移动速度为10-100mm/s，示例性地，上述狭缝涂布的移动速度可以为10mm/s、30mm/s、50mm/s、80mm/s、90mm/s、100mm/s，或它们中任意两个数值所组成的范围之间的值。
本公开中通过在上述范围内适当地调整狭缝涂布法的注液速度和移动速度以及风刀处理的出风量，使得电子传输层覆盖于钙钛矿层的晶界处，而部分覆盖钙钛矿层，使得电子传输层提供有效的电子传输通道，改善电子传输效率。
在一些实施方式中，上述狭缝涂布法的注液速度为100-240ul/s，可选地140-240ul/s；移动速度为60-100mm/s，可选地80-100mm/s；上述风刀处理的出风量为70-200ul/s，可选地90-160ul/s。
对于通过如上狭缝涂布和风刀处理所涂布的电子传输层的量，相当于在几乎完全平整的基板涂布厚度为10nm-20nm的电子传输层，例如基板可以为光滑平整的纯玻璃。通过上述处理可以形成部分覆盖钙钛矿层的电子传输层，所得电子传输层覆盖在钙钛矿层的晶界处。
本公开对第一电极的制备不做特别限制，通常可以通过市购获得，或者可以采用本领域常规使用的方法制备即可。
本公开对空穴传输层的制备方法不做特别限制，采用本领域常规使用的方法即可。示例性地，空穴传输层的制备可以采用旋涂法、气相沉积法(例如，磁控溅射法)等。
本公开对钙钛矿层的制备方法不做特别限制，采用本领域常规使用的方法即可。示例性地，钙钛矿层的制备可以采用旋涂法、狭缝涂法、刮涂法等液相法，也可以采用蒸镀等气相法，或气液相结合的方法。
本公开对第二电极的制备方法不做特别限制，采用本领域常规使用的方法即可。示例性地，第二电极的制备可以采用磁控溅射法、蒸镀法等。
另外，本公开还提供一种光伏组件。通常情况下，光伏组件包括上述钙钛矿太阳能电池、将多个钙钛矿太阳能电池连接的焊带、用于电流传输的接线盒、电池封装部件。
在一些实施方式中，电池封装部件包括光伏玻璃，光伏玻璃覆盖于上述钙钛矿太阳能电池，起到保护钙钛矿太阳能电池的作用。同时，光伏玻璃具有非常好的透光性和很高的硬度，可以适应很大的昼夜温差和恶劣的天气环境。
在一些实施方式中，电池封装部件包括乙烯-醋酸乙烯酯共聚物(EVA)薄膜，布置于光伏玻璃和钙钛矿太阳能电池之间，用于粘接光伏玻璃和太阳能电池。
在一些实施方式中，电池封装部件包括光伏背板，光伏背板同样起到保护钙钛矿太阳能电池的作用。
可选地，光伏背板的材料可以为聚氟乙烯复合膜或者热塑性弹性材料。光伏背板的材料具有绝缘、防水、耐老化等特性。
在一些实施方式中，电池封装部件包括太阳能铝边框，包括铝合金材质，具有强度高、耐腐蚀性好等特点。可以起到支撑和保护太阳能电池的作用。
另外，本公开还提供一种发电装置，包括上述实施例提供的钙钛矿太阳能电池。
另外，本公开还提供一种用电装置，包括上述实施例提供的钙钛矿太阳能电池。
在一些实施例中，用电装置还可以为照明设备、储能设备等，本公开实施例包括但不限于此。例如，用电装置可以为太阳能热水器、太阳能路灯、太阳能光伏发电机等。
实施例
以下，说明本公开的实施例。下面描述的实施例是示例性的，仅用于解释本公开，而不能理解为对本公开的限制。除非另外说明，所用试剂均为市购，所用设备均为常规设备。
以下通过实施例进一步说明本公开。
实施例1
钙钛矿太阳能电池的制备：
1)制备第一电极：将规格为30*30cm2的FTO玻璃采用水、丙酮、异丙醇依次超声清洗刻蚀后的FTO导电玻璃数次，然后用氮气吹干备用；然后将上述清洗吹干的FTO导电玻璃进行紫外臭氧处理备用。
2)空穴传输层的制备：采用磁控溅射，在上述第一电极上形成厚度约为20nm的NiOx，在300℃条件下退火60min，得到空穴传输层。
3)钙钛矿层的制备：采用一步法制备钙钛矿光吸收材料。称量0.05molCsI、0.95mol FAI、1molPbI2放入666ml的DMF中，常温搅拌6h，用0.22um滤嘴过滤，装填于涂布机采用狭缝涂布法(涂布模头移动速度为50mm/s，注液速度为200ul/s)将上述制得的钙钛矿光吸收材料置于烘箱，在140℃条件下退火20min，得到厚度为500nm的钙钛矿层FA0.9Cs0.1PbI3。通过原子力显微镜(AFM)测定，所得钙钛矿层的均方根粗糙度为35nm。
4)电子传输层的制备：将100mg的PC61BM与10ml的氯苯溶液混合搅拌，500rpm转动速度下搅拌8小时制得电子传输层墨水(浓度10mg/ml)。使用狭缝涂布法在上述钙钛矿层上涂布电子传输层墨水，其中涂布模头移动速度为100mm/s，注液速度为200ul/s。风刀设置于涂布头后面，与涂布机共同行进，通过控制风刀一边涂布一边干燥，以进行保形处理，其中，风刀出风速度为120uL/s，以形成电子传输层。
5)第二电极的制备：将上述制备有电子传输层的片材放入蒸镀仪，待蒸镀真空度至5*10-4Pa以下，以0.1A/s的速率蒸镀80nm金属背电极Cu，得到钙钛矿太阳能电池。
钙钛矿太阳能电池的色度分析
将上述制备有电子传输层的片材采用蔡司GeminiSEM的扫描电镜进行扫描电镜分析，拍摄SEM图像。将所获得的SEM图像采用colorpix软件进行色度分析，识别每个像素的R、G、B三通道的色度值，并通过公式RGB平均值＝(R通道色度值+B通道色度值+G通道色度值)/3来计算每个像素的RGB平均值。根据RGB平均值区分电子传输层覆盖的区域(即第一类色)和电子传输层未覆盖的区域(第二类色)，然后利用公式：电子传输层覆盖率＝第一类色的色块面积/(第一类色的色块面积+第二类色的色块面积)×100％来计算电子传输层的覆盖率。具体参见图2所示。
钙钛矿太阳能电池的表面电势测试
将上述形成电子传输层后的片材采用BRUKER开尔文探针力显微镜(KPFM)进行表面电势测试，获得KPFM图谱，具体参见图3所示。
由图3可见，在钙钛矿层上覆盖有上述电子传输层的区域的表面与未覆盖上述电子传输层的区域的表面存在电势差，电势差的存在表明电子传输层未完全覆盖钙钛矿层。
钙钛矿太阳能电池的器件测试
采用Keithley2400SMU，AM1.5Gsolarirradiation在1000W/m2的光源下对制得的钙钛矿太阳能电池进行器件测试。将Keithley2400SMU正极接在钙钛矿太阳能电池阳极(即空穴端)，负极接在钙钛矿太阳能电池阴极(即电子端)，将起始电压设置为-0.1V，结束电压设置为1.2V，扫描方式设置为reverse scan，进行测试。分别记录测得电池工作输出功率(Pout)、入射光功率(Popt)。采用如下公式计算钙钛矿电池的能量转化效率：
PCE＝Pout/Popt
实施例2-13
按照实施例1的方法制备钙钛矿太阳能电池，区别之处在于：通过调整步骤4)中的工艺参数获得不同的覆盖率，具体数值如表1所示。
按照与实施例1相同的方法进行性能测试，测试结果参见表1。
实施例14
按照实施例1的方法制备钙钛矿太阳能电池，区别之处在于：将步骤3)中的溶剂DMF替换为DMSO/DMF体积比1：9的混合溶剂，所得钙钛矿层的均方根粗糙度为8nm。
实施例15
按照实施例1的方法制备钙钛矿太阳能电池，区别之处在于：将步骤3)中的退火温度替换为120℃，所得钙钛矿层的均方根粗糙度为40nm。
实施例16
按照实施例1的方法制备钙钛矿太阳能电池，区别之处在于：步骤3)与步骤4)之间增加制备钝化层的步骤，具体的，
使用狭缝涂布法将哌嗪碘的异丙醇溶液(浓度0.5mg/mL)涂布在上述钙钛矿层上，涂布模头移动速度为50mm/s，注液速度为300ul/s，风刀干燥，得到上钝化层，厚度约为2nm。之后使用狭缝涂布法将电子传输层墨水涂布在上述上钝化层上，其余同实施例1。
对比例1
按照实施例1的方法制备钙钛矿太阳能电池，区别之处在于：步骤5)中使得电子传输层完全覆盖钙钛矿层，覆盖率为100％。其电子传输层的SEM色块分析图如图4所示。
按照与实施例1相同的方式进行性能测试，测试结果参见表1。
表1
由表1的数据可以看出，与对比例1这样的电子传输层完全覆盖钙钛矿层的钙钛矿太阳能电池相比，本公开中通过使电子传输层部分覆盖钙钛矿层，钙钛矿太阳能电池的光电转化效率提高。
本公开不限定于上述实施方式。上述实施方式仅为示例，在本公开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公开的技术范围内。此外，在不脱离本公开主旨的范围内，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公开的范围内。

Claims (20)

  1. 一种钙钛矿太阳能电池，所述钙钛矿太阳能电池包括第一电极和第二电极，在所述第一电极和所述第二电极之间，沿第一方向依次排布有钙钛矿层和电子传输层，其中，所述电子传输层部分覆盖钙所述钛矿层；所述第一方向为光入射方向。
  2. 根据权利要求1所述的钙钛矿太阳能电池，其中，所述电子传输层对所述钙钛矿层的覆盖率为30％-90％。
  3. 根据权利要求1或2所述的钙钛矿太阳能电池，其中，所述电子传输层对所述钙钛矿层的覆盖率为42％-62％。
  4. 根据权利要求1至3中任一项所述的钙钛矿太阳能电池，其中，所述钙钛矿层的均方根粗糙度为8nm-40nm。
  5. 根据权利要求1至4中任一项所述的钙钛矿太阳能电池，其中，所述电子传输层的表面与所述电子传输层未覆盖的所述钙钛矿层的表面，存在100mV-200mV的电势差。
  6. 根据权利要求1至5任一项所述的钙钛矿太阳能电池，其中，所述电子传输层包括电子传输材料，所述电子传输材料包括富勒烯及其衍生物、金属氧化物、金属氟化物中的至少一种。
  7. 根据权利要求6所述的钙钛矿太阳能电池，其中，所述富勒烯及其衍生物包括富勒烯C60、富勒烯C70、[6,6]-苯基C61丁酸甲酯、[6,6]-苯基C71丁酸甲酯、茚-C 60双加合物中的一种或几种。
  8. 根据权利要求6所述的钙钛矿太阳能电池，其中，所述金属氧化物包括二氧化锡、氧化锌的一种或两种。
  9. 根据权利要求6所述的钙钛矿太阳能电池，其中，所述金属氟化物包括氟化锂、氟化钙的一种或两种。
  10. 一种钙钛矿太阳能电池的制备方法，包括如下步骤：
    在第一电极上形成钙钛矿层；
    在所述钙钛矿层上形成电子传输层，所述电子传输层部分覆盖所述钙钛矿层；和
    在所述电子传输层上形成第二电极。
  11. 根据权利要求10所述的制备方法，其中，所述电子传输层对所述钙钛矿层的覆盖率为30％-90％。
  12. 根据权利要求11所述的制备方法，其中，所述电子传输层对所述钙钛矿层的覆盖率为42％-62％。
  13. 根据权利要求10至12中任一项所述的制备方法，其中，在所述钙钛矿层上形成电子传输层包括：通过狭缝涂布将电子传输层墨水涂布在所述钙钛矿层上形成湿膜的同时，进行风刀处理。
  14. 根据权利要求13所述的制备方法，其中，所述湿膜的厚度为6μm以下。
  15. 根据权利要求14所述的制备方法，其中，所述风刀处理的出风量为60-200ul/s。
  16. 根据权利要求15所述的制备方法，其中，所述电子传输层墨水的浓度为5-30mg/ml，所述狭缝涂布的注液速度为70-300ul/s，所述狭缝涂布的移动速度为10-100mm/s。
  17. 根据权利要求15或16所述的制备方法，其中，所述风刀处理的出风量为70-200ul/s；所述狭缝涂布法的注液速度为100-240ul/s；移动速度为60-100mm/s。
  18. 一种光伏组件，所述光伏组件包括权利要求1至9中任一项所述的钙钛矿太阳能电池或权利要求10至17中任一项所述的制备方法制得的钙钛矿太阳能电池。
  19. 一种发电装置，所述发电装置包括权利要求1至9中任一项所述的钙钛矿太阳能电池或权利要求10至17中任一项所述的制备方法制得的钙钛矿太阳能电池。
  20. 一种用电装置，所述用电装置包括权利要求1至9中任一项所述的钙钛矿太阳能电池或权利要求10至17中任一项所述的制备方法制得的钙钛矿太阳能电池。
PCT/CN2025/095460 2024-05-22 2025-05-16 钙钛矿太阳能电池及其制备方法、光伏组件、发电装置和用电装置 Pending WO2025242003A1 (zh)

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