WO2023143157A1 - 钙钛矿太阳能电池及其制备方法 - Google Patents

钙钛矿太阳能电池及其制备方法 Download PDF

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WO2023143157A1
WO2023143157A1 PCT/CN2023/072276 CN2023072276W WO2023143157A1 WO 2023143157 A1 WO2023143157 A1 WO 2023143157A1 CN 2023072276 W CN2023072276 W CN 2023072276W WO 2023143157 A1 WO2023143157 A1 WO 2023143157A1
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transport layer
hole transport
nickel
perovskite
layer
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PCT/CN2023/072276
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French (fr)
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梁伟风
涂保
苏硕剑
郭永胜
陈国栋
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宁德时代新能源科技股份有限公司
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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
    • H10K30/10—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
    • H10K30/40—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
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • 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
    • 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 perovskite solar cells, in particular to a perovskite solar cell with high photoelectric conversion efficiency and good stability and a preparation method thereof.
  • perovskite solar cells are favored due to their advantages such as high photoelectric conversion efficiency, simple manufacturing process, low production cost and material cost.
  • nickel-containing materials are often used to prepare hole transport layers.
  • the interaction between the nickel oxide hole transport layer and the perovskite layer prepared in this way would degrade the performance of perovskite solar cells.
  • most of the ways to reduce or prevent the interaction between nickel oxide and perovskite are to cover the surface of nickel oxide with a layer of passivation material.
  • this method may increase the time cost, economic cost and environmental cost of cell preparation and is not conducive to the extraction of carriers by the hole transport layer in perovskite solar cells, thus affecting the photoelectric conversion efficiency of the cell.
  • the present application is made in view of the above problems, and its purpose is to provide a perovskite solar cell with high photoelectric conversion efficiency and good long-term use stability, and its preparation method is lower cost and more efficient.
  • the first aspect of the present application provides a perovskite solar cell, which includes a transparent conductive glass, a hole transport layer, a perovskite layer, an electron transport layer and an electrode, and the hole transport layer includes three Nivalent nickel and nickel divalent, wherein the molar ratio of nickel trivalent to nickel divalent on the surface of the hole transport layer facing the perovskite layer is in the range of 0 to 0.20, optionally 0 to 0.10.
  • Both trivalent nickel and divalent nickel in the hole transport layer can be used to collect and extract holes from the perovskite layer.
  • the trivalent nickel on the surface of the hole transport layer will cause the perovskite (for example, the perovskite with the structural formula ABX 3 ) to decompose, mainly in that it will cause the A site and the X site of the perovskite to be oxidized and become a gas, This results in deep level defects in perovskite.
  • This application reduces or even eliminates the decomposition of perovskite caused by trivalent nickel by reducing the trivalent nickel on the surface of the hole transport layer to divalent nickel that can also collect and extract holes , thereby improving the efficiency and stability of perovskite solar cells.
  • no trivalent nickel is present on the surface of the hole transport layer facing the perovskite layer.
  • the hole transport layer is a nickel oxide hole transport layer.
  • Nickel oxide hole transport layer is a commonly used hole transport layer.
  • Nickel oxide is generally expressed as NiOx, which may represent one or more of nickel oxide, nickel trioxide, nickelous oxide, and the like.
  • the hole transport layer is doped with other hole transport materials than nickel oxide.
  • the other hole transport material may be a material other than nickel oxide used in the art for a hole transport layer.
  • the hole transport layer is doped with one or more ions selected from Li + , Na + , K + , Ru + , Cs + .
  • the perovskite solar cell is an inverse perovskite solar cell.
  • the perovskite solar cells described in this application are suitable for trans-structure.
  • the perovskite solar cell sequentially includes conductive glass, a hole transport layer, a perovskite layer, an electron transport layer and a metal electrode.
  • the perovskite layer and the electron transport layer are There is a passivation layer between them; optionally, there is a buffer layer between the electron transport layer and the metal electrode.
  • the second aspect of the present application provides a method for preparing a perovskite solar cell, which includes the steps of preparing a hole transport layer, preparing a perovskite layer, optionally preparing a passivation layer, preparing an electron transport layer, optionally The step of preparing a buffer layer and the step of making a metal back electrode, wherein no other layers are arranged between the hole transport layer and the perovskite layer, and the step of preparing a hole transport layer includes the following operations:
  • Step S1 preparing a solution of a hole transport layer material, adding it on the conductive glass, and then annealing to obtain a hole transport layer 1; wherein the hole transport layer material includes a nickel-containing substance;
  • Step S2 Using a reducing substance to reduce the trivalent nickel on the surface of the hole transport layer 1 obtained in step S1 to obtain the final hole transport layer.
  • the content of trivalent nickel on the surface of the hole transport layer facing the perovskite layer can be reduced,
  • the increase of divalent nickel content is beneficial to prevent the decomposition of perovskite caused by the reaction between trivalent nickel and perovskite, thereby improving the photoelectric conversion efficiency and stability of solar cells.
  • the nickel-containing substance is selected from nickel oxide, nickel nitrate, nickel acetate, nickel acetylacetonate or a mixture thereof.
  • the nickel oxide may be nickel oxide nanoparticles.
  • the nickel nitrate may be hydrated nickel nitrate, such as nickel nitrate hexahydrate.
  • the nickel acetate may be hydrated nickel acetate, such as nickel acetate tetrahydrate.
  • step S1 includes the following operations:
  • the solvent is selected from methanol, One or more of ethylenediamine and water.
  • step S2 includes the following operations:
  • the hole transport layer 1 is ultrasonically reduced using ultrasonic waves in a solution of a reducing substance and/or in an atmosphere of a reducing substance.
  • the hole transport layer 1 is placed in a reducing environment, such as a reducing substance solution or atmosphere, and the trivalent nickel on the surface of the hole transport layer can be easily reduced to divalent nickel by using ultrasonic waves, Moreover, the processing steps are simple and efficient, saving economic cost and time cost.
  • step S2 after the ultrasonic reduction, the molar ratio of trivalent nickel to divalent nickel on the surface of the hole transport layer facing the perovskite layer ranges from 0 to 0.2, more optionally 0 to 0.1.
  • the reducing substance in the reducing substance solution is selected from:
  • the concentration of the solution of the reducing substance is 1mg/L to 100g/L; optionally, in the ultrasonic step, the temperature of the solution of the reducing substance is -20°C-100°C, which can be 10°C-100°C is selected, more preferably 50°C-60°C.
  • the solution of the reducing substance is an aqueous solution.
  • the reducing substance in the atmosphere of the reducing substance is selected from hydrogen, carbon monoxide or a mixture thereof; optionally, the temperature of the atmosphere of the reducing substance is -20°C-100°C, optionally 10°C-100°C, more preferably 50°C-60°C.
  • argon and hydrogen may be used, wherein the volume ratio of argon to hydrogen may range from 80:20 to 99:1, more preferably from 90:10 to 99:1.
  • the ultrasonic frequency range is 10-100 Hz, optionally 20-60 Hz; optionally, the ultrasonic time range is 0.1-60 min, optionally 0.1-30 min, and more optionally 0.1-20min.
  • the photoelectric conversion efficiency of the perovskite solar cell prepared by performing the ultrasonic step is higher, and the stability is better.
  • Figure 1 is a schematic structural view of a perovskite solar cell in an embodiment of the present application, from top to bottom are metal electrodes, buffer layers, electron transport layers, perovskite layers, hole transport layers, fluorine-doped tin oxide (FTO ) Conductive thin film, glass substrate, wherein sunlight enters the solar cell from the lower glass substrate, wherein the fluorine-doped tin oxide (FTO) conductive thin film and the glass substrate together form a conductive glass.
  • FTO fluorine-doped tin oxide
  • a "range” disclosed herein is defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Also, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following The ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-6.
  • the numerical range “ab” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
  • step (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c) , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b) and so on.
  • the “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: 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).
  • nickel oxide is usually used as the hole transport material.
  • divalent nickel and trivalent nickel exist in the hole transport layer at the same time due to the difference in the preparation process.
  • Trivalent nickel has a good transport effect in the process of hole transport, but if trivalent nickel exists on the surface of the hole transport layer, It will react with perovskite and cause perovskite to decompose, which is not conducive to the transmission of carriers and will reduce the filling of the battery. At the same time, it will increase the resistance of the battery and is not conducive to the long-term stability of the battery.
  • the method to solve the above problems is mainly to prepare a passivation layer composed of p-type passivation material on the surface of nickel oxide.
  • the preparation of the passivation layer requires various processes such as spin coating, annealing or vacuuming, which increases the time, energy consumption and economical cost of battery preparation.
  • the currently used interface passivation materials are difficult to synthesize and are difficult to apply in the later stage.
  • the increase of the passivation layer also increases the number of interfaces, resulting in more defects at the interface.
  • the inventors of the present application have unexpectedly found that when the trivalent nickel on the surface of the hole transport layer is treated to reduce the content of trivalent nickel on the surface of the hole transport layer, the performance of the perovskite solar cell can be improved. Transformation efficiency and long-term stability. Further research by the inventors found that by reducing the surface of the hole transport layer containing trivalent nickel, the content of trivalent nickel on the surface of the hole transport layer can be effectively reduced without affecting the content of trivalent nickel inside the hole transport layer. In this way, without using other materials to cover the surface of the hole transport layer, the hole transport effect of the hole transport layer is guaranteed and the trivalent nickel on the surface of the hole transport layer is prevented from being damaged by the perovskite.
  • the inventors also found that when reducing the surface of the hole transport layer containing trivalent nickel, using ultrasonic waves for reduction is simple, efficient, easy to handle and low in cost.
  • the first aspect of the present application provides a perovskite solar cell, which includes a transparent conductive glass, a hole transport layer, a perovskite layer, an electron transport layer and an electrode, and the hole transport layer includes trivalent nickel and divalent nickel Nickel, wherein the molar ratio of trivalent nickel to divalent nickel on the surface of the hole transport layer facing the perovskite layer ranges from 0 to 0.20, more preferably from 0 to 0.10, more preferably from 0 to 0.05.
  • the hole transport layer is used to collect, extract and transport holes from the perovskite layer.
  • the hole transport layer described herein contains trivalent nickel and divalent nickel.
  • the hole transport layer material can be prepared using nickel-containing substances available in the art.
  • Both trivalent nickel and divalent nickel in the hole transport layer can be used to collect and extract holes from the perovskite layer.
  • the trivalent nickel on the surface of the hole transport layer will cause the perovskite (for example, the perovskite with the structural formula ABX 3 ) to decompose, mainly in the A site of the perovskite and the X Bits are oxidized to gas, which causes deep-level defects in perovskite.
  • the present application reduces or even eliminates the decomposition of trivalent nickel to perovskite by reducing the trivalent nickel on the surface of the hole transport layer to divalent nickel that can also collect and extract holes. This improves the efficiency and stability of perovskite solar cells.
  • the content of trivalent nickel on the surface of the hole transport layer decreases, and the content of divalent nickel increases correspondingly.
  • Divalent nickel does not cause perovskite decomposition and also has the ability to extract and transport holes, so the reduction of trivalent nickel on the surface of the hole transport layer is a favorable choice.
  • no trivalent nickel is present on the surface of the hole transport layer facing the perovskite layer.
  • the molar ratio of trivalent nickel to divalent nickel on the surface of the hole transport layer can be tested by X-ray photoelectron spectroscopy (XPS). The test can be performed on the surface of the hole transport layer facing the perovskite layer. According to the test results, the molar ratio of trivalent nickel to divalent nickel can be calculated.
  • XPS X-ray photoelectron spectroscopy
  • the hole transport layer is a nickel oxide hole transport layer.
  • Nickel oxide hole transport layer is a commonly used hole transport layer.
  • Nickel oxide is generally expressed as NiOx, which may represent one or more of nickel oxide, nickel trioxide, nickelous oxide, and the like.
  • NiO, Ni(OH) 2 , Ni 2 O 3 , NiOOH and the like may exist in the hole transport layer.
  • no interfacial passivation material optionally no p-type interfacial passivation material, is present on the surface of the hole transport layer facing the perovskite layer.
  • there is no passivation layer between the hole transport layer and the perovskite layer ie a passivation layer for passivating the hole transport layer.
  • the hole transport layer may be doped, for example may be a doped nickel oxide layer.
  • the hole transport layer is doped with other hole transport materials than nickel oxide.
  • the other hole transport material may be a material other than nickel oxide used in the art for a hole transport layer.
  • the hole transport layer includes not only nickel oxide, but also other materials conventionally used in the field for hole transport layers.
  • Other materials conventionally used in the art for hole transport layers may include, for example, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3, 4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), poly-3-hexylthiophene (P3HT), poly[bis(4-phenyl)(4-butylphenyl)amine](poly- TPD), cuprous thiocyanate (CuSCN), etc.
  • PTAA poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]
  • PEDOT:PSS poly(3, 4-ethylenedioxythiophene)-polystyrenesulfonic acid
  • P3HT poly-3-hexylthiophene
  • CuSCN cuprous thiocyanate
  • the hole transport layer is doped with one or more ions selected from Li + , Na + , K + , Ru + , Cs + .
  • the hole transport layer may optionally be doped with one or more ions selected from Li + , Na + , K + , Ru + , and Cs + .
  • the thickness of the hole transport layer is 5-50 nm, optionally 10-40 nm, more optionally 20-30 nm.
  • the perovskite solar cell is an inverse perovskite solar cell.
  • the trans perovskite solar cell from the light incident surface, there are conductive glass, a hole transport layer, a perovskite layer, an electron transport layer, and a metal back electrode.
  • the perovskite solar cell sequentially includes a conductive glass, a hole transport layer, a perovskite layer, an electron transport layer, and a metal electrode.
  • the perovskite layer and the electron transport layer are There is a passivation layer between them; optionally, there is a buffer layer between the electron transport layer and the metal electrode.
  • Conductive glass usually has a certain degree of transparency. Generally, transparent conductive glass is used. Conductive glass usually consists of a glass substrate and an oxide thin film (TCO for short) conductive layer. The glass substrate and conductive layer are of any thickness used in the art. Optionally, the thickness of the conductive layer is in the range of 100-1000 nm. Optionally, the thickness of the glass substrate is generally in the range of 0.1-3 cm. Commonly used TCOs include indium tin oxide (ITO) and fluorine-doped tin oxide (FTO), but the present application is not limited thereto. Conductive glass needs to be cleaned before use, such as ultrasonic cleaning with detergent, deionized water and ethanol.
  • ITO indium tin oxide
  • FTO fluorine-doped tin oxide
  • Conductive glass is used to conduct charge carriers out.
  • the perovskite used for the perovskite layer may have the chemical formula ABX 3 ,
  • A may be methylamine (abbreviated as MA), formamidine (abbreviated as FA) or cesium (Cs)
  • B may be lead (Pb) or tin ( Sn)
  • X can be iodine (I) or bromine (Br).
  • lead formamidine iodide (FAPbI 3 ) system is used as perovskite layer material.
  • the perovskite layer can be prepared by conventional technical means in this field, and can also be prepared by the following method (take the trans perovskite solar cell as an example): Weigh the perovskite precursor material, for example, formamidine iodide (FAI), iodine Lead chloride (PbI 2 ), methylamine chloride (MACl), methylamine iodide (MAI), cesium iodide (CsI), etc., dissolved in a solvent (for example, dimethylformamide (DMF), dimethyl sulfoxide ( DMSO) or its mixture, etc.), stir evenly, filter, and take the supernatant; cover the supernatant on the prepared hole transport layer.
  • a solvent for example, dimethylformamide (DMF), dimethyl sulfoxide ( DMSO) or its mixture, etc.
  • the spin coating time can be 5-50 seconds; anti-solvent can be added dropwise during covering (optionally using spin coating), and annealing is performed after covering (optionally spin coating),
  • the annealing temperature may be 80-150° C.
  • the annealing time may be 0-60 min, and the perovskite layer can be obtained after annealing.
  • the anti-solvent may be, for example, chlorobenzene, ethyl acetate, toluene, etc., but is not limited thereto.
  • the thickness of the perovskite layer can be any thickness used in the art.
  • the thickness of the perovskite layer is in the range of 200-1000 nm.
  • a passivation layer may exist between the electron transport layer and the perovskite layer for passivating defects at the interface between the electron transport layer and the perovskite layer.
  • the thickness of the passivation layer can be any thickness used in the art.
  • the thickness of the passivation layer is in the range of 1-20nm.
  • Electron transport layer and buffer layer are Electron transport layer and buffer layer
  • the electron transport layer and buffer layer can be prepared by conventional techniques in the art.
  • the preparation method is as follows: the fullerene or fullerene derivative is dissolved in an organic solvent (such as chlorobenzene, dichlorobenzene, toluene, dichlorobenzene, Toluene or its mixture), prepare a fullerene derivative solution with a concentration ranging from 5-50 mg/mL.
  • an organic solvent such as chlorobenzene, dichlorobenzene, toluene, dichlorobenzene, Toluene or its mixture
  • the coating method can be spin-coated with a homogenizer, wherein the speed can be 500-5000rpm/s, and the spin-coating time can be 5-50 seconds , annealing is performed after spin coating, the annealing temperature may be 80-150° C., the annealing time may be 0-60 min, and an electron transport layer is obtained after annealing.
  • a buffer layer is used between the electron transport layer and the metal electrode to enhance the performance of perovskite solar cells.
  • bathocuproine BCP
  • BCP bathocuproine
  • the thickness of the electron transport layer can be any thickness used in the art.
  • the thickness of the electron transport layer is in the range of 10-100 nm.
  • the metal back electrode can be gold (Au), silver (Ag), copper (Cu), but not limited thereto.
  • the metal back electrode can be prepared by vapor deposition.
  • the thickness of the metal back electrode can be any thickness used in the art.
  • the thickness of the metal back electrode is in the range of 10-200 nm.
  • the metal back electrode is also referred to as a metal electrode or electrode.
  • the second aspect of the present application provides a method for preparing a perovskite solar cell, which includes the steps of preparing a hole transport layer, preparing a perovskite layer, optionally preparing a passivation layer, preparing an electron transport layer, optionally The step of preparing a buffer layer and the step of making a metal back electrode, wherein no other layers are arranged between the hole transport layer and the perovskite layer, and the step of preparing a hole transport layer includes the following operations:
  • Step S1 preparing a solution of a hole transport layer material, adding it on the conductive glass, and then annealing to obtain a hole transport layer 1; wherein the hole transport layer material includes a nickel-containing substance;
  • Step S2 Using a reducing substance to reduce the trivalent nickel on the surface of the hole transport layer 1 obtained in step S1 to obtain the final hole transport layer.
  • the steps of preparing the hole transport layer, preparing the perovskite layer, preparing the passivation layer, preparing the electron transport layer, preparing the buffer layer and preparing the metal back electrode can all adopt conventional preparation methods in the art.
  • an operation of reducing the trivalent nickel on the surface to divalent nickel is added, such as reduction, such as ultrasonic reduction.
  • the method for preparing a perovskite solar cell comprises the following steps:
  • step (4) Part of the functional layer (including hole transport layer, perovskite layer, optional passivation layer, electron transport layer, optional buffer layer) is scraped off the object obtained in step (4), exposing the conductive glass layer , and then wipe off the remaining functional layer with lotion, then put the object into the evaporation mask plate, scrape off the electrode position, wipe off the residual functional layer with lotion, put it into the evaporation mask
  • the metal that can be used as an electrode is evaporated in a vacuum evaporation equipment. After evaporation, a complete perovskite solar cell is obtained.
  • the passivation material mentioned above is a material suitable for passivating the interface between the electron transport layer and the perovskite layer used in the art.
  • the "covering” at least includes technical means such as “spin coating”, “spray coating” and “sputtering” used in the art.
  • the reduction step there is no special limitation in the reduction step, as long as the trivalent nickel on the surface of the hole transport layer can be reduced to divalent nickel without adversely affecting the performance of the perovskite solar cell.
  • the content of trivalent nickel on the surface of the hole transport layer facing the perovskite layer can be reduced,
  • the increase of divalent nickel content is beneficial to prevent the decomposition of the perovskite layer and the reaction of trivalent nickel and perovskite, thereby improving the photoelectric conversion efficiency and stability of the solar cell.
  • the reaction of reducing trivalent nickel to divalent nickel is an oxidation-reduction reaction, and the reducibility of the required reducing substance should be sufficient to reduce trivalent nickel to divalent nickel.
  • any reducing substance that can reduce trivalent nickel to divalent nickel without any adverse effect on perovskite solar cells can be used in the reduction step described in this application.
  • the hole transport layer 1 is prepared by a sol-gel method in step S1, which includes the following steps: adding the supernatant of the nickel-containing substance solution onto the conductive glass,
  • the amount of dripping is 0.01-1mL, and then rotate, the rotation speed can be 1000-8000rpm/s, the rotation time can be 10-60s, and then annealing is performed.
  • the annealing procedure is as follows: keep warm at 80°C 1-100min, then increase the temperature to 200-500°C within 10-50min, keep at 200-500°C for 0.1-5h, and then cool to below 100°C; the hole transport layer 1 is obtained after annealing.
  • a nickel oxide hole transport layer can be prepared by dissolving nickel nitrate, nickel acetylacetonate, or nickel acetate in methanol and spin-coating it on cleaned conductive glass at 500-5000rpm/s, spin coating time 5-50 seconds, annealing is performed after spin coating, the annealing temperature is 80-400°C, and the annealing time is 0-120min.
  • the hole transport layer 1 is prepared by spray pyrolysis in step S1, including the following operations: dissolving the nickel-containing substance in a solvent to obtain a solution of the nickel-containing substance, stirring, and filtering , take the supernatant, make it into a spray, spray it on the surface of the conductive glass, and then sinter.
  • the sintering temperature range of the sintering is 100-500°C, optionally 300-400°C, and the sintering time is 10- 120 min, optionally 60-80 min; the hole transport layer 1 is obtained after cooling.
  • the hole transport layer 1 is prepared by magnetron sputtering in step S1, including the following operations: dissolving the nickel-containing substance in a solvent to obtain a nickel-containing substance solution, stirring, Filter, get the supernatant, and use magnetron sputtering to sputter the supernatant on the surface of transparent conductive glass, optionally, wherein oxygen and nitrogen are used, and the volume ratio of oxygen to nitrogen is 1:20 to 1: 5, optional from 1:12 to 1:8.
  • the nickel-containing substance is any nickel-containing substance that can be used to prepare the hole transport layer.
  • the nickel-containing substance is selected from nickel oxide, nickel nitrate, nickel acetate, nickel acetylacetonate or a mixture thereof.
  • the nickel oxide may be nickel oxide nanoparticles.
  • the nickel nitrate may be hydrated nickel nitrate, such as nickel nitrate hexahydrate.
  • the nickel acetate may be hydrated nickel acetate, such as nickel acetate tetrahydrate.
  • step S1 includes the following operations:
  • the solvent is selected from methanol, One or more of ethylenediamine and water.
  • step S2 includes the following operations:
  • the hole transport layer 1 is ultrasonically reduced using ultrasonic waves in a solution of a reducing substance and/or in an atmosphere of a reducing substance.
  • the hole transport layer 1 is placed in a reducing environment, such as a reducing substance solution or atmosphere, and by using ultrasonic waves, the three parts on the surface of the hole transport layer can be easily removed.
  • the valent nickel is reduced to divalent nickel, and the processing steps are simple and efficient, saving economic cost and time cost.
  • the step of using ultrasound to reduce the hole transport layer 1 may include: immersing the hole transport layer 1 with conductive glass in a solution of a reducing substance or placing it in an atmosphere of a reducing substance, and then turning on the ultrasound, keeping After a period of time, the ultrasonic wave is stopped after the reduction reaction is completed, and the hole transport layer is taken out, washed and dried. In this way, trivalent nickel on the surface of the hole transport layer is reduced to divalent nickel.
  • the degree of the reduction reaction can be controlled by controlling the concentration of the reducing substance, the soaking time of the hole transport layer in the reducing solution or the placement time in the reducing atmosphere, ultrasonic frequency, ultrasonic power, and ultrasonic time , and thus the content of trivalent nickel and divalent nickel on the surface of the hole transport layer can be adjusted.
  • the reducing solution or reducing atmosphere can be used repeatedly by replenishing raw materials to reduce the generation of waste.
  • the ultrasonic treatment also has the beneficial effect of high safety.
  • step S2 after the ultrasonic reduction, the molar ratio of trivalent nickel to divalent nickel on the surface of the hole transport layer facing the perovskite layer ranges from 0 to 0.2, more optionally 0 to 0.1.
  • the reducing substance in the reducing substance solution is selected from:
  • the concentration of the solution of the reducing substance is 1mg/L to 100g/L; optionally, in the ultrasonic step, the temperature of the solution of the reducing substance is -20°C-100°C, which can be 10°C-100°C is selected, more preferably 50°C-60°C.
  • the solution of the reducing substance is an aqueous solution.
  • the reducing substance in the reducing substance atmosphere is selected from hydrogen, carbon monoxide or a mixture thereof; optionally, the temperature of the reducing substance atmosphere is -20°C-100°C, optionally 10°C-100°C, more preferably 50°C-60°C.
  • the carrier is used for mixing, that is, the mixed gas of the carrier and the reducing gas is used.
  • the carrier may be an inert gas such as argon or nitrogen.
  • argon is used as a carrier gas, wherein the volume ratio of argon and hydrogen may be in the range of 80:20 to 99:1, more preferably 90:10 to 99 :1.
  • the present application has no special restrictions on the type, temperature, and concentration of the reducing substance, as long as it can reduce the trivalent nickel on the surface of the hole transport layer to divalent nickel and will not bring great harm to the perovskite solar cell. adverse effects.
  • the type, temperature, and concentration of the above-mentioned reducing substances are optional, but the present application is not limited thereto.
  • the ultrasonic frequency range is 10-100 Hz, optionally 20-60 Hz; optionally, the ultrasonic time range is 0.1-60 min, optionally 0.1-30 min, more optionally 0.1-20min.
  • ultrasonic frequency and ultrasonic time are optional, and the present application is not limited thereto.
  • the description of the first aspect of the present application is applicable to the second aspect of the present application.
  • the hole transport layer after the hole transport layer is prepared, it is reduced, optionally ultrasonically reduced so that the moles of trivalent nickel and divalent nickel on the surface of the hole transport layer facing the perovskite layer
  • the ratio ranges from 0 to 0.2, more preferably from 0 to 0.1.
  • nickel-containing substances are used to prepare the nickel oxide hole transport layer; or, in addition to using nickel-containing substances, other hole transport materials can also be used, so that the hole transport layer obtained after preparation In addition to nickel oxide, other hole transport materials are also contained.
  • the nickel-containing hole transport layer (nickel oxide hole transport layer) is doped with one or more hole transport materials containing Li + , Na + , K + , Ru + , Cs + plasma.
  • the perovskite solar cells it is also possible to directly prepare the perovskite layer after the preparation of the hole transport layer, or after the preparation of the perovskite layer, The hole transport layer was directly prepared such that no other layers existed between the hole transport layer and the perovskite layer.
  • the perovskite solar cell prepared by the method described in the second aspect of the present application is an inverse perovskite solar cell.
  • the photoelectric conversion efficiency of the perovskite solar cell prepared by performing the ultrasonic step is higher, and the stability is better.
  • Conductive glass with a fluorine-doped tin oxide (FTO) film wherein the thickness of the conductive layer is 500nm, and the thickness of the glass is 1.5cm, commercially available, cleaned and used directly.
  • FTO fluorine-doped tin oxide
  • Reducing substance solution preparation prepare an aqueous solution of vitamin C with a concentration of 5g/L, and stir until completely dissolved (no insoluble matter is visible in the solution).
  • Reduction reaction Soak the hole transport layer 1 obtained in the previous step in the prepared vitamin C solution, and at 25°C (this is the temperature of the reduction reaction), sonicate at 60 Hz for 10 minutes (this is the time of the reduction reaction) ) and take it out, then rinse off the surface with water For element C, the moisture on the surface was blown off with an air gun, and dried in vacuum to obtain the final hole transport layer, with a thickness of 30nm that was basically unchanged.
  • perovskite solution Dissolve 80mg of formamidine iodide (FAI), 223mg of lead iodide (PbI 2 ), and 15mg of methylamine chloride (MACl) in 1mL of solvent, which is N,N-dimethylformamide A mixed solvent of (DMF) and dimethyl sulfoxide (DMSO), wherein the volume ratio of DMF to DMSO is 4:1 (DMF: DMSO), the perovskite solution was stirred for 1 h at room temperature using a magnetic stirrer, filtered , take the supernatant for later use.
  • solvent which is N,N-dimethylformamide
  • DMF dimethyl sulfoxide
  • DMSO dimethyl sulfoxide
  • Formamidine iodide (FAI), lead iodide (PbI 2 ), and methylamine chloride (MACl) were purchased from Xi'an Baolight Optoelectronic Materials Co., Ltd., and DMF and DMSO were purchased from Sigma.
  • passivation layer solution 5 mg of phenylethylamine hydroiodide (passivation material) was dissolved in 1 ml of chlorobenzene (anti-solvent) to obtain a chlorobenzene solution of phenethylamine hydroiodide.
  • the hole transport layer obtained in the previous step was irradiated with UV for 15 min, and then 60 ⁇ L of the supernatant of the perovskite solution was added dropwise on the hole transport layer.
  • 600 ⁇ L of the prepared phenylethylamine hydroiodide solution in chlorobenzene was annealed at 150° C. for 1 h to obtain a perovskite layer with a thickness of 480 nm and a passivation layer with a thickness of 10 nm.
  • bathocuproine (BCP, commercially available) solution the concentration is 0.5 mg/mL, and the solvent is isopropanol;
  • the object with conductive glass, hole transport layer, perovskite layer, passivation layer, electron transport layer, and buffer layer prepared in the previous step is used according to the mask (Mask) diagram with a blade.
  • Scrape off part of the functional layer including hole transport layer, perovskite layer, passivation layer, electron transport layer, buffer layer
  • the evaporation mask scrape out the electrode position, and wipe off the residual functional layer with the lotion
  • put it into the evaporation mask (Mask) and evaporate 80nm silver in the vacuum evaporation equipment, and the evaporation rate is 0.1A/s. After evaporation, a complete perovskite solar cell is obtained.
  • the perovskite solar cells of Examples 2 and 3 were performed similarly to Example 1, except that the temperatures of the reduction reaction in the preparation of the hole transport layer were 50°C and 75°C, respectively.
  • the perovskite solar cells of Examples 4-6 are carried out similarly to Example 1, except that the reducing substances in the preparation of the hole transport layer are all sodium sulfite, and the concentration of the reducing substances in Example 4 is 5g/L, The time of reduction reaction is 10min; The concentration of reducing substance is 10g/L among the embodiment 5, and the time of reduction reaction is 15min; The concentration of reducing substance among the embodiment 6 is 10g/L, and the time of reduction reaction is 20min.
  • the perovskite solar cells of Examples 7-9 are carried out similarly to Example 1, except that the reducing substances in the preparation of the hole transport layer are a mixture of argon (as a carrier gas) and hydrogen (hereinafter referred to as "argon") Hydrogen mixed gas”), and the volume ratio of argon to hydrogen in the argon-hydrogen mixed gas in Example 7 is 99:1, and the reduction reaction time is 5min; the volume ratio of argon to hydrogen in the argon-hydrogen mixed gas in Example 8 is 95:5, and the reduction reaction time is 10 min; the volume ratio of argon to hydrogen in the argon-hydrogen mixed gas in Example 9 is 90:10, and the reduction reaction time is 1 min.
  • the reducing substances in the preparation of the hole transport layer are a mixture of argon (as a carrier gas) and hydrogen (hereinafter referred to as "argon") Hydrogen mixed gas”)
  • the volume ratio of argon to hydrogen in the argon-hydrogen mixed gas in Example 7 is 99:1, and
  • the perovskite solar cell of Example 10 was performed similarly to Example 1, except that ultrasound was not used, and only immersion in vitamin C solution for 10 minutes was performed.
  • the perovskite solar cell of Example 11 was performed similarly to Example 10, except that it was soaked in vitamin C solution for 1 hour.
  • the perovskite solar cell of Comparative Example 1 was carried out similarly to Example 1, except that in the preparation of the hole transport layer, the reduction reaction was not carried out, but the nickel oxide layer with conductive glass was placed in pure water , sonicate at 25 °C for 10 min.
  • the perovskite solar cell of Comparative Example 2 was carried out similarly to Example 1, except that in the preparation of the hole transport layer, neither reduction reaction nor ultrasound was performed, that is, the nickel oxide with conductive glass layer is directly used in the preparation of the perovskite layer.
  • the perovskite solar cell of Comparative Example 1 was carried out similarly to Example 1, except that in the preparation of the hole transport layer, a layer of common passivation was added between the hole transport layer and the perovskite layer.
  • the passivation layer uses poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA) with a thickness of 2nm.
  • the molar ratios of trivalent nickel and divalent nickel (Ni 3+ /Ni 2+ ) on the surface of the hole transport layer prepared in the above examples and comparative examples were determined by XPS.
  • the test is carried out according to the national standard IEC61215, in which the test is carried out under the condition of light, using a digital source meter, the light source is provided by a solar simulator, and the light emitted by the light source conforms to the AM 1.5G standard solar spectrum.
  • the photoelectric conversion efficiencies of the perovskite solar cells prepared in the examples and the comparative examples were measured on the 3rd day and the 30th day, respectively.
  • the perovskite solar cells prepared in Examples 1-11 all have good 30-day stability. It can be seen that the reduction of the surface of the hole transport layer, no matter which method is used, can improve the stability of the perovskite solar cell.
  • the calcium prepared by reducing the nickel oxide hole transport layer Compared with conventional solar cells, the titanium ore solar cell significantly improves the photoelectric conversion efficiency, and the method is simple and efficient, saves time cost and material cost, and has good economic value.
  • the present application is not limited to the above-mentioned embodiments.
  • the above-mentioned embodiments are merely examples, and within the scope of the technical solutions of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same effects are included in the technical scope of the present application.
  • various modifications conceivable by those skilled in the art are added to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application. .

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Abstract

本申请提供一种钙钛矿太阳能电池，其包括透明导电玻璃、空穴传输层、钙钛矿层、电子传输层和电极，所述空穴传输层包括三价镣和二价镣，其中，所述空穴传输层的朝向钙钛矿层的表面上三价镣与二价镣的摩尔比范围为0至0.2。本申请提供的钙钛矿太阳能电池的光电转化效率高且具有长期稳定性。本申请还提供一种制备所述钙钛矿太阳能电池的方法。

Description

钙钛矿太阳能电池及其制备方法
相关申请的交叉引用
本申请要求享有于2022年1月27日提交的名称为“钙钛矿太阳能电池及其制备方法”的中国专利申请202210100612.2的优先权，该项专利申请的全部内容通过引用并入本文中。
技术领域
本申请涉及钙钛矿太阳能电池技术领域，尤其涉及一种光电转化效率高且稳定性好的钙钛矿太阳能电池及其制备方法。
背景技术
随着新能源领域的快速发展，钙钛矿太阳能电池凭借其高光电转化效率、简单的制作工艺、低的生产成本和材料成本等优势而备受青睐。在钙钛矿太阳能电池中，常常采用含镍材料制备空穴传输层。然而，这样制备的氧化镍空穴传输层和钙钛矿层之间会发生相互作用，劣化钙钛矿太阳能电池的性能。目前，减少或防止氧化镍和钙钛矿之间相互作用的方式大多是在氧化镍的表面覆盖一层钝化材料。然而该方式可能会导致电池制备的时间成本、经济成本和环境成本提高并且不利于钙钛矿太阳能电池中空穴传输层对载流子的提取，因而会影响电池的光电转化效率。
因此，仍需要一种成本更低的、能够进一步提高钙钛矿太阳能电池的性能的解决方案。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种钙钛矿太阳能电池，其具有高的光电转化效率和良好的长期使用稳定性，并且其制备方法成本更低、更有效率。
为了实现上述目的，本申请的第一方面提供了一种钙钛矿太阳能电池，其包括透明导电玻璃、空穴传输层、钙钛矿层、电子传输层和电极，所述空穴传输层包括三价镍和二价镍，其中，所述空穴传输层的朝向钙钛矿层的表面上三价镍与二价镍的摩尔比范围为0至0.20，可选为0至0.10。
空穴传输层中的三价镍和二价镍皆可用于收集和提取来自钙钛矿层的空穴。然而空穴传输层表面的三价镍会导致钙钛矿(例如，结构式为ABX3的钙钛矿)分解，主要体现在会导致钙钛矿的A位与X位被氧化而变成气体，从而造成钙钛矿的深能级缺陷。本申请通过对空穴传输层表面的三价镍进行还原，使其还原为同样能够收集和提取空穴的二价镍，从而减少或甚至消除了三价镍导致的钙钛矿的分解的现象，由此提高了钙钛矿太阳能电池的效率和稳定性。此外，当空穴传输层表的三价镍与二价镍的摩尔比超过0.20时，由于空穴传输层表面三价镍含量较高，对钙钛矿的分解作用较大，不利于钙钛矿太阳能电池的光电转化效率和长期稳定性。
可选地，所述空穴传输层的朝向钙钛矿层的表面上不存在三价镍。
在任意实施方式中，所述空穴传输层为氧化镍空穴传输层。
氧化镍空穴传输层是常用的空穴传输层。氧化镍一般表示为NiOx，其可代表氧化镍、三氧化二镍、氧化亚镍等中的一种或多种。
可选地，所述空穴传输层和钙钛矿层之间不存在任何其它层。
在任意实施方式中，所述空穴传输层掺杂有除氧化镍以外的其他空穴传输材料。所述其他空穴传输材料可为本领域中使用的用于空穴传输层的除氧化镍以外的材料。
在任意实施方式中，所述空穴传输层掺杂有一种或多种选自Li+、Na+、K+、Ru+、Cs+的离子。
在任意实施方式中，所述钙钛矿太阳能电池为反式钙钛矿太阳能电池。
本申请所述的钙钛矿太阳能电池适合采用反式结构。
在任意实施方式中，所述钙钛矿太阳能电池依次包括导电玻璃、空穴传输层、钙钛矿层、电子传输层和金属电极，可选地，所述钙钛矿层和所述电子传输层之间存在钝化层；可选地，所述电子传输层和所述金属电极之间存在缓冲层。
本申请的第二方面提供一种制备钙钛矿太阳能电池的方法，其中包括制备空穴传输层步骤、制备钙钛矿层步骤、任选地制备钝化层步骤、制备电子传输层步骤、任选地制备缓冲层步骤和制金属背电极的步骤，其中，所述空穴传输层和所述钙钛矿层之间不设置其它层，所述制备空穴传输层步骤包括以下操作：
步骤S1：配制空穴传输层材料的溶液，添加在导电玻璃上，然后退火，得到空穴传输层1；其中所述空穴传输层材料包括含镍物质；
步骤S2：采用还原性物质将步骤S1中得到的空穴传输层1表面的三价镍还原，得到最终的空穴传输层。
根据本申请所述的钙钛矿太阳能电池的制备中，通过对包括含镍物质的空穴传输层进行还原步骤，能够使空穴传输层朝向钙钛矿层的表面上的三价镍含量降低，二价镍含量增加，有利于防止因三价镍与钙钛矿反应导致的钙钛矿分解，从而提高太阳能电池的光电转化效率和稳定性。
在任意实施方式中，所述含镍物质选自氧化镍、硝酸镍、醋酸镍、乙酰丙酮镍或其混合物。
所述氧化镍可选为氧化镍纳米颗粒。
所述硝酸镍可选为含水的硝酸镍，例如六水合硝酸镍。
所述醋酸镍可选为含水的醋酸镍，例如四水合醋酸镍。
在任意实施方式中，步骤S1包括以下操作：
将所述含镍物质溶于溶剂中，得到含镍物质的溶液，搅拌，过滤，取上清液，将所述上清液添加在导电玻璃上；可选地所述溶剂为选自甲醇、乙二胺、水中的一种或多种。
在任意实施方式中，步骤S2包括以下操作：
使用超声波在还原性物质的溶液和/或还原性物质的气氛中对所述空穴传输层1进行超声还原。
将所述空穴传输层1置于还原性环境中，例如还原性物质溶液或气氛中，通过使用超声波，可以很容易地将所述空穴传输层表面的三价镍还原为二价镍，而且处理步骤简单高效，节省了经济成本和时间成本。
在任意实施方式中，步骤S2中，在所述超声还原之后所述空穴传输层的朝向钙钛矿层的表面上三价镍与二价镍的摩尔比范围为0至0.2，更可选为0至0.1。
在任意实施方式中，所述还原性物质的溶液中的还原性物质选自：
(1)水合肼、LiAlH4、硼氢化钾、硼氢化钠；
(2)抗坏血酸、甲酸钠、甲酸铵、维生素C；
(3)葡萄糖、麦芽糖、苯甲醛；
(4)Na2S、Na2SO3、NaHSO3；
(5)FeSO4；或
上述物质的混合物，
可选地，所述还原性物质的溶液的浓度为1mg/L至100g/L；可选地，所述超声步骤中，所述还原性物质的溶液的温度为-20℃-100℃，可选为10℃-100℃，更可选为50℃-60℃。
可选地，所述还原性物质的溶液为水溶液。
在任意实施方式中，所述还原性物质的气氛中的还原性物质选自氢气、一氧化碳或其混合物；可选地，所述还原性物质的气氛的温度为-20℃-100℃，可选为10℃-100℃，更可选为50℃-60℃。
可选地，可使用氩气和氢气的混合气，其中氩气和氢气的体积比范围可选为80:20至99:1，更可选为90:10至99:1。
在任意实施方式中，所述超声频率范围为10-100Hz，可选为20-60Hz；可选地，所述超声的超声时间范围为0.1-60min，可选为0.1-30min，更可选为0.1-20min。
根据本申请，与未进行所述超声步骤而制备的钙钛矿太阳能电池相比，进行所述超声步骤而制备的钙钛矿太阳能电池的光电转化效率更高，且稳定性更好。
附图说明
图1为本申请一实施方式中的钙钛矿太阳能电池的结构示意图，从上到下依次为金属电极、缓冲层、电子传输层、钙钛矿层、空穴传输层、掺氟氧化锡(FTO)导电薄膜、玻璃基底，其中太阳光从下面玻璃基底处进入该太阳能电池，其中掺氟氧化锡(FTO)导电薄膜和玻璃基底一起组成导电玻璃。
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申请的钙钛矿太阳能电池及其制备方法的实施方式。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申请而提供的，并不旨在限定权利要求书所记载的主题。
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2-6。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，可选是顺序进行的。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)。
在钙钛矿太阳能电池中，通常使用氧化镍作为空穴传输材料。然而，在采用氧化镍制备空穴传输层的过程中，由于制备工艺的差异，导致在空穴传输层中同时存在二价镍和三价镍。三价镍在空穴传输的过程中有着较好的传输作用，但若三价镍存在于空穴传输层的表面， 会与钙钛矿发生反应，导致钙钛矿分解，不利于载流子的传输且会降低电池的填充，同时会增大电池的电阻，也不利于电池的长期稳定性。目前，解决上述问题的方法主要是在氧化镍表面上制备一层由p型钝化材料组成的钝化层。然而，钝化层的制备需要旋涂、退火或抽真空等多种工艺，增加了电池制备的时间、能耗及经济上方面的成本。并且，目前所用的界面钝化材料合成难度较高，很难在后期应用。此外，钝化层的增加也使得界面数量增多，导致界面处的缺陷增多。
在实践中，本申请发明人出乎意料地发现，当对空穴传输层表面的三价镍进行处理，使空穴传输层表面的三价镍含量降低之后，能够提高钙钛矿太阳能电池的转化效率和长期稳定性。经发明人进一步研究发现，通过对含有三价镍的空穴传输层的表面进行还原，可有效降低空穴传输层表面的三价镍的含量但是不影响空穴传输层内部的三价镍的存在，这样，可以在不使用其他材料覆盖空穴传输层表面的情况下，既保证了空穴传输层的空穴传输作用又防止了空穴传输层表面上的三价镍对钙钛矿的分解作用，从而提高了钙钛矿太阳能电池的光电效率和长期稳定性。发明人还发现，在对含有三价镍的空穴传输层的表面进行还原时，采用超声波进行还原，简单高效且容易处理并且成本低廉。
因此，本申请第一方面提供一种钙钛矿太阳能电池，其包括透明导电玻璃、空穴传输层、钙钛矿层、电子传输层和电极，所述空穴传输层包括三价镍和二价镍，其中，所述空穴传输层的朝向钙钛矿层的表面上三价镍与二价镍的摩尔比范围为0至0.20，更可选为0至0.10，更可选为0至0.05。
空穴传输层用于收集、提取和传输来自钙钛矿层的空穴。本申请所述的空穴传输层含有三价镍和二价镍。空穴传输层材料可采用本领域中可用的含镍物质制备。
空穴传输层中的三价镍和二价镍皆可用于收集和提取来自钙钛矿层的空穴。然而空穴传输层表面的三价镍会导致钙钛矿(例如，结构式为ABX3的钙钛矿)分解，主要体现在会导致钙钛矿的A位与X 位被氧化而变成气体，从而造成钙钛矿的深能级缺陷。本申请通过对空穴传输层表面的三价镍进行还原，使其还原为同样能够收集和提取空穴的二价镍，从而减少或甚至消除了三价镍对钙钛矿的分解现象，由此提高了钙钛矿太阳能电池的效率和稳定性。此外，当空穴传输层表的三价镍与二价镍的摩尔比超过0.20时，由于空穴传输层表面三价镍含量较高，对钙钛矿的分解作用较大，不利于钙钛矿太阳能电池的光电转化效率和长期稳定性。
当将含三价镍的空穴传输层表面进行还原处理后，空穴传输层表面上的三价镍含量减少，二价镍含量相应地增加。二价镍不会导致钙钛矿分解并且同样具有提取和传输空穴的能力，因此，对空穴传输层表面上的三价镍进行还原是有利的选择。
可选地，所述空穴传输层的朝向钙钛矿层的表面上不存在三价镍。
所述空穴传输层表面上三价镍与二价镍的摩尔比可通过X射线光电子能谱分析法(XPS)进行测试。所述测试可在空穴传输层朝向钙钛矿层的表面上进行。可根据测试结果，计算三价镍与二价镍的摩尔比。
在一些实施方式中，所述空穴传输层为氧化镍空穴传输层。
氧化镍空穴传输层是常用的空穴传输层。氧化镍一般表示为NiOx，其可代表氧化镍、三氧化二镍、氧化亚镍等中的一种或多种。
在一些可选的实施方式中，所述空穴传输层中可存在NiO、Ni(OH)2、Ni2O3、NiOOH等物质。
因此，在一些实施方式中，所述空穴传输层的朝向钙钛矿层的表面上不存在界面钝化材料，可选地不存在p型界面钝化材料。换言之，所述空穴传输层和钙钛矿层之间不存在钝化层，即，用于钝化空穴传输层的钝化层。可选地，所述空穴传输层和钙钛矿层之间不存在任何其它层。
即使所述空穴传输层和钙钛矿层之间不存在钝化层，根据本申请，也能够保证钙钛矿太阳能电池的性能和稳定性，并且还节省了材料成本、时间成本和环境成本，具有很好的经济效益。另外，有界面存在 的地方就会有缺陷，本申请中在空穴传输层和钙钛矿层之间不使用钝化层，减少了界面数量，从而减少了因界面存在而导致的缺陷和非辐射符合，提高了钙钛矿太阳能电池的性能。
根据本申请，所述空穴传输层可进行掺杂，例如可为掺杂的氧化镍层。在一些实施方式中，所述空穴传输层掺杂有除氧化镍以外的其他空穴传输材料。所述其他空穴传输材料可为本领域中使用的用于空穴传输层的除氧化镍以外的材料。
在一些可选实施方式中，空穴传输层不仅仅包括氧化镍，还可包括本领域中常规用于空穴传输层的其他材料。本领域中常规用于空穴传输层的其他材料可包括，例如，聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、聚3-己基噻吩(P3HT)、聚[双(4-苯基)(4-丁基苯基)胺](poly-TPD)、硫氰酸亚铜(CuSCN)等。
在一些实施方式中，所述空穴传输层掺杂有一种或多种选自Li+、Na+、K+、Ru+、Cs+的离子。
原则上，本申请中可使用本领域中常用的任何掺杂手段和掺杂物质进行掺杂。可选使用一种或多种选自Li+、Na+、K+、Ru+、Cs+的离子对空穴传输层进行掺杂。
可选地，所述空穴传输层厚度为5-50nm，可选为10-40nm，更可选为20-30nm。
在一些实施方式中，所述钙钛矿太阳能电池为反式钙钛矿太阳能电池。
所述反式钙钛矿太阳能电池的结构中，从入光面依次为导电玻璃、空穴传输层、钙钛矿层、电子传输层、金属背电极。
在一些实施方式中，所述钙钛矿太阳能电池依次包括导电玻璃、空穴传输层、钙钛矿层、电子传输层和金属电极，可选地，所述钙钛矿层和所述电子传输层之间存在钝化层；可选地，所述电子传输层和所述金属电极之间存在缓冲层。
下面详细介绍本申请所述的钙钛矿太阳能电池的除空穴传输层以外的其他结构，但本申请不限于此。
导电玻璃
导电玻璃通常具有一定的透明度。一般采用透明导电玻璃。导电玻璃通常由玻璃基底和氧化物薄膜(简称TCO)导电层组成。玻璃基底和导电层具有为本领域中使用的任何厚度。可选地，导电层厚度在100-1000nm范围内。可选地，玻璃基底的厚度一般在0.1-3cm范围内。常规使用的TCO有氧化铟锡(ITO)和掺氟的氧化锡(FTO)，但本申请不限于此。导电玻璃在使用前需清洗，例如用清洗剂、去离子水和乙醇等超声清洗。
导电玻璃用于将载流子导出。
钙钛矿层
用于所述钙钛矿层的的钙钛矿可具有化学式ABX3，A可为甲胺(简称MA)、甲脒(简称FA)或铯(Cs)，B可为铅(Pb)或锡(Sn)，X可为碘(I)或溴(Br)。
可选地，使用碘化铅甲脒(FAPbI3)体系作为钙钛矿层材料。
钙钛矿层可采用本领域常规技术手段制备，也可以采用以下方法制备(以反式钙钛矿太阳能电池为例)：称取钙钛矿前驱体材料，例如，碘甲脒(FAI)、碘化铅(PbI2)、氯甲胺(MACl)、碘甲胺(MAI)、碘化铯(CsI)等，溶于溶剂(例如，二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)或其混合物等)中，搅拌均匀，过滤，取上清液；将所述上清液覆盖在制备好的空穴传输层上，覆盖方式可采用匀胶机进行旋涂，其中转速可为500-5000rpm/s，旋涂时间可为5-50秒；在覆盖(任选地使用旋涂方式进行覆盖)期间可滴加反溶剂，覆盖(任选地旋涂)完毕后进行退火，退火温度可为80-150℃，退火时间可为0-60min，退火后即得钙钛矿层。所述反溶剂可为，例如，氯苯、乙酸乙酯、甲苯等，但不限于此。
钙钛矿层的厚度可为本领域中使用的任何厚度。可选地，钙钛矿层厚度范围为200-1000nm。
钝化层
可选地，电子传输层和钙钛矿层之间可以存在钝化层，用于钝化电子传输层和钙钛矿层之间界面上的缺陷。
钝化层的厚度可为本领域中使用的任何厚度。可选地，钝化层厚度范围为1-20nm。
电子传输层和缓冲层
电子传输层和缓冲层可采用本领域常规技术手段制备。举例而言，使用富勒烯或其衍生物作为电子传输层时，制备方法如下：将所述富勒烯或富勒烯衍生物溶解在有机溶剂(例如氯苯、二氯苯、甲苯、二甲苯或其混合物)中，配制浓度范围为5-50mg/mL的富勒烯衍生物溶液。然后覆盖在钝化层或钙钛矿层(如果不含钝化层)表面，覆盖方式可采用匀胶机进行旋涂，其中转速可为500-5000rpm/s，旋涂时间可为5-50秒，旋涂后进行退火，退火温度可为80-150℃，退火时间可为0-60min，退火后得到电子传输层。
通常，在电子传输层和金属电极之间使用缓冲层以提高钙钛矿太阳能电池的性能。例如，使用浴铜灵(BCP)制备缓冲层。
电子传输层的厚度可为本领域中使用的任何厚度。可选地，电子传输层厚度范围为10-100nm。
金属背电极
金属背电极可采用金(Au)、银(Ag)、铜(Cu)，但不限于此。可采用蒸镀的方式制备金属背电极。
金属背电极的厚度可为本领域中使用的任何厚度。可选地，金属背电极的厚度范围为10-200nm。
本申请中，金属背电极也称为金属电极或电极。
本申请的第二方面提供一种制备钙钛矿太阳能电池的方法，其中包括制备空穴传输层步骤、制备钙钛矿层步骤、任选地制备钝化层步骤、制备电子传输层步骤、任选地制备缓冲层步骤和制金属背电极的步骤，其中，所述空穴传输层和所述钙钛矿层之间不设置其它层，所述制备空穴传输层步骤包括以下操作：
步骤S1：配制空穴传输层材料的溶液，添加在导电玻璃上，然后退火，得到空穴传输层1；其中所述空穴传输层材料包括含镍物质；
步骤S2：采用还原性物质将步骤S1中得到的空穴传输层1表面的三价镍还原，得到最终的空穴传输层。
原则上，制备空穴传输层步骤、制备钙钛矿层步骤、制备钝化层步骤、制备电子传输层步骤、制备缓冲层步骤和制金属背电极的步骤均可采用本领域中常规的制备方法，其中在制备空穴传输层步骤中，在空穴传输层制备之后增加一个将其表面的三价镍还原为二价镍的操作，例如还原，如超声还原等。
在一些可选实施方式中，制备钙钛矿太阳能电池的方法包括以下步骤：
(1)配制空穴传输层材料的溶液，使其覆盖导电玻璃上，然后退火，得到带空穴传输层1；其中所述空穴传输层材料包括含镍物质；然后进行还原步骤，将前一步骤中得到的空穴传输层1表面的三价镍还原，得到最终的空穴传输层；
(2)配制钙钛矿溶液，过滤，取上清液；任选地，将钝化材料溶于反溶剂中得到钝化材料溶液；
(3)将过滤后的钙钛矿溶液的上清液覆盖(任选地旋涂)在所述空穴传输层上；覆盖(任选地旋涂)过程中，可滴加反溶剂，若使用钝化层，则可将钝化材料溶于反溶剂中；覆盖(任选地旋涂)完毕后退火，得到钙钛矿层和任选地钝化层；
(4)配制好电子传输层材料的溶液和任选地浴铜灵溶液，将所述电子传输层材料溶液覆盖钙钛矿层或任选地钝化层上，然后退火，冷却至室温，得到电子传输层；然后任选地将浴铜灵溶液覆盖所述电子传输层表面，得到缓冲层；
(5)将步骤(4)中获得的物件刮去部分功能层(包括空穴传输层、钙钛矿层、任选地钝化层、电子传输层、任选地缓冲层)，露出导电玻璃层，然后用洗液擦去残留的功能层，之后将该物件放入蒸镀掩膜板中，刮出电极位置，并用洗液擦去残留的功能层，放入蒸镀掩 模板(Mask)中，在真空蒸镀设备中蒸镀可用作电极的金属。蒸镀完毕后得到完整的钙钛矿太阳能电池。
上述钝化材料为本领域中使用的适合置于电子传输层和钙钛矿层之间的用于钝化界面的材料。
本申请中，所述“覆盖”至少包括本领域中使用的“旋涂”、“喷涂”、“溅射”等技术手段。
原则上，所述还原步骤中，没有特殊限制，只要能将空穴传输层表面上的三价镍还原为二价镍并且对钙钛矿太阳能电池性能不产生不利影响即可。
根据本申请所述的钙钛矿太阳能电池的制备中，通过对包括含镍物质的空穴传输层进行还原步骤，能够将空穴传输层朝向钙钛矿层的表面上的三价镍含量降低，二价镍含量增加，有利于防止钙钛矿层的分解以及三价镍与钙钛矿的反应，从而提高太阳能电池的光电转化效率和稳定性。
将三价镍还原为二价镍的反应为氧化还原反应，需要的还原物质的还原性应足以将三价镍还原为二价镍。理论上，凡是能够将三价镍还原成二价镍且对钙钛矿太阳能电池没有任何不利影响的还原性物质均可用于本申请所述的还原步骤。
在一些可选实施方式中，步骤S1中采用溶胶凝胶法制备所述空穴传输层1，包括以下步骤：将所述含镍物质的溶液的上清液滴加在所述导电玻璃上，可选地滴加量为0.01-1mL，然后旋转，转速可选为1000-8000rpm/s，旋转时间可选为10-60s，之后进行退火，可选地，退火程序如下：在80℃下保温1-100min，然后在10-50min内升温至200-500℃，在200-500℃的温度下保持0.1-5h，然后冷却至低于100℃；退火后得到所述空穴传输层1。
在一些可选实施方式中，例如，氧化镍空穴传输层可通过以下方法制备：将硝酸镍、乙酰丙酮镍或醋酸镍溶解在甲醇中，将其旋涂在清洗后的导电玻璃上，转速为500-5000rpm/s，旋涂时间 为5-50秒，旋涂后进行退火，退火温度为80-400℃，退火时间为0-120min。
在一些可选实施方式中，步骤S1中采用喷雾热解法制备所述空穴传输层1，包括以下操作：将所述含镍物质溶于溶剂中，得到含镍物质的溶液，搅拌，过滤，取上清液，做成喷雾，喷在导电玻璃表面，然后进行烧结，可选地，所述烧结的烧结温度范围为100-500℃，可选为300-400℃，烧结时间为10-120min，可选为60-80min；冷却后得到所述空穴传输层1。
在一些可选实施方式中，步骤S1中采用磁控溅射法制备所述空穴传输层1，包括以下操作：将所述含镍物质溶于溶剂中，得到含镍物质的溶液，搅拌，过滤，取上清液，采用磁控溅射将所述上清液溅射在透明导电玻璃表面，可选地，其中采用氧气和氮气，且氧气与氮气的体积比为1:20至1:5，可选为1:12至1:8。
本申请中，所述含镍物质为可用于制备空穴传输层的任何含镍物质。
在一些实施方式中，所述含镍物质选自氧化镍、硝酸镍、醋酸镍、乙酰丙酮镍或其混合物。
所述氧化镍可选为氧化镍纳米颗粒。
所述硝酸镍可选为含水的硝酸镍，例如六水合硝酸镍。
所述醋酸镍可选为含水的醋酸镍，例如四水合醋酸镍。
在一些实施方式中，步骤S1包括以下操作：
将所述含镍物质溶于溶剂中，得到含镍物质的溶液，搅拌，过滤，取上清液，将所述上清液添加在导电玻璃上；可选地所述溶剂为选自甲醇、乙二胺、水中的一种或多种。
在一些实施方式中，步骤S2包括以下操作：
使用超声波在还原性物质的溶液和/或还原性物质的气氛中对所述空穴传输层1进行超声还原。
将所述空穴传输层1置于还原性环境中，例如还原性物质溶液或气氛中，通过使用超声波，可以很容易地将所述空穴传输层表面的三 价镍还原为二价镍，而且处理步骤简单高效，节省了经济成本和时间成本。
使用超声对所述空穴传输层1进行还原的步骤可包括：将带导电玻璃的空穴传输层1浸泡在还原性物质的溶液中或置于还原性物质的气氛中，然后开启超声，保持一段时间，待还原反应完成后停止超声，并将空穴传输层取出并清洗、烘干。如此，空穴传输层表面的三价镍被还原成了二价镍。在制备过程中，可通过控制还原性物质的浓度、空穴传输层在还原性溶液中的浸泡时间或在还原性气氛中的放置时间、超声频率、超声功率、超声时间来控制还原反应的程度，并因此可调控空穴传输层表面上三价镍和二价镍的含量。
此外，在处理过程中，还可以通过补充原料的方式反复利用还原性溶液或还原性气氛，减少废弃物的产生。
另外，所述超声处理还具有安全性高的有益效果。
在一些实施方式中，步骤S2中，在所述超声还原之后所述空穴传输层的朝向钙钛矿层的表面上三价镍与二价镍的摩尔比范围为0至0.2，更可选为0至0.1。
在一些实施方式中，所述还原性物质的溶液中的还原性物质选自：
(1)水合肼、LiAlH4、硼氢化钾、硼氢化钠；
(2)抗坏血酸、甲酸钠、甲酸铵、维生素C；
(3)葡萄糖、麦芽糖、苯甲醛；
(4)Na2S、Na2SO3、NaHSO3；
(5)FeSO4；或
上述物质的混合物，
可选地，所述还原性物质的溶液的浓度为1mg/L至100g/L；可选地，所述超声步骤中，所述还原性物质的溶液的温度为-20℃-100℃，可选为10℃-100℃，更可选为50℃-60℃。
可选地，所述还原性物质的溶液为水溶液。
在一些实施方式中，所述还原性物质的气氛中的还原性物质选自氢气、一氧化碳或其混合物；可选地，所述还原性物质的气氛的温度为-20℃-100℃，可选为10℃-100℃，更可选为50℃-60℃。
可选地，在使用还原性气体时，使用载体进行混合，即使用载体和还原性气体的混合气。所述载体可为氩气、氮气等惰性气体。
可选地，可使用氩气和氢气的混合气，其中氩气作为载气，其中氩气和氢气的体积比范围可选为80:20至99:1，更可选为90:10至99:1。
原则上，本申请对还原性物质的种类、温度、浓度没有特殊限制，只要其能够将空穴传输层表面的三价镍还原成二价镍并且对钙钛矿太阳能电池不会带来较大的不利影响即可。上述还原性物质的种类、温度、浓度是可选的，但是本申请不限于此。
在一些实施方式中，所述超声频率范围为10-100Hz，可选为20-60Hz；可选地，所述超声的超声时间范围为0.1-60min，可选为0.1-30min，更可选为0.1-20min。
原则上，本申请中，对超声频率和超声时间没有特殊限制，只要其能够将空穴传输层表面的三价镍还原成二价镍并且对钙钛矿太阳能电池不会带来较大的不利影响即可。
上述超声频率和超声时间是可选的，本申请不限于此。
本申请针对第一方面的描述、尤其是针对第一方面中空穴传输层的描述，适用于本申请的第二方面。例如，在制备空穴传输层时，在空穴传输层制备后将其还原、可选地超声还原使得所述空穴传输层的朝向钙钛矿层的表面上三价镍与二价镍的摩尔比范围为0至0.2，更可选为0至0.1。还例如，制备空穴传输层时，使用含镍物质制备氧化镍空穴传输层；或者，除了使用含镍物质外，还可以使用其他空穴传输材料，以使得制备后得到的空穴传输层除了氧化镍之外还含有其他空穴传输材料。可选地，使用一种或多种含有Li+、Na+、K+、Ru+、Cs+等离子的空穴传输材料对含镍空穴传输层(氧化镍空穴传输层)进行掺杂。另外，在钙钛矿太阳能电池的制备中，还可能的是，在制备空穴传输层之后，直接制备钙钛矿层，或者在制备钙钛矿层之后， 直接制备空穴传输层，以使得空穴传输层和钙钛矿层之间不存在其他层。可选地，本申请第二方面所述的方法制备的钙钛矿太阳能电池为反式钙钛矿太阳能电池。
根据本申请，与未进行所述超声步骤而制备的钙钛矿太阳能电池相比，进行所述超声步骤而制备的钙钛矿太阳能电池的光电转化效率更高，且稳定性更好。
实施例
下面以反式钙钛矿太阳能电池为例通过实施例对本申请进行详细描述，但本申请不限于此。
I.钙钛矿太阳能电池的制备
实施例1
【导电玻璃】
带有掺氟的氧化锡(FTO)薄膜的导电玻璃，其中导电层厚度为500nm，玻璃厚度为1.5cm，商购获得，清洗干净后直接使用。
【空穴传输层】
将洗净的导电玻璃在紫外臭氧机下照射10min。称取六水合硝酸镍50mg溶于1mL甲醇中。通过磁粒搅拌仪搅拌2h，得到淡绿色的透明澄清液体。过滤，取上清液，将所述上清液旋旋涂导电玻璃上，然后按照以下程序进行退火：在80℃的温度下保持10min，在30min内升温至345℃，然后在345℃下保持30min，然后冷却至100℃后取出，得到空穴传输层1，厚度为30nm；
还原步骤：
还原性物质溶液配制：配制浓度为5g/L的维生素C的水溶液，搅拌至完全溶解(溶液中无可见不溶物)。
还原反应：将前一步骤得到空穴传输层1浸泡在配制好的维生素C溶液中，在25℃(此即为还原反应的温度)下，在60Hz下超声10min(此即为还原反应的时间)后取出，然后用水冲去表面的维生 素C，用气枪吹去表面的水分，真空烘干，得到最终的空穴传输层，厚度基本没有改变，为30nm。
【钙钛矿层和钝化层】
配制钙钛矿溶液：将80mg碘甲脒(FAI)、223mg碘化铅(PbI2)、15mg氯甲胺(MACl)溶于1mL溶剂中，所述溶剂为N,N-二甲基甲酰胺(DMF)与二甲基亚砜(DMSO)的混合溶剂，其中DMF与DMSO体积比为4:1(DMF：DMSO)，将所述钙钛矿溶液在室温下使用磁力搅拌仪搅拌1h，过滤，取上清液待用。
碘甲脒(FAI)、碘化铅(PbI2)、氯甲胺(MACl)购自西安宝莱特光电材料股份有限公司，DMF和DMSO购自Sigma公司。
配制钝化层溶液：将5mg苯乙胺氢碘酸盐(钝化材料)溶于1ml氯苯(反溶剂)中，得到苯乙胺氢碘酸盐的氯苯溶液。
将前一步骤中得到的空穴传输层在UV下照射15min，然后在空穴传输层上滴加60μL钙钛矿溶液的上清液，采用匀胶机旋30s后，在第15s时滴加600μL配制好的苯乙胺氢碘酸盐的氯苯溶液，在150℃下退火1h，得到厚度为480nm的钙钛矿层和厚度为10nm的钝化层。
【电子传输层和缓冲层】
配制[6,6]-苯基-C61-丁酸甲酯(PCBM，可商购)溶液：浓度为20mg/ml，溶剂为氯苯；
配制浴铜灵(BCP，可商购)溶液：浓度为0.5mg/mL，溶剂为异丙醇；
采用雷博匀胶机，将配制好的60μL的PCBM溶液旋涂制备好钙钛矿层的导电玻璃上，旋涂时间为30s。然后在100℃下退火10min，之后从仪器上取下冷却至室温，得到电子传输层；再将60μL的BCP溶液旋涂在电子传输层表面，旋涂时间为30s。旋涂完毕，得到厚度为70nm的电子传输层和厚度为5nm的缓冲层。
【金属背电极】
将前一步骤中制备的依次带有导电玻璃、空穴传输层、钙钛矿层、钝化层、电子传输层、缓冲层的物件用刀片根据掩膜板(Mask)图 案刮去部分功能层(包括空穴传输层、钙钛矿层、钝化层、电子传输层、缓冲层)，露出导电玻璃层，然后用洗液擦去残留的功能层，之后将该物件放入蒸镀掩膜板中，刮出电极位置，并用洗液擦去残留的功能层，放入蒸镀掩模板(Mask)中，在真空蒸镀设备中蒸镀80nm的银，蒸镀速率为0.1A/s。蒸镀完毕后得到完整的钙钛矿太阳能电池。
实施例2和3
实施例2和3的钙钛矿太阳能电池类似于实施例1进行，不同之处在于空穴传输层制备中还原反应的温度分别为50℃、75℃。
实施例4-6
实施例4-6的钙钛矿太阳能电池类似于实施例1进行，不同之处在于空穴传输层制备中还原性物质均为亚硫酸钠，且实施例4中还原性物质的浓度为5g/L，还原反应的时间为10min；实施例5中还原性物质的浓度为10g/L，还原反应的时间为15min；实施例6中还原性物质的浓度为10g/L，还原反应的时间为20min。
实施例7-9
实施例7-9的钙钛矿太阳能电池类似于实施例1进行，不同之处在于空穴传输层制备中还原性物质均为氩气(作为载气)和氢气的混合气(下文简称“氩氢混合气”)，且实施例7中氩氢混合气中氩气与氢气的体积比为99:1，还原反应时间为5min；实施例8中氩氢混合气中氩气与氢气的体积比为95:5，还原反应时间为10min；实施例9中氩氢混合气中氩气与氢气的体积比为90:10，还原反应时间为1min。
实施例10
实施例10的钙钛矿太阳能电池类似于实施例1进行，不同之处在于不使用超声，只在维生素C溶液中浸泡10min。
实施例11
实施例11的钙钛矿太阳能电池类似于实施例10进行，不同之处在于在维生素C溶液中浸泡1小时。
对比例1
对比例1的钙钛矿太阳能电池类似于实施例1进行，不同之处在于空穴传输层的制备中，不进行还原反应，而是将所述带导电玻璃的氧化镍层放置在纯水中，在25℃下超声10分钟。
对比例2
对比例2的钙钛矿太阳能电池类似于实施例1进行，不同之处在于在空穴传输层的制备中，既不进行还原反应也不进行超声，即，将所述带导电玻璃的氧化镍层直接用于钙钛矿层的制备。
对比例3
对比例1的钙钛矿太阳能电池类似于实施例1进行，不同之处在于在空穴传输层的制备中，在所述空穴传输层和所述钙钛矿层之间添加一层常用的钝化层，该钝化层使用聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)，厚度为2nm。
II.钙钛矿太阳能电池性能测定
1.空穴传输层表面上三价镍和二价镍摩尔比(Ni3+/Ni2+)的测试
通过XPS对上述各实施例和对比例中制备的空穴传输层表面的三价镍和二价镍摩尔比(Ni3+/Ni2+)进行测定。
2.光电转化效率测定
根据国家标准IEC61215进行测试，其中测试是在光照的情况下，使用数字源表进行的，光源通过太阳光模拟器提供，光源发出的光符合AM 1.5G标准太阳光谱。
3.稳定性测定
分别在第3天和第30天对各实施例和对比例中制备的钙钛矿太阳能电池进行光电转化效率测定。
各实施例和对比例中使用的还原剂、还原反应条件以及所得钙钛矿太阳能电池的性能测试结果参见表1。
与对比例1-3相比，实施例1-11中制备的钙钛矿太阳能电池均具有良好的30天稳定性。可见，对空穴传输层表面进行还原，无论是采用哪种方式，都能够提高钙钛矿太阳能电池的稳定性。
通过将实施例1-9和10-11进行比较可知，超声有助于提高钙钛矿太阳能电池的光电转化效率和稳定性。
通过比较实施例1-3可知，对于相同的还原剂维生素C，在相同的浓度下，在25℃、50℃、75℃的还原反应温度(即，还原剂溶液的温度)下，所得到的钙钛矿太阳能电池光电转化效率都很高且稳定性优异。
通过比较实施例4-6可知，对于相同的还原剂亚硫酸钠，将其浓度由5g/L增加至10g/L并且将超声时间由10分钟增加至15分钟、20分钟，所得到的钙钛矿电池光电转化效率有所升高。
通过比较实施例7-9可知，对于气态还原剂(氩氢混合气)，提高氢气的占比会使所得到的钙钛矿电池光电转化效率有所升高。
通过比较对氧化镍空穴传输层进行还原处理的实施例1-11和采用现有技术中的常规方式钝化的对比例3可知，经过对氧化镍空穴传输层进行还原处理而制备的钙钛矿太阳能电池与常规太阳能电池相比，显著提高了光电转化效率，并且方法简单高效，节省了时间成本和材料成本，具有很好的经济价值。
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 (15)

  1. 一种钙钛矿太阳能电池，其包括透明导电玻璃、空穴传输层、钙钛矿层、电子传输层和电极，所述空穴传输层包括三价镍和二价镍，其中，所述空穴传输层的朝向钙钛矿层的表面上三价镍与二价镍的摩尔比范围为0至0.2，更可选为0至0.1。
  2. 根据权利要求1所述的钙钛矿太阳能电池，其中，所述空穴传输层为氧化镍空穴传输层。
  3. 根据权利要求1或2所述的钙钛矿太阳能电池，其中，所述空穴传输层和钙钛矿层之间不存在其他层。
  4. 根据权利要求1-3中任一项所述的钙钛矿太阳能电池，其中，所述空穴传输层掺杂有除氧化镍以外的其他空穴传输材料。
  5. 根据权利要求1-4中任一项所述的钙钛矿太阳能电池，其中，所述空穴传输层掺杂有一种或多种选自Li+、Na+、K+、Ru+、Cs+的离子。
  6. 根据权利要求1-5中任一项所述的钙钛矿太阳能电池，其中，所述钙钛矿太阳能电池为反式钙钛矿太阳能电池。
  7. 根据权利要求1-6中任一项所述的钙钛矿太阳能电池，其中，所述钙钛矿太阳能电池依次包括导电玻璃、空穴传输层、钙钛矿层、电子传输层和金属电极，可选地，所述钙钛矿层和所述电子传输层之间存在钝化层；可选地，所述电子传输层和所述金属电极之间存在缓冲层。
  8. 制备钙钛矿太阳能电池的方法，其中包括制备空穴传输层步骤、制备钙钛矿层步骤、任选地制备钝化层步骤、制备电子传输层步骤、任选地制备缓冲层步骤和制金属背电极的步骤，其中，所述空穴传输层和所述钙钛矿层之间不设置其它层，所述制备空穴传输层步骤包括以下操作：
    步骤S1：配制空穴传输层材料的溶液，添加在导电玻璃上，然后退火，得到空穴传输层1；其中所述空穴传输层材料包括含镍物质；
    步骤S2：采用还原性物质将步骤S1中得到的空穴传输层1表面的三价镍还原，得到最终的空穴传输层。
  9. 根据权利要求8所述的制备钙钛矿太阳能电池的方法，其中，所述含镍物质选自氧化镍、硝酸镍、醋酸镍、乙酰丙酮镍或其混合物。
  10. 根据权利要求8或9所述的制备钙钛矿太阳能电池的方法，其中，步骤S1包括以下操作：
    将所述含镍物质溶于溶剂中，得到含镍物质的溶液，搅拌，过滤，取上清液，将所述上清液添加在导电玻璃上；可选地所述溶剂为选自甲醇、乙二胺、水中的一种或多种。
  11. 根据权利要求8-10中任一项所述的制备钙钛矿太阳能电池的方法，其中，步骤S2包括以下操作：
    使用超声波在还原性物质的溶液和/或还原性物质的气氛中对所述空穴传输层1进行超声还原。
  12. 根据权利要求8-11中任一项所述的制备钙钛矿太阳能电池的方法，其中，步骤S2中，在所述超声还原之后所述空穴传输层的朝向钙钛矿层的表面上三价镍与二价镍的摩尔比范围为0至0.2，更可选为0至0.1。
  13. 根据权利要求8-12中任一项所述的制备钙钛矿太阳能电池的方法，其中，所述还原性物质的溶液中的还原性物质选自：
    (1)水合肼、LiAlH4、硼氢化钾、硼氢化钠；
    (2)抗坏血酸、甲酸钠、甲酸铵、维生素C；
    (3)葡萄糖、麦芽糖、苯甲醛；
    (4)Na2S、Na2SO3、NaHSO3；
    (5)FeSO4；或
    上述物质的混合物，
    可选地，所述还原性物质的溶液的浓度为1mg/L至100g/L；可选地，所述超声步骤中，所述还原性物质的溶液的温度为-20℃-100℃，可选为10℃-100℃，更可选为50℃-60℃。
  14. 根据权利要求8-13中任一项所述的制备钙钛矿太阳能电池的方法，其中，所述还原性物质的气氛中的还原性物质选自氢气、一氧化碳 或其混合物；可选地，所述还原性物质的气氛的温度为-20℃-100℃，可选为10℃-100℃，更可选为50℃-60℃。
  15. 根据权利要求8-14中任一项所述的制备钙钛矿太阳能电池的方法，其中，所述超声频率范围为10-100Hz，可选为20-60Hz；可选地，所述超声的超声时间范围为0.1-60min，可选为0.1-30min，更可选为0.1-20min。
PCT/CN2023/072276 2022-01-27 2023-01-16 钙钛矿太阳能电池及其制备方法 WO2023143157A1 (zh)

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