WO2023051494A1 - 一种大面积钙钛矿层及其制备方法 - Google Patents

一种大面积钙钛矿层及其制备方法 Download PDF

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WO2023051494A1
WO2023051494A1 PCT/CN2022/121561 CN2022121561W WO2023051494A1 WO 2023051494 A1 WO2023051494 A1 WO 2023051494A1 CN 2022121561 W CN2022121561 W CN 2022121561W WO 2023051494 A1 WO2023051494 A1 WO 2023051494A1
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perovskite
preparation
optionally
perovskite layer
area
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PCT/CN2022/121561
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English (en)
French (fr)
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夏锐
陈艺琦
王尧
邹杨
刘成法
张学玲
陈达明
陈奕峰
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天合光能股份有限公司
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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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • 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
    • 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 application belongs to the technical field of solar cells, and in particular relates to a large-area perovskite layer and a preparation method thereof.
  • the energy conversion efficiency of a solar cell device is one of the key performances of the device.
  • the crystalline silicon solar cells currently occupying the absolute majority of the photovoltaic market have a material absorption band gap of 1.12eV, which cannot make reasonable use of short-wavelength light in the solar spectrum.
  • perovskite materials which have received continuous attention in the field of photovoltaics, can not only achieve controllable adjustment of their bandgap in the range of 1.5 to 2.3eV by changing the composition of perovskite materials. At the same time, perovskite materials are cheap and easy to prepare.
  • the crystalline silicon cell is used as the substrate and the wide-bandgap perovskite top cell is deposited to form a tandem solar cell, the spectral response can be broadened to a greater extent with a slight increase in cost, thereby greatly improving the efficiency of the device.
  • the theoretical efficiency of the two-terminal laminated solar cell of the crystalline silicon bottom cell-perovskite top cell can reach 44%, which is the next generation of new photovoltaic cell technology that is very expected to disrupt the market.
  • perovskite materials are very sensitive to factors such as water and oxygen in the air, so currently high-efficiency perovskite solar cells are mainly prepared in glove boxes.
  • the preparation of the perovskite precursor solution still needs to be in contact with water and oxygen in the air.
  • some solvents that are easily miscible with water are easy to absorb water and are not easy to be removed after entering the precursor solution; on the other hand
  • the components in the precursor are easily oxidized, resulting in insufficient reaction of each component, forming defects, and affecting device performance.
  • the perovskite laminated battery is to be commercialized, it needs to meet the preparation of the device in the air and be able to adapt to changes in different humidity.
  • CN109065725A discloses a method for preparing a highly efficient and stable perovskite solar cell by adding a surfactant to the perovskite layer.
  • the perovskite solar cell consists of a conductive glass substrate, an electron transport layer, a perovskite layer, a hole transport layer and a metal
  • the electrodes are stacked in sequence.
  • the invention prepares a perovskite layer by adding a cationic surfactant to the perovskite precursor solution and adjusting the content of the cationic surfactant, which reduces the surface defects of the film and regulates the perovskite active layer.
  • the film morphology and crystallinity of the perovskite solar cell are improved, and the photoelectric conversion efficiency and battery stability of the perovskite solar cell are improved, which provides a new preparation method for the preparation of a high-efficiency and stable perovskite solar cell.
  • the invention has simple process and low cost, helps to improve the photoelectric performance and stability of the perovskite solar cell, and has good commercial application prospects.
  • CN110718632A discloses a method for preparing a large-area perovskite layer and a perovskite solar cell, the method comprising the following steps: coating a perovskite precursor solution on a substrate to form a perovskite precursor layer; adding a mixed anti-solvent, The perovskite layer is obtained by annealing; the mixed anti-solvent is a mixed solvent formed by mixing A solvent and B solvent, and the A solvent is selected from any one of toluene, chlorobenzene, methylene chloride, ethyl acetate, anisole, and ether , B solvent is selected from any one of toluene, chlorobenzene, methylene chloride, ethyl acetate, anisole, monohydric alcohols with 3-6 carbon atoms, A solvent is different from B solvent, and A solvent accounts for the mixed anti-solvent The volume ratio is 10-90%.
  • the invention uses a mixed anti-solvent to reduce the supersaturation in the crystallization process of the perovskite precursor liquid, so that the crystallization nucleation sites are uniformly generated, and finally a perovskite film with uniform film formation and large grain size is obtained.
  • the field of titanium ore devices has a good application prospect.
  • the existing perovskite layer has the problems of high preparation process requirements, poor uniformity and large-area preparation. Therefore, how to meet the requirements of low preparation process requirements and large-area preparation under the condition of ensuring good uniformity of the perovskite layer, become an urgent problem to be solved.
  • the purpose of this application is to provide a large-area perovskite layer and its preparation method, by dissolving the raw material of the perovskite in an ionic liquid, or a mixture of an ionic liquid and an organic solvent, to form calcium
  • the titanium precursor reduces the influence of water and oxygen in the air on the perovskite precursor, so that the perovskite layer can be prepared in an air atmosphere, and further combined with the coating method, a large-area perovskite layer can be prepared , suitable for industrial production.
  • the present application provides a method for preparing a large-area perovskite layer, the preparation method comprising:
  • the perovskite raw material is dissolved in an ionic liquid, or a mixture of an ionic liquid and an organic solvent, and the influence of water and oxygen in the air is reduced during the preparation of the perovskite layer from the precursor.
  • the perovskite layer prepared by the application has a uniform shape, and has the advantages of simple preparation method, suitable for industrial production and low cost Features.
  • the preparation process of the large-area perovskite layer is carried out under an air atmosphere.
  • the raw materials of the perovskite include metal halides and additives.
  • the molar ratio of the metal halide to the additive is (0.5-1.5):1, such as 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1 :1, 1.2:1, 1.3:1, 1.4:1, or 1.5:1.
  • the metal halide includes one or a combination of at least two of SnI 2 , SnBr 2 , SnF 2 , SnCl 2 , PbI 2 , PbBr 2 or PbCl 2 .
  • the additives include CH 3 NH 3 I, CH 3 NH 3 Cl, CH 3 NH 3 Br, CH 2 (NH 2 ) 2 I, CH 2 (NH 2 ) 2 Br, CH 2 (NH 2 ) 2 One or a combination of at least two of Cl, CsI, RbI, KI, CsBr or CsCl.
  • the molar concentration of the perovskite raw material in the perovskite precursor is 0.1-5 mol/L, such as 0.1 mol/L, 0.5 mol/L, 1.0 mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4.0mol/L, 4.5mol/L or 5.0mol/L.
  • the volume ratio of the organic solvent to the ionic liquid is (0-1000):1, such as 10:1, 50:1, 100:1, 200:1, 300:1, 400:1, 500 :1, 600:1, 700:1, 800:1, 900:1 or 1000:1, further optional (0 to 100):1.
  • the ionic liquid includes 1,1,1-trifluoroethylammonium iodide, methylamine formate, methylammonium acetate, methylammonium difluoroacetate or 1-butyl-3- One or a combination of at least two of methylimidazole tetrafluoroborate.
  • the organic solvent includes one or a combination of at least two of N,N-dimethylformamide, dimethyl sulfoxide, tetramethylene sulfoxide, sulfolane or N-methylpyrrolidone.
  • the coating step includes: first coating the perovskite precursor on the surface of the substrate, and then performing spin coating to process the remaining solvent in the film.
  • the substrate includes one or at least two of a glass substrate deposited with ITO, a glass substrate deposited with FTO, a flexible polyimide substrate, a flexible substrate of ethylene naphthalate or a crystalline silicon substrate The combination.
  • the crystalline silicon substrate includes one of a single crystal silicon wafer, a doped single crystal silicon wafer, a polycrystalline silicon wafer, a doped polycrystalline silicon wafer, an amorphous silicon wafer or a doped amorphous silicon wafer. one or a combination of at least two.
  • the coating speed is 0.01-1m/s, such as 0.01m/s, 0.05m/s, 0.1m/s, 0.2m/s, 0.3m/s, 0.4m/s, 0.5m/s, 0.6m/s, 0.7m/s, 0.8m/s, 0.9m/s or 1.0m/s.
  • the rotation speed of the spin coating is 100-6000 rpm, such as 100 rpm, 600 rpm, 1200 rpm, 1800 rpm, 2400 rpm, 3000 rpm, 3600 rpm, 4200 rpm, 4800 rpm, 5400 rpm or 6000 rpm.
  • the spin coating time is 10-1000s, for example, 10s, 50s, 100s, 200s, 300s, 400s, 500s, 600s, 700s, 800s, 900s or 1000s.
  • the spin coating process uses a spin coater.
  • heat treatment is performed after the coating.
  • the temperature of the heat treatment is 70-150°C, such as 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C.
  • the heat treatment time is 1 to 120 min, such as 1 min, 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min, further optionally 10 min ⁇ 60min.
  • the preparation method specifically includes the following steps:
  • the metal halide and the additive are mixed according to the molar ratio of (0.5-1.5): 1, and dissolved in the mixture of the ionic liquid and the organic solvent, and the volume ratio of the organic solvent to the ionic liquid is 0-1. 1000:1, forming a perovskite precursor, the molar concentration of the perovskite raw material in the perovskite precursor is 0.1-5mol/L;
  • the perovskite precursor After the perovskite precursor is coated on the surface of the substrate at a speed of 0.01-1m/s, it is spin-coated at 100-6000rpm for 10-1000s, and then heated at 70-150°C for 1-120min to prepare perovskite layer.
  • the present application provides a large-area perovskite layer, the large-area perovskite layer has a uniform appearance, and the large-area perovskite layer is prepared by the method for preparing the large-area perovskite layer described in the first aspect get.
  • the bandgap of the large-area perovskite layer is 1.3-1.8eV, such as 1.30eV, 1.35eV, 1.40eV, 1.45eV, 1.50eV, 1.53eV, 1.56eV, 1.59eV eV, 1.62eV, 1.65eV, 1.68eV, 1.71eV, 1.74eV, 1.77eV, or 1.80eV.
  • the area of the large-area perovskite layer is 5-1000cm 2 , for example, 5cm 2 , 10cm 2 , 50cm 2 , 100cm 2 , 200cm 2 , 300cm 2 , 400cm 2 , 500cm 2 , 600cm 2 , 700cm 2 , 800cm 2 , 900cm 2 or 1000cm 2 .
  • the perovskite raw material is dissolved in an ionic liquid, or a mixture of an ionic liquid and an organic solvent, and the influence of water and oxygen in the air is reduced during the preparation of the perovskite layer from the precursor. Further, combined with the coating operation , realize the more efficient large-area preparation of the perovskite layer in the air, thereby improving the production efficiency of the perovskite-based battery, and the perovskite layer prepared by the application has a uniform shape, and has the advantages of simple preparation method, suitable for industrial production and low cost Features.
  • Fig. 1 is the schematic flow chart of the preparation method of the large-area perovskite layer provided in the embodiment 1-4 of the present application;
  • Fig. 2 is the edge topography figure of the large-area perovskite layer provided in embodiment 1 of the present application;
  • Fig. 3 is the central topography diagram of the large-area perovskite layer provided in Example 1 of the present application;
  • Fig. 4 is the edge section topography figure of the large-area perovskite layer provided in embodiment 1 of the present application;
  • FIG. 5 is a central cross-sectional topography diagram of the large-area perovskite layer provided in Example 1 of the present application.
  • This embodiment provides a method for preparing a large-area perovskite layer, as shown in Figure 1, specifically comprising the following steps:
  • This embodiment provides a method for preparing a large-area perovskite layer, as shown in Figure 1, specifically comprising the following steps:
  • This embodiment provides a method for preparing a large-area perovskite layer, as shown in Figure 1, specifically comprising the following steps:
  • This embodiment provides a method for preparing a large-area perovskite layer, as shown in Figure 1, specifically comprising the following steps:
  • the surface and cross-section of the large-area perovskite layer prepared in Example 1 were characterized by SEM.
  • the topography of the edge of the silicon wafer is shown in Figure 2
  • the topography of the middle is shown in Figure 3
  • the topography of the edge cross-section is shown in Figure 4
  • the topography of the central section is shown in Figure 5.
  • this application reduces the influence of water and oxygen in the air during the preparation of the perovskite layer from the precursor solution by dissolving the perovskite raw material in the ionic liquid. Further, combined with coating operation to achieve more efficient large-area preparation of the perovskite layer in the air, thereby improving the production efficiency of crystalline silicon/perovskite laminated cells, and the perovskite layer prepared by this application has a uniform appearance and can be prepared on a large scale with an area of 5
  • the perovskite layer of ⁇ 1000cm 2 has the characteristics of simple preparation method, suitable for industrial production and low cost.

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Abstract

本申请提供了一种大面积钙钛矿层及其制备方法，所述制备方法包括：将组成钙钛矿的原料溶于离子液体，或离子液体与有机溶剂的混合物中，形成钙钛矿前驱体，将钙钛矿前驱体涂布于晶体硅底电池的表面，制备得到钙钛矿层。本申请通过将钙钛矿的原料溶于离子液体，或离子液体和有机溶剂的混合物中，形成钙钛矿前驱体，减少了空气中的水氧对从钙钛矿前驱体的影响，从而能够在空气气氛下进行钙钛矿层的制备，进一步地结合涂布的方式，能够制备大面积钙钛矿层，适合工业化生产。

Description

一种大面积钙钛矿层及其制备方法 技术领域
本申请属于太阳能电池技术领域，尤其涉及一种大面积钙钛矿层及其制备方法。
背景技术
太阳能电池器件的能量转换效率是器件的关键性能之一。目前占据光伏市场绝对主体的晶体硅太阳电池，其材料吸收带隙为1.12eV，不能合理利用太阳光谱中短波长的光。而近年来获得光伏领域持续关注的钙钛矿材料，不仅可以通过改变钙钛矿材料的组分，实现其带隙在1.5至2.3eV范围内的可控调节。同时钙钛矿材料成本低廉，制备简便。若以晶体硅电池为基底，沉积宽带隙钙钛矿顶电池构成叠层太阳电池，就能在成本增加甚微的前提下，更大限度的拓宽光谱响应，进而极大的提高器件的效率。晶体硅底电池-钙钛矿顶电池的两端叠层太阳电池的理论效率可达44％，是非常有望颠覆市场的下一代新型光伏电池技术。
然而，钙钛矿材料对空气中的水氧等因素十分敏感，因此目前高效钙钛矿太阳电池主要在手套箱内制备完成。目前现有常规技术方案中，钙钛矿前驱体溶液制备仍需接触空气中的水氧，一方面，一些易与水互溶的溶剂，容易吸收水份，进入前驱体溶液后不易被去除；另一方面，前驱体中的组分容易被氧化，造成各组分反应不充分，形成缺陷，影响器件性能。而钙钛矿叠层电池要想走向商业化，需满足器件在空气中的制备，并能适应不同湿度的变化。
CN109065725A公开了一种在钙钛矿层加入表面活性剂制备高效稳定的钙钛矿太阳能电池的方法，钙钛矿太阳能电池由导电玻璃衬底、电子传输层、钙 钛矿层、空穴传输层和金属电极依次堆叠组成，该发明通过在钙钛矿前驱体溶液中加入阳离子表面活性剂并调控阳离子表面活性剂的含量，制备成钙钛矿层，降低了薄膜的表面缺陷，调控了钙钛矿活性层的薄膜形貌和结晶性，同时提高了钙钛矿太阳能电池的光电转换效率及其电池稳定性，为制备高效稳定的钙钛矿太阳能电池提供了新的制备途径。该发明工艺简单，成本低廉，有助于提高钙钛矿太阳能电池的光电性能及其稳定性，具有良好的商业应用前景。
CN110718632A公开了一种制备大面积钙钛矿层的方法和钙钛矿太阳能电池，该方法包括以下步骤：在基体上涂覆钙钛矿前驱体溶液形成钙钛矿前驱体层；加入混合反溶剂，退火处理制得钙钛矿层；混合反溶剂为A溶剂和B溶剂混合形成的混合溶剂，A溶剂选自甲苯、氯苯、二氯甲烷、乙酸乙酯、苯甲醚、乙醚中的任一种，B溶剂选自甲苯、氯苯、二氯甲烷、乙酸乙酯、苯甲醚、3-6个碳原子的一元醇中的任一种，A溶剂与B溶剂不同，A溶剂占混合反溶剂的体积比为10～90％。该发明利用混合反溶剂减少了钙钛矿前驱液结晶过程的过饱和度，使得结晶成核位点均匀生成，最终得到成膜均一、晶粒尺寸大的钙钛矿薄膜，在制备大面积钙钛矿器件领域具有良好的应用前景。
现有钙钛矿层存在制备工艺要求高、均匀性差和不能大面积制备的问题，因此如何在保证钙钛矿层具有均匀性好的情况下，还能够达到制备工艺要求低和大面积制备的要求，成为目前迫切需要解决的问题。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
针对现有技术存在的不足，本申请的目的在于提供一种大面积钙钛矿层及其制备方法，通过将钙钛矿的原料溶于离子液体，或离子液体和有机溶剂的混 合物中，形成钙钛矿前驱体，减少了空气中的水氧对从钙钛矿前驱体的影响，从而能够在空气气氛下进行钙钛矿层的制备，进一步地结合涂布的方式，能够制备大面积钙钛矿层，适合工业化生产。
为达此目的，本申请采用以下技术方案：
第一方面，本申请提供了一种大面积钙钛矿层的制备方法，所述制备方法包括：
将组成钙钛矿的原料溶于离子液体，或离子液体与有机溶剂的混合物中，形成钙钛矿前驱体，将钙钛矿前驱体涂布于晶体硅底电池的表面，制备得到钙钛矿层。本申请通过将钙钛矿原料溶于离子液体，或离子液体和有机溶剂的混合物中，在前驱体制备钙钛矿层过程中，减少了空气中的水氧的影响，进一步地，结合涂布操作，实现钙钛矿层在空气中更加高效的大面积制备，从而提升钙钛矿基电池的生产效率，而且本申请制备得到的钙钛矿层形貌均匀，具有制备方法简单、适合工业化生产和成本低等特点。
作为本申请的一个可选技术方案，所述大面积钙钛矿层的制备过程在空气气氛下进行。
作为本申请的一个可选技术方案，所述钙钛矿的原料包括金属卤化物和添加剂。
可选地，所述金属卤化物和添加剂的摩尔比为(0.5～1.5):1，例如为0.5:1、0.6:1、0.7:1、0.8:1、0.9:1、1.0:1、1.1:1、1.2:1、1.3:1、1.4:1或1.5:1。
可选地，所述金属卤化物包括SnI 2、SnBr 2、SnF 2、SnCl 2、PbI 2、PbBr 2或PbCl 2中的一种或至少两种的组合。
可选地，所述添加剂包括CH 3NH 3I、CH 3NH 3Cl、CH 3NH 3Br、CH 2(NH 2) 2I、CH 2(NH 2) 2Br、CH 2(NH 2) 2Cl、CsI、RbI、KI、CsBr或CsCl中的一种或至少两种 的组合。
作为本申请的一个可选技术方案，所述钙钛矿前驱体中钙钛矿的原料的摩尔浓度为0.1～5mol/L，例如为0.1mol/L、0.5mol/L、1.0mol/L、1.5mol/L、2.0mol/L、2.5mol/L、3.0mol/L、3.5mol/L、4.0mol/L、4.5mol/L或5.0mol/L。
可选地，所述有机溶剂与离子液体的体积比为(0～1000):1，例如为10:1、50:1、100:1、200:1、300:1、400:1、500:1、600:1、700:1、800:1、900:1或1000:1，进一步可选为(0～100):1。
作为本申请的一个可选技术方案，所述离子液体包括1,1,1-三氟乙基碘化铵、甲酸甲胺、醋酸甲铵、二氟乙酸甲铵或1-丁基-3-甲基咪唑四氟硼酸盐中的一种或至少两种的组合。
可选地，所述有机溶剂包括N,N-二甲基甲酰胺、二甲基亚砜、四亚甲基亚砜、环丁砜或N-甲基吡咯烷酮中的一种或至少两种的组合。
作为本申请的一个可选技术方案，所述涂布的步骤包括：先将钙钛矿前驱体涂布于基底表面，再进行旋涂处理薄膜中剩余的溶剂。
可选地，所述基底包括沉积有ITO的玻璃基底、沉积有FTO的玻璃基底、聚酰亚胺柔性基底、萘二乙酸乙二醇酯柔性基底或晶体硅基底中的一种或至少两种的组合。
可选地，所述晶体硅基底包括单晶硅硅片、掺杂单晶硅硅片、多晶硅硅片、掺杂多晶硅硅片、非晶硅硅片或掺杂非晶硅硅片中的一种或至少两种的组合。
作为本申请的一个可选技术方案，所述涂布的速度为0.01～1m/s，例如为0.01m/s、0.05m/s、0.1m/s、0.2m/s、0.3m/s、0.4m/s、0.5m/s、0.6m/s、0.7m/s、0.8m/s、0.9m/s或1.0m/s。
可选地，所述旋涂的旋转速度为100～6000rpm，例如为100rpm、600rpm、 1200rpm、1800rpm、2400rpm、3000rpm、3600rpm、4200rpm、4800rpm、5400rpm或6000rpm。
可选地，所述旋涂的时间为10～1000s，例如为10s、50s、100s、200s、300s、400s、500s、600s、700s、800s、900s或1000s。
可选地，所述旋涂的过程采用旋涂仪。
作为本申请的一个可选技术方案，所述涂布后进行加热处理。
可选地，所述加热处理的温度为70～150℃，例如为70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃或150℃。
可选地，所述加热处理的时间为1～120min，例如为1min、5min、10min、20min、30min、40min、50min、60min、70min、80min、90min、100min、110min或120min，进一步可选为10～60min。
作为本申请的一个可选技术方案，所述制备方法具体包括以下步骤：
(Ⅰ)在空气气氛下，将金属卤化物和添加剂按照摩尔比为(0.5～1.5):1混合，并溶于离子液体和有机溶剂的混合物中，有机溶剂与离子液体的体积比为0～1000:1，形成钙钛矿前驱体，钙钛矿前驱体中钙钛矿的原料的摩尔浓度为0.1～5mol/L；
(Ⅱ)将钙钛矿前驱体以0.01～1m/s的速度涂布于基底的表面后，在100～6000rpm下旋涂10～1000s，再在70～150℃下加热1～120min，制备得到钙钛矿层。
第二方面，本申请提供了一种大面积钙钛矿层，所述大面积钙钛矿层的形貌均匀，所述大面积钙钛矿层由第一方面所述大面积钙钛矿层的制备方法制备得到。
作为本申请的一个可选技术方案，所述大面积钙钛矿层的带隙为1.3～1.8eV， 例如为1.30eV、1.35eV、1.40eV、1.45eV、1.50eV、1.53eV、1.56eV、1.59eV、1.62eV、1.65eV、1.68eV、1.71eV、1.74eV、1.77eV或1.80eV。
可选地，所述大面积钙钛矿层的面积为5～1000cm 2，例如为5cm 2、10cm 2、50cm 2、100cm 2、200cm 2、300cm 2、400cm 2、500cm 2、600cm 2、700cm 2、800cm 2、900cm 2或1000cm 2。
本申请所述的数值范围不仅包括上述例举的点值，还包括没有例举出的上述数值范围之间的任意的点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
与现有技术相比，本申请的有益效果为：
本申请通过将钙钛矿原料溶于离子液体，或离子液体和有机溶剂的混合物中，在前驱体制备钙钛矿层过程中，减少了空气中的水氧的影响，进一步地，结合涂布操作，实现钙钛矿层在空气中更加高效的大面积制备，从而提升钙钛矿基电池的生产效率，而且本申请制备得到的钙钛矿层形貌均匀，具有制备方法简单、适合工业化生产和成本低等特点。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
图1为本申请实施例1-4中提供的大面积钙钛矿层的制备方法的流程示意图；
图2为本申请实施例1中提供的大面积钙钛矿层的边缘形貌图；
图3为本申请实施例1中提供的大面积钙钛矿层的中心形貌图；
图4为本申请实施例1中提供的大面积钙钛矿层的边缘截面形貌图；
图5为本申请实施例1中提供的大面积钙钛矿层的中心截面形貌图。
具体实施方式
为更好地说明本申请，便于理解本申请的技术方案，下面对本申请进一步详细说明。但下述的实施例仅是本申请的简易例子，并不代表或限制本申请的权利保护范围，本申请保护范围以权利要求书为准。
实施例1
本实施例提供了一种大面积钙钛矿层的制备方法，如图1所示，具体包括以下步骤：
(Ⅰ)在空气气氛下，空气湿度为30％，将PbI 2和添加剂按照摩尔比为1:1混合，添加剂为CH 2(NH 2) 2Br、CsI和CH 2(NH 2) 2I的混合，FA代表CH 2(NH 2) 2 +，形成化学式为FA 0.8Cs 0.2Pb(I 0.75Br 0.25) 3的钙钛矿的原料，并溶于二氟乙酸甲铵中，二氟乙酸甲铵中还添加N,N-二甲基甲酰胺，N,N-二甲基甲酰胺与甲酸甲胺的体积比为3:7，形成钙钛矿前驱体，钙钛矿前驱体中钙钛矿的原料的摩尔浓度为1.4mol/L；
(Ⅱ)将钙钛矿前驱体以0.05m/s的速度涂布于158*158mm 2硅片边缘，并涂满整个表面，利用旋涂仪在4000rpm下旋涂处理20s，再在130℃下加热20min，制备得到钙钛矿层，带隙为1.7eV。
实施例2
本实施例提供了一种大面积钙钛矿层的制备方法，如图1所示，具体包括以下步骤：
(Ⅰ)在空气气氛下，空气湿度为50％，将PbI 2和CH 2(NH 2) 2I按照摩尔比为1:1混合，并溶于甲酸甲胺中，甲酸甲胺中还添加N,N-二甲基甲酰胺，N,N-二甲基甲酰胺与甲酸甲胺的体积比为2:8，形成钙钛矿前驱体，钙钛矿前驱体中钙钛矿的原料的摩尔浓度为1.3mol/L；
(Ⅱ)将钙钛矿前驱体以0.01m/s的速度涂布于210*210mm 2硅片边缘，并 涂满整个表面，利用旋涂仪在5000rpm下旋涂处理30s，再在100℃下加热30min，制备得到钙钛矿层，带隙为1.5eV。
实施例3
本实施例提供了一种大面积钙钛矿层的制备方法，如图1所示，具体包括以下步骤：
(Ⅰ)在空气气氛下，空气湿度为40％，将PbI 2和CH 3NH 3Br按照摩尔比为1.5:1混合，并溶于1,1,1-三氟乙基碘化铵中，形成钙钛矿前驱体，前驱体溶液中钙钛矿的原料的摩尔浓度为1.4mol/L；
(Ⅱ)将钙钛矿前驱体以0.1m/s的速度涂布于158*158mm 2硅片边缘，并涂满整个表面，利用旋涂仪在100rpm下旋涂处理120s，再在150℃下加热10min，制备得到钙钛矿层，带隙为1.8eV。
实施例4
本实施例提供了一种大面积钙钛矿层的制备方法，如图1所示，具体包括以下步骤：
(Ⅰ)在空气气氛下，空气湿度为30％，将PbCl 2和CsI按照摩尔比为0.5:1混合，并溶于醋酸甲铵中，形成钙钛矿前驱体，钙钛矿前驱体中钙钛矿的原料的摩尔浓度为1.4mol/L；
(Ⅱ)将钙钛矿前驱体以1m/s的速度涂布于200*200cm 2硅片边缘，并涂满整个表面，利用旋涂仪在6000rpm下旋涂处理25s，再在70℃下加热120min，制备得到钙钛矿层，带隙为1.6eV。
对实施例1制备得到的大面积钙钛矿层的表面以及截面进行SEM表征，硅片边缘形貌图如图2所示，中间形貌图如图3所示，边缘截面形貌图如图4所示，中心截面形貌图如图5所示。
通过图2-5可以看出，本申请通过将钙钛矿原料溶于离子液体中，在前驱体溶液制备钙钛矿层过程中，减少了空气中的水氧的影响，进一步地，结合涂布操作，实现钙钛矿层在空气中更加高效的大面积制备，从而提升晶体硅/钙钛矿叠层电池的生产效率，而且本申请制备得到的钙钛矿层形貌均匀，能够规模制备面积为5～1000cm 2的钙钛矿层，具有制备方法简单、适合工业化生产和成本低等特点。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。

Claims (11)

  1. 一种大面积钙钛矿层的制备方法，其中，所述制备方法包括：
    将组成钙钛矿的原料溶于离子液体，或离子液体与有机溶剂的混合物中，形成钙钛矿前驱体，将钙钛矿前驱体涂布于晶体硅底电池的表面，制备得到钙钛矿层。
  2. 根据权利要求1所述的制备方法，其中，所述大面积钙钛矿层的制备过程在空气气氛下进行。
  3. 根据权利要求1所述的制备方法，其中，所述钙钛矿的原料包括金属卤化物和添加剂；
    可选地，所述金属卤化物和添加剂的摩尔比为(0.5～1.5):1，进一步可选为(0.9～1.1):1；
    可选地，所述金属卤化物包括SnI 2、SnBr 2、SnF 2、SnCl 2、PbI 2、PbBr 2或PbCl 2中的一种或至少两种的组合；
    可选地，所述添加剂包括CH 3NH 3I、CH 3NH 3Cl、CH 3NH 3Br、CH 2(NH 2) 2I、CH 2(NH 2) 2Br、CH 2(NH 2) 2Cl、CsI、RbI、KI、CsBr或CsCl中的一种或至少两种的组合。
  4. 根据权利要求1或2或3所述的制备方法，其中，所述钙钛矿前驱体中钙钛矿的原料的摩尔浓度为0.1～5mol/L；
    可选地，所述有机溶剂与离子液体的体积比为(0～1000):1，进一步可选为(0～100):1。
  5. 根据权利要求1-4任一项所述的制备方法，其中，所述离子液体包括1,1,1-三氟乙基碘化铵、甲酸甲胺、醋酸甲铵、二氟乙酸甲铵或1-丁基-3-甲基咪唑四氟硼酸盐中的一种或至少两种的组合；
    可选地，所述有机溶剂包括N,N-二甲基甲酰胺、二甲基亚砜、四亚甲基亚 砜、环丁砜或N-甲基吡咯烷酮中的一种或至少两种的组合。
  6. 根据权利要求1-5任一项所述的制备方法，其中，所述涂布的步骤包括：先将钙钛矿前驱体涂布于基底表面，再进行旋涂处理薄膜中剩余的溶剂；
    可选地，所述基底包括沉积有ITO的玻璃基底、沉积有FTO的玻璃基底、聚酰亚胺柔性基底、萘二乙酸乙二醇酯柔性基底或晶体硅基底中的一种或至少两种的组合；
    可选地，所述晶体硅基底包括单晶硅硅片、掺杂单晶硅硅片、多晶硅硅片、掺杂多晶硅硅片、非晶硅硅片或掺杂非晶硅硅片中的一种或至少两种的组合。
  7. 根据权利要求1-6任一项所述的制备方法，其中，所述涂布的速度为0.01～1m/s；
    可选地，所述旋涂的旋转速度为100～6000rpm；
    可选地，所述旋涂的时间为10～1000s；
    可选地，所述旋涂的过程采用旋涂仪。
  8. 根据权利要求1-7任一项所述的制备方法，其中，所述涂布后进行加热处理；
    可选地，所述加热处理的温度为70～150℃；
    可选地，所述加热处理的时间为1～120min，进一步可选为10～60min。
  9. 根据权利要求1-8任一项所述的制备方法，其中，所述制备方法具体包括以下步骤：
    (Ⅰ)在空气气氛下，将金属卤化物和添加剂按照摩尔比为(0.5～1.5):1混合，并溶于离子液体和有机溶剂的混合物中，有机溶剂与离子液体的体积比为0～1000:1，形成钙钛矿前驱体，钙钛矿前驱体中钙钛矿的原料的摩尔浓度为0.1～5mol/L；
    (Ⅱ)将钙钛矿前驱体以0.01～1m/s的速度涂布于基底的表面后，在100～6000rpm下旋涂10～1000s，再在70～150℃下加热1～120min，制备得到钙钛矿层。
  10. 一种大面积钙钛矿层，其中，所述大面积钙钛矿层的形貌均匀，所述大面积钙钛矿层由权利要求1-9任一项所述大面积钙钛矿层的制备方法制备得到。
  11. 根据权利要求10所述的大面积钙钛矿层，其中，所述大面积钙钛矿层的带隙为1.3～1.8eV；
    可选地，所述大面积钙钛矿层的面积为5～1000cm 2。
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