WO2025200091A1 - 一种合成纯α相甲脒铅碘钙钛矿粉末及调控物相的方法 - Google Patents

一种合成纯α相甲脒铅碘钙钛矿粉末及调控物相的方法

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WO2025200091A1
WO2025200091A1 PCT/CN2024/092780 CN2024092780W WO2025200091A1 WO 2025200091 A1 WO2025200091 A1 WO 2025200091A1 CN 2024092780 W CN2024092780 W CN 2024092780W WO 2025200091 A1 WO2025200091 A1 WO 2025200091A1
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pure
perovskite powder
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刘芳洋
潘逸宁
曾强
李林鸿
马綮蔓
廖响
张茗珺
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
    • 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

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  • Halide perovskites due to their excellent optoelectronic properties, have been widely used in optoelectronic devices such as solar cells, photodetectors, and light-emitting diodes.
  • optoelectronic devices such as solar cells, photodetectors, and light-emitting diodes.
  • formamidinium-based lead halide perovskites exhibit superior thermal stability, a more suitable bandgap, and a wider spectral response than other organic-inorganic hybrid perovskite materials.
  • formamidinium-based lead iodide (FAPbI 3 ) exhibits both a room-temperature stable ⁇ phase and a photovoltaic-capable ⁇ phase.
  • the perovskite material typically exists in the device as a thin film.
  • a recently developed strategy for preparing thin films using pre-synthesized perovskite microcrystalline powder as a precursor can avoid the stoichiometric deviations and other issues associated with mixing binary halide raw materials.
  • the pre-synthesized powder can be used not only in solution deposition processes but also in evaporation deposition.
  • Aqueous synthesis methods do not rely on organic solvents as reaction solvents, and the synthesized powders are of high purity.
  • the purpose of the present invention is to provide an environmentally friendly strategy for the controllable synthesis of pure ⁇ -phase and ⁇ -phase perovskite powders in an aqueous solution system.
  • a method for synthesizing pure ⁇ -phase formamidinium lead iodide perovskite powder comprises the following steps:
  • step (2) Weighing an excess of formamidine acetate and adding it to the clear and transparent solution obtained in step (1), maintaining the temperature and stirring rapidly until the solution becomes clear and transparent again;
  • step (3) adding a certain amount of hydroiodic acid at 50-80° C. to the clear and transparent solution obtained in step (2) to adjust the pH of the mixed solution to ⁇ 2, maintaining the temperature and rapidly stirring until a large amount of precipitate is generated;
  • the concentration of the acetic acid aqueous solution in step (1) is 25-100%.
  • the formamidine acetate is in excess of 0-3 times relative to the lead source in terms of molar ratio.
  • the concentration of hydroiodic acid in step (3) is 45%-55%; the molar ratio of hydroiodic acid to lead source is 1:1-1:8; and the stirring time is 3-24 hours.
  • a method for regulating the phase of aqueous synthesis of formamidinium lead iodide perovskite powder comprises the following steps:
  • step (3) adding a certain amount of hydroiodic acid at 50-80° C. to the clear and transparent solution obtained in step (2) to adjust the pH of the mixed solution to ⁇ 2, maintaining the temperature and rapidly stirring until a large amount of precipitate is generated;
  • step (3) (4) adding one or both of ethyl acetate and isopropanol to the precipitate obtained in step (3) for washing, and then washing with an organic washing solvent, and then filtering and collecting the solid product and placing it in an oven, and drying it under controlled temperature to obtain pure ⁇ -phase or pure ⁇ -phase perovskite powder, wherein the organic washing solvent is one or more of ether, anhydrous ethanol, acetonitrile and acetone.
  • the organic washing solvent is one or more of ether, anhydrous ethanol, acetonitrile and acetone.
  • the drying temperature in step (4) is 130-200°C.
  • the present invention proposes a strategy for controllably synthesizing pure ⁇ -phase and ⁇ -phase perovskite powders in an aqueous solution system, and uses this strategy to apply the prepared perovskite powders to the preparation of perovskite films with excellent photoelectric response.
  • Figure 2 X-ray diffraction pattern of pure ⁇ -phase perovskite powder synthesized in Example 1;
  • Figure 5 Microscopic morphology of pure ⁇ -phase perovskite powder synthesized in Example 3.
  • Figure 6 X-ray diffraction pattern of pure ⁇ -phase perovskite powder synthesized in Example 3;
  • Figure 7 Microscopic morphology of pure ⁇ -phase perovskite powder synthesized in Example 4.
  • Figure 8 X-ray diffraction pattern of pure ⁇ -phase perovskite powder synthesized in Example 4.
  • Example 1 Preparation of pure ⁇ -phase perovskite powder
  • step C Heat 20 mL of 55% hydroiodic acid to 70°C and add to the clear solution obtained in step B. Maintain the temperature at 70°C and continue stirring for 6 h.
  • step D Collect the precipitate obtained in step C by filtration, rinse the filtered solid product 1-3 times with 50 ml of isopropanol, and then dry the solid product in an oven at 50° C. for 24 hours to obtain the final product.
  • Example 3 Preparation of pure ⁇ -phase perovskite powder by phase regulation
  • the preparation steps of this embodiment are basically the same as the steps from step A to D of embodiment 2, except that the drying temperature in step D is 160°C.
  • the product micromorphology is shown in Figure 5, and the X-ray diffraction results are shown in Figure 6.
  • the final product is a microcrystalline ⁇ - FAPbI3 powder with no XRD peaks from impurity phases. ICP testing confirmed a purity of 99.995%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

本发明公开一种调控水系合成甲脒铅碘钙钛矿粉末物相的方法，可合成纯α相和δ相钙钛矿粉末，包括步骤：首先将铅源溶于乙酸水溶液中，然后加入乙酸甲脒，搅拌得到的澄清透明溶液，再加入氢碘酸，获得大量沉淀，再将沉淀过滤收集，用洗涤剂冲洗沉淀后收集固体产物并放置于烘箱中，干燥后获得钙钛矿粉末。可通过控制洗涤溶剂种类和干燥温度获得纯α相和δ相钙钛矿粉末。

Description

一种合成纯α相甲脒铅碘钙钛矿粉末及调控物相的方法 技术领域
本发明属于光电功能半导体材料领域，具体涉及一种合成纯α相甲脒铅碘钙钛矿粉末及调控物相的方法。
背景技术
卤化物钙钛矿材料凭借其优异的光电性质已广泛应用于太阳电池、光电探测器和发光二极管等光电子器件中。在卤化物钙钛矿材料家族中，甲脒基铅卤化物钙钛矿材料相对于其他有机无机杂化钙钛矿材料具有更好的热稳定性、更合适的禁带宽度和光谱响应范围。如甲脒铅碘(FAPbI3)，其存在室温稳定的δ相，及具有光伏特性的α相。
在钙钛矿太阳电池中，钙钛矿材料通常是以薄膜的形态存在于器件中，近年来发展的一种使用预先合成好的钙钛矿微晶粉末为前驱体制备薄膜的策略可以避免二元卤化物原料混合所带来的化学计量比偏差等问题，且预合成粉末不仅可用于溶液法沉积工艺，还可应用于蒸发法沉积。水系合成方法不依赖有机溶剂作为反应溶剂，且合成粉末纯度高。通过调控水系合成甲脒铅碘物相，可制备出便于运输及长期保存的δ相粉末，及可直接应用于高质量钙钛矿薄膜制备的α相粉末。
发明内容
本发明的目的在于提供一种环境友好的，在水溶液体系中可控合成纯α相、δ相钙钛矿粉末策略。
本发明采用如下技术方案：
一种合成纯α相甲脒铅碘钙钛矿粉末的方法，包括以下步骤：
(1)将一定量的铅源加入到一定浓度的乙酸水溶液中，控制温度为40-80℃并搅拌形成澄清透明的溶液；
(2)称取过量的乙酸甲脒加入到步骤(1)得到的澄清透明溶液中，保持温度迅速搅拌至溶液再次变澄清透明；
(3)向步骤(2)获得的澄清透明溶液中加入一定量的50-80℃的氢碘酸，使混合溶液的pH<2，保持温度并迅速搅拌直至生成大量沉淀；
(4)向步骤(3)获得的沉淀中加入乙酸乙酯或异丙醇中的一种或两种进行清洗，随后过滤收集固体产物并放置于烘箱中，干燥后获得纯α相钙钛矿粉末。
优选地，步骤(1)中所述铅源包括氧化铅、碳酸铅或草酸铅中的一种或多种。
优选地，步骤(1)中所述乙酸水溶液浓度为25-100％。
优选地，按摩尔比，步骤(2)中所述乙酸甲脒对于铅源过量0-3倍。
优选地，步骤(3)中所述氢碘酸浓度为45％-55％；按摩尔比，氢碘酸与铅源的比例为1:1-1:8；所述搅拌时间为3-24h。
一种调控水系合成甲脒铅碘钙钛矿粉末物相的方法，包括以下步骤：
(1)将一定量的铅源加入到一定浓度的乙酸水溶液中，控制温度为40-80℃并搅拌形成澄清透明的溶液；
(2)称取过量的乙酸甲脒加入到步骤(1)得到的澄清透明溶液中，保持温度迅速搅拌至溶液再次变澄清透明；
(3)向步骤(2)获得的澄清透明溶液中加入一定量的50-80℃的氢碘酸，使混合溶液的pH<2，保持温度并迅速搅拌直至生成大量沉淀；
(4)向步骤(3)获得的沉淀中加入乙酸乙酯或异丙醇中的一种或两种进行清洗，之后再使用有机洗涤溶剂洗涤，随后过滤收集固体产物并放置于烘箱中，控制温度干燥后获得纯α相或纯δ相钙钛矿粉末，其中，有机洗涤溶剂为乙醚、无水乙醇、乙腈和丙酮中的一种或多种。
优选地，当需合成纯δ相钙钛矿粉末时，步骤(4)中干燥温度为50-125℃。
优选地，当需合成纯α相钙钛矿粉末时，步骤(4)中干燥温度为130-200℃。
本发明提出一种在水溶液体系中可控合成纯α相和δ相钙钛矿粉末的策略，并采用该策略将制备的钙钛矿粉末应用于具有优异光电响应的钙钛矿薄膜制备。
附图说明
图1：实施例1合成的纯α相钙钛矿粉末微观形貌；
图2：实施例1合成的纯α相钙钛矿粉末X射线衍射图；
图3：实施例2合成的纯δ相钙钛矿粉末微观形貌；
图4：实施例2合成的纯δ相钙钛矿粉末X射线衍射图；
图5：实施例3合成的纯α相钙钛矿粉末微观形貌；
图6：实施例3合成的纯α相钙钛矿粉末X射线衍射图；
图7：实施例4合成的纯δ相钙钛矿粉末微观形貌；
图8：实施例4合成的纯δ相钙钛矿粉末X射线衍射图。
具体实施方式
下面结合附图和实施例对本发明作进一步的详细说明。可以理解的是，此处所描述的具体实施例仅仅用于解释本发明，而非对本发明的限定。
实施例1：纯α相钙钛矿粉末的制备
A、称量9g氧化铅倒入烧瓶中，再量取11ml浓度为60％的乙酸水溶液加入装有氧化铅的烧瓶中，在70℃下持续搅拌至溶液澄清透明；
B、称量7g乙酸甲脒固体加入圆底烧瓶中，保持温度为70℃，持续搅拌至溶液再次澄清透明；
C、将20mL 55％氢碘酸加热至70℃后加入步骤B获得的澄清透明的溶液中，保持温度为70℃不变持续搅拌6h；
D、将步骤C获得的沉淀过滤收集，取50ml异丙醇冲洗过滤得到的固体产物1-3次，随后将固体产物放进烘箱在50℃干燥24h后得到最终产物。
产物微观形貌请参照图1，X射线衍射结果如图2所示，最终产物为α-FAPbI3微晶粉末，不存在杂质相XRD峰。经过ICP检测，产品纯度达到99.996％。
实施例2：纯δ相钙钛矿粉末的制备
A、称量9g氧化铅倒入烧瓶中，再量取11ml浓度为60％的乙酸水溶液加入装有氧化铅的烧瓶中，在50℃下持续搅拌至溶液澄清透明；
B、称量7g乙酸甲脒固体加入圆底烧瓶中，保持温度为50℃，持续搅拌至溶液再次澄清透明；
C、将20mL 55％氢碘酸加热至50℃后加入步骤B获得的澄清透明的溶液中，保持温度为50℃度不变持续搅拌6h；
D、将步骤C获得的沉淀过滤收集，取50ml乙酸乙酯冲洗过滤得到的固 体产物1次，再取50ml乙腈冲洗2次以上，随后将固体产物放进烘箱在50℃干燥24h后得到最终产物。
产物微观形貌请参照图3，X射线衍射结果如图4所示，最终产物为δ-FAPbI3微晶粉末，不存在杂质相XRD峰。经过ICP检测，产品纯度达到99.998％。
实施例3：通过物相调控制备纯α相钙钛矿粉末
本实施例制备步骤与实施例2从步骤A至D的步骤基本相同，区别在于，步骤D中干燥温度为160℃。
产物微观形貌请参照图5，X射线衍射结果如图6所示，最终产物为α-FAPbI3微晶粉末，不存在杂质相XRD峰。经过ICP检测，产品纯度达到99.995％。
实施例4：通过物相调控制备纯δ相钙钛矿粉末
本实施例制备步骤与实施例1从步骤A至D的步骤基本相同，区别在于，步骤D中采用丙酮洗涤1-3次。
产物微观形貌请参照图7，X射线衍射结果如图8所示，最终产物为δ-FAPbI3微晶粉末，不存在杂质相XRD峰。经过ICP检测，产品纯度达到99.992％。

Claims (8)

  1. 一种合成纯α相甲脒铅碘钙钛矿粉末的方法，其特征在于，包括以下步骤：
    (1)将一定量的铅源加入到一定浓度的乙酸水溶液中，控制温度为40-80℃并搅拌形成澄清透明的溶液；
    (2)称取过量的乙酸甲脒加入到步骤(1)得到的澄清透明溶液中，保持温度迅速搅拌至溶液再次变澄清透明；
    (3)向步骤(2)获得的澄清透明溶液中加入一定量的50-80℃的氢碘酸，使混合溶液的pH<2，保持温度并迅速搅拌直至生成大量沉淀；
    (4)向步骤(3)获得的沉淀中加入乙酸乙酯或异丙醇中的一种或两种进行清洗，随后过滤收集固体产物并放置于烘箱中，干燥后获得纯α相钙钛矿粉末。
  2. 如权利要求1所述的方法，其特征在于，步骤(1)中所述铅源包括氧化铅、碳酸铅或草酸铅中的一种或多种。
  3. 如权利要求1所述的方法，其特征在于，步骤(1)中所述乙酸水溶液浓度为25-100％。
  4. 如权利要求1所述的方法，其特征在于，按摩尔比，步骤(2)中所述乙酸甲脒对于铅源过量0-3倍。
  5. 如权利要求1所述的方法，其特征在于，步骤(3)中所述氢碘酸浓度为45％-55％；按摩尔比，氢碘酸与铅源的比例为1:1-1:8；所述搅拌时间为3-24h。
  6. 一种调控水系合成甲脒铅碘钙钛矿粉末物相的方法，其特征在于，包括以下步骤：
    (1)将一定量的铅源加入到一定浓度的乙酸水溶液中，控制温度为40-80℃并搅拌形成澄清透明的溶液；
    (2)称取过量的乙酸甲脒加入到步骤(1)得到的澄清透明溶液中，保持温度迅速搅拌至溶液再次变澄清透明；
    (3)向步骤(2)获得的澄清透明溶液中加入一定量的50-80℃的氢碘酸，使混合溶液的pH<2，保持温度并迅速搅拌直至生成大量沉淀；
    (4)向步骤(3)获得的沉淀中加入乙酸乙酯或异丙醇中的一种或两种进行清洗，之后再使用有机洗涤溶剂洗涤，随后过滤收集固体产物并放置于烘箱中，控制温度干燥后获得纯α相或纯δ相钙钛矿粉末，其中，有机洗涤溶剂为乙醚、无水乙醇、乙腈和丙酮中的一种或多种。
  7. 如权利要求6所述的方法，其特征在于，当需合成纯δ相钙钛矿粉末时，步骤(4)中干燥温度为50-125℃。
  8. 如权利要求6所述的方法，其特征在于，当需合成纯α相钙钛矿粉末时，步骤(4)中干燥温度为130-200℃。
PCT/CN2024/092780 2024-03-29 2024-05-13 一种合成纯α相甲脒铅碘钙钛矿粉末及调控物相的方法 Pending WO2025200091A1 (zh)

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