WO2020113972A1 - 可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液 - Google Patents

可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液 Download PDF

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WO2020113972A1
WO2020113972A1 PCT/CN2019/098046 CN2019098046W WO2020113972A1 WO 2020113972 A1 WO2020113972 A1 WO 2020113972A1 CN 2019098046 W CN2019098046 W CN 2019098046W WO 2020113972 A1 WO2020113972 A1 WO 2020113972A1
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precursor solution
composite perovskite
stabilizer
iodide
organic solvent
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吴刚
连小梅
陈杰焕
陈红征
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Zhejiang University
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  • the invention relates to a Pb/Sn composite perovskite precursor solution which can be stably stored.
  • organic-inorganic hybrid perovskite materials have developed rapidly, which has the advantages of high optical absorption coefficient, high carrier mobility, simple solution preparation methods, etc., making this material widely used in the field of solar cells.
  • the maximum efficiency of solar cells made of inorganic hybrid perovskite materials has exceeded 23%.
  • high-performance organic-inorganic perovskites are based on heavy metal lead materials, which are not environmentally friendly and limit the practical application of this material.
  • the Pb/Sn composite perovskite prepared by partially replacing lead with stannous ions has attracted more and more attention because it can reduce the impact of lead on the environment and humans.
  • stannous ions are extremely unstable, and they are easily oxidized to tetravalent tin ions even in trace water and oxygen environments.
  • the presence of tetravalent tin ions in the precursor will cause the performance of the prepared Pb/Sn composite perovskite to deteriorate, and greatly reduce the efficiency of the solar cell based on the Pb/Sn composite perovskite as the light absorbing layer. Therefore, the preparation of Pb/Sn composite perovskite materials must use freshly prepared precursor solutions.
  • the method of the invention adds a stabilizer during the preparation process, protects the stannous ions through the strong coordination effect of the stabilizer and the stannous ions, inhibits the oxidation of stannous ions, and realizes the precursor solution for Pb/Sn composite perovskite Stable storage.
  • the Pb/Sn composite perovskite precursor solution after 120 days of long-term storage showed that the efficiency of the prepared Pb/Sn composite perovskite solar cell did not change more than 5%. This is of great significance for the large-scale preparation of Pb/Sn composite perovskite materials with stable performance.
  • the object of the present invention is to solve the defect that the precursor solution in the prior art is prone to large-scale deterioration during long-term storage, and to provide a Pb/Sn composite perovskite precursor solution that can be stably stored.
  • a precursor solution for Pb/Sn composite perovskite that can be stored stably is obtained by mixing and dissolving lead iodide, stannous iodide, and a stabilizer in an organic solvent.
  • the stabilizer is ammonium thiocyanate, methylamine thiocyanate, thiocyanic acid or lead thiocyanate.
  • the organic solvent is one or a mixture of N,N-dimethylformamide, dimethylsulfoxide and formamide.
  • the ratio of lead iodide to organic solvent is 100-800 mg: 1 ml.
  • the molar ratio of lead iodide: stannous iodide is 1:9 to 9:1.
  • the molar ratio of lead iodide: stabilizer is 1:0.1 ⁇ 1:1.
  • Another object of the present invention is to provide a Pb/Sn composite perovskite material prepared from the precursor solution described in any of the above solutions.
  • Another object of the present invention is to provide a solar cell using the Pb/Sn composite perovskite material as a light absorbing layer.
  • the present invention obtains a Pb/Sn composite perovskite that can be stored stably without affecting the subsequent preparation of the Pb/Sn composite perovskite by adding a stabilizer to the lead iodide and stannous iodide solutions.
  • Precursor solution The performance of the prepared Pb/Sn composite perovskite is little affected by the storage time of the precursor solution.
  • the Pb/Sn composite perovskite was prepared with the newly prepared precursor solution and the precursor solution stored for 120 days, and the Pb/Sn composite perovskite was used as the light absorption layer to prepare the solar cell, and the efficiency change did not exceed 5%. This is of great significance for large-scale preparation of Pb/Sn composite perovskite materials with stable performance.
  • FIG. 1 is a graph showing the efficiency of a solar cell prepared with a precursor solution for Pb/Sn composite perovskite that can be stably stored and a precursor solution added with a stabilizer, as a function of storage time of the precursor solution.
  • the preparation process of the Pb/Sn composite perovskite precursor solution that can be stably stored is as follows: lead iodide, stannous iodide, and stabilizer are mixed and dissolved in an organic solvent to obtain a precursor solution, and the combination of lead iodide and organic solvent
  • the mixing ratio is 100-800 mg: 1 ml; lead iodide: stannous iodide (molar ratio) is 1:9 ⁇ 9:1; lead iodide: stabilizer (molar ratio) is 1:0.1 ⁇ 1:1 .
  • the stabilizer is ammonium thiocyanate, methylamine thiocyanate, thiocyanic acid or lead thiocyanate
  • the organic solvent is one of N,N-dimethylformamide, dimethylsulfoxide and formamide Or a mixture thereof.
  • the precursor solution can be used to prepare a Pb/Sn composite perovskite material, and the Pb/Sn composite perovskite material is used as a light absorption layer to prepare a solar cell.
  • the lead iodide, stannous iodide, and stabilizer were mixed and dissolved in an organic solvent, and stirred at 70°C overnight to obtain a precursor solution.
  • the ratio of lead iodide to organic solvent is 800 mg: 1 ml; lead iodide: stannous iodide (molar ratio) is 1:9; lead iodide: stabilizer (molar ratio) is 1 :1.
  • the stabilizer is ammonium thiocyanate;
  • the organic solvent is a mixture of N,N-dimethylformamide and dimethyl sulfoxide in a ratio of 8:3 (volume ratio).
  • Table 1 shows the performance of the Pb/Sn composite perovskite solar cell prepared with the above-prepared precursor solution.
  • the efficiency of Pb/Sn composite perovskite solar cells prepared by storing the added and unadded stabilizer precursor solutions at different times varies with the storage time of the precursor solution, and the solution without stabilizers added After 120 days of storage, the device efficiency fell below 60% of the initial value. After 120 days of storage with the stabilizer added, the device efficiency dropped by less than 5%, indicating that the storage stability of the precursor solution was greatly enhanced after the stabilizer was added.
  • Lead iodide, stannous iodide, and stabilizer were mixed and dissolved in an organic solvent, and stirred at 70°C overnight to obtain a precursor solution.
  • the ratio of lead iodide to organic solvent is 100 mg: 1 ml; lead iodide: stannous iodide (molar ratio) is 9:1; lead iodide: stabilizer (molar ratio) is 1 :0.1.
  • the stabilizer is ammonium thiocyanate;
  • the organic solvent is a mixture of N,N-dimethylformamide and formamide, the ratio is 9:1 (volume ratio).
  • the Pb/Sn composite perovskite solar cells prepared with the added and unstabilized precursor solutions stored at different times were investigated, and the change of battery efficiency with the storage time of the precursor solution was investigated.
  • the curve shape obtained was similar to that in Figure 1. It shows that the storage stability of the precursor solution is greatly enhanced after the stabilizer is added.
  • Lead iodide, stannous iodide, and stabilizer were mixed and dissolved in an organic solvent, and stirred at 70°C overnight to obtain a precursor solution.
  • the ratio of lead iodide to organic solvent is 400 mg: 1 ml; lead iodide: stannous iodide (molar ratio) is 4:6; lead iodide: stabilizer (molar ratio) is 1 :0.25.
  • the stabilizer is thiocyanic acid; the organic solvent is a mixture of dimethyl sulfoxide and formamide, the ratio is 1:9 (volume ratio).
  • the Pb/Sn composite perovskite solar cells prepared with the added and unstabilized precursor solutions stored at different times were investigated, and the change of battery efficiency with the storage time of the precursor solution was investigated.
  • the curve shape obtained was similar to that in Figure 1. It shows that the storage stability of the precursor solution is greatly enhanced after the stabilizer is added.
  • the lead iodide, stannous iodide, and stabilizer were mixed and dissolved in an organic solvent, and stirred at 70°C overnight to obtain a precursor solution.
  • the ratio of lead iodide to organic solvent is 500 mg: 1 ml; lead iodide: stannous iodide (molar ratio) is 7:3; lead iodide: stabilizer (molar ratio) is 1 :0.4.
  • the stabilizer is lead thiocyanate; the organic solvent is N,N-dimethylformamide.
  • the Pb/Sn composite perovskite solar cells prepared with the added and unstabilized precursor solutions stored at different times were investigated, and the change of battery efficiency with the storage time of the precursor solution was investigated.
  • the curve shape obtained was similar to that in Figure 1. It shows that the storage stability of the precursor solution is greatly enhanced after the stabilizer is added.
  • the lead iodide, stannous iodide, and stabilizer were mixed and dissolved in an organic solvent, and stirred at 70°C overnight to obtain a precursor solution.
  • the ratio of lead iodide to organic solvent is 600 mg: 1 ml; lead iodide: stannous iodide (molar ratio) is 3:7; lead iodide: stabilizer (molar ratio) is 1 : 0.6.
  • the stabilizer is methylamine thiocyanate; the organic solvent is formamide.
  • the Pb/Sn composite perovskite solar cells prepared with the added and unstabilized precursor solutions stored at different times were investigated, and the change of battery efficiency with the storage time of the precursor solution was investigated.
  • the curve shape obtained was similar to that in Figure 1. It shows that the storage stability of the precursor solution is greatly enhanced after the stabilizer is added.
  • the lead iodide, stannous iodide, and stabilizer were mixed and dissolved in an organic solvent, and stirred at 70°C overnight to obtain a precursor solution.
  • the ratio of lead iodide to organic solvent is 700 mg: 1 ml; lead iodide: stannous iodide (molar ratio) is 6:4; lead iodide: stabilizer (molar ratio) is 1:0.8.
  • the stabilizer is ammonium thiocyanate; the organic solvent is dimethyl sulfoxide.
  • the Pb/Sn composite perovskite solar cells prepared with the added and unstabilized precursor solutions stored at different times were investigated, and the change of battery efficiency with the storage time of the precursor solution was investigated. The curve shape obtained was similar to that in Figure 1. It shows that the storage stability of the precursor solution is greatly enhanced after the stabilizer is added.
  • Lead iodide, stannous iodide, and stabilizer were mixed and dissolved in an organic solvent, and stirred at 70°C overnight to obtain a precursor solution.
  • the ratio of lead iodide to organic solvent is 300 mg: 1 ml; lead iodide: stannous iodide (molar ratio) is 4:6; lead iodide: stabilizer (molar ratio) is 1:0.8.
  • the stabilizer is methylamine thiocyanate;
  • the organic solvent is a mixed solution of N,N-dimethylformamide, dimethylsulfoxide and formamide, the ratio is 8:1:1 (volume ratio).
  • the Pb/Sn composite perovskite solar cells prepared with the added and unstabilized precursor solutions stored at different times were investigated, and the change of battery efficiency with the storage time of the precursor solution was investigated.
  • the curve shape obtained was similar to that in Figure 1. It shows that the storage stability of the precursor solution is greatly enhanced after the stabilizer is added.

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Abstract

一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液，该前驱体溶液是将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂中获得的。该前驱体溶液可以后续用于Pb/Sn复合钙钛矿的制备，制备得到的Pb/Sn复合钙钛矿的性能受前驱体溶液存储时间的影响很小。分别以新制备的前驱体溶液和储存120天的前驱体溶液制备Pb/Sn复合钙钛矿，并以Pb/Sn复合钙钛矿为光吸收层制备太阳电池，效率变化不超过5％。这对于实现性能稳定的Pb/Sn复合钙钛矿材料的大规模制备具有十分重要的意义。

Description

可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液 技术领域
本发明涉及一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液。
技术背景
近年来有机-无机杂化钙钛矿材料发展迅速，其具有高光学吸收系数，高载流子迁移率，简单的溶液制备方法等优点，使得这一材料被广泛应用于太阳电池领域，由有机-无机杂化钙钛矿材料制备的太阳电池最高效率已超23％。然而，高性能有机-无机钙钛矿都是基于重金属铅的材料，环境友好性不够，限制了这一材料的实际应用。
相比于全铅三维钙钛矿材料，用亚锡离子部分取代铅制备的Pb/Sn复合钙钛矿，因其能减少铅对环境和人类的影响而越来越被关注。然而亚锡离子极不稳定，即使是在微量水和氧气的环境中也易被氧化成四价锡离子。四价锡离子存在于前驱体中，会导致制备得到的Pb/Sn复合钙钛矿性能劣化，并大幅度降低基于以Pb/Sn复合钙钛矿为吸光层的太阳能电池效率。因此，Pb/Sn复合钙钛矿材料的制备必须采用新鲜制备的前驱体溶液。
目前，相关研究都集中于解决前驱体溶液转变为钙钛矿过程中，防止亚锡离子氧化成四价锡离子的问题，采用的方法是在前驱体溶液中加入氟化亚锡、肼、维生素A等物质。尚未有研究能够解决前驱体溶液储存过程中亚锡离子的稳定性问题，更没有相关研究成果能够确保Pb/Sn复合钙钛矿太阳能电池性能不会因为前驱体溶液的长时间储存而产生大幅度的劣化，而该问题对于实际的连续化大规模制备是十分重要的。
本发明通过在制备过程中添加稳定剂的方法，通过稳定剂与亚锡离子的强配位作用保护亚锡离子，抑制亚锡离子的氧化，实现了Pb/Sn复合钙钛矿用前驱体溶液的稳定储存。长期储存120天后的Pb/Sn复合钙钛矿用前驱体溶液与新制备的前驱体溶液相比较，制备得到的Pb/Sn 复合钙钛矿太阳能电池效率变化不超过5％。这对于实现性能稳定的Pb/Sn复合钙钛矿材料的大规模制备具有十分重要的意义。
发明内容
本发明的目的是解决现有技术中前驱体溶液的长时间储存容易产生大幅度劣化的缺陷，并提供一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液。
本发明具体采用的技术方案如下：
可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液，该前驱体溶液是将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂中获得的。
优选的，所述的稳定剂为硫氰酸铵、硫氰酸甲胺、硫氰酸或硫氰酸铅。
优选的，所述的有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜、甲酰胺中的一种或其混合物。
优选的，前驱体溶液中，碘化铅与有机溶剂的配比为100-800毫克:1毫升。
优选的，前驱体溶液中，以摩尔比计，碘化铅:碘化亚锡为1:9～9:1。
优选的，前驱体溶液中，以摩尔比计，碘化铅:稳定剂为1:0.1～1:1。
本发明的另一目的在于提供一种由上述任一方案所述前驱体溶液制备的Pb/Sn复合钙钛矿材料。
本发明的另一目的在于提供一种以上述Pb/Sn复合钙钛矿材料作为光吸收层的太阳电池。
本发明通过在碘化铅、碘化亚锡溶液中添加稳定剂的方法，在不影响后续Pb/Sn复合钙钛矿制备的前提下，获得了能够稳定储存的Pb/Sn复合钙钛矿用前驱体溶液。制备得到的Pb/Sn复合钙钛矿的性能受前驱体溶液存储时间的影响很小。分别以新制备的前驱体溶液和储存120天的前驱体溶液制备Pb/Sn复合钙钛矿，并Pb/Sn复合钙钛矿为光吸收层制备太阳电池，效率变化不超过5％。这对于实现性能稳定的Pb/Sn复合钙钛矿材料的大规模制备具有十 分重要的意义。
附图说明
图1是分别以可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液、为加稳定剂的前驱体溶液制备得到的太阳能电池效率，随前驱体溶液储存时间的变化图。
具体实施方式
可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液的制备过程为：将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂中获得前驱体溶液，碘化铅与有机溶剂的配比为100-800毫克:1毫升；碘化铅:碘化亚锡(摩尔比)为1:9～9:1；碘化铅:稳定剂(摩尔比)为1:0.1～1:1。其中，稳定剂为硫氰酸铵、硫氰酸甲胺、硫氰酸或硫氰酸铅，有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜、甲酰胺中的一种或其混合物。该前驱体溶液可用于制备得到Pb/Sn复合钙钛矿材料，并以Pb/Sn复合钙钛矿材料作为光吸收层制备太阳电池。
下面通过如下实施例对本发明作进一步的详述：
实施例1：
将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂，70℃搅拌过夜获得前驱体溶液。本实施例中，碘化铅与有机溶剂的配比为800毫克:1毫升；碘化铅:碘化亚锡(摩尔比)为1:9；碘化铅:稳定剂(摩尔比)为1:1。其中，稳定剂为硫氰酸铵；有机溶剂为N,N-二甲基甲酰胺和二甲基亚砜混合物，比例为8:3(体积比)。以上述新配置的前驱体溶液制备得到的Pb/Sn复合钙钛矿太阳电池性能如表1所示。
表1 Pb/Sn复合钙钛矿为光吸收层制备的太阳能电池的性能指标
Figure PCTCN2019098046-appb-000001
如图1所示，分别用储存不同时间的添加、未添稳定剂前驱体溶液制备得到的Pb/Sn复合钙钛矿太阳电池的效率随前驱体溶液储存时间的变化，没有添加稳定剂的溶液储存了120天后 器件效率降到初始的60％以下，添加了稳定剂的溶液储存120天后器件效率只降了不到5％，表明加入稳定剂后，前驱体溶液的储存稳定性大大增强。
实施例2：
将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂，70℃搅拌过夜获得前驱体溶液。本实施例中，碘化铅与有机溶剂的配比为100毫克:1毫升；碘化铅:碘化亚锡(摩尔比)为9:1；碘化铅:稳定剂(摩尔比)为1:0.1。其中，稳定剂为硫氰酸铵；有机溶剂为N,N-二甲基甲酰胺和甲酰胺混合物，比例为9:1(体积比)。分别用储存不同时间的添加、未添稳定剂前驱体溶液制备得到的Pb/Sn复合钙钛矿太阳电池，考察电池效率随前驱体溶液储存时间的变化，得到的曲线形状与图1相类似，表明加入稳定剂后，前驱体溶液的储存稳定性大大增强。
实施例3：
将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂，70℃搅拌过夜获得前驱体溶液。本实施例中，碘化铅与有机溶剂的配比为400毫克:1毫升；碘化铅:碘化亚锡(摩尔比)为4:6；碘化铅:稳定剂(摩尔比)为1:0.25。其中，稳定剂为硫氰酸；有机溶剂为二甲基亚砜和甲酰胺混合物，比例为1:9(体积比)。分别用储存不同时间的添加、未添稳定剂前驱体溶液制备得到的Pb/Sn复合钙钛矿太阳电池，考察电池效率随前驱体溶液储存时间的变化，得到的曲线形状与图1相类似，表明加入稳定剂后，前驱体溶液的储存稳定性大大增强。
实施例4：
将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂，70℃搅拌过夜获得前驱体溶液。本实施例中，碘化铅与有机溶剂的配比为500毫克:1毫升；碘化铅:碘化亚锡(摩尔比)为7:3；碘化铅:稳定剂(摩尔比)为1:0.4。其中，稳定剂为硫氰酸铅；有机溶剂为N,N-二甲基甲酰胺。分别用储存不同时间的添加、未添稳定剂前驱体溶液制备得到的Pb/Sn复合钙钛矿太阳电池，考察电池效率随前驱体溶液储存时间的变化，得到的曲线形状与图1相类似，表明加入稳定剂后，前驱体溶液的储存稳定性大大增强。
实施例5：
将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂，70℃搅拌过夜获得前驱体溶液。本实施例中，碘化铅与有机溶剂的配比为600毫克:1毫升；碘化铅:碘化亚锡(摩尔比)为3:7；碘化铅:稳定剂(摩尔比)为1:0.6。其中，稳定剂为硫氰酸甲胺；有机溶剂为甲酰胺。分别用储存不同时间的添加、未添稳定剂前驱体溶液制备得到的Pb/Sn复合钙钛矿太阳电池，考察电池效率随前驱体溶液储存时间的变化，得到的曲线形状与图1相类似，表明加入稳定剂后，前驱体溶液的储存稳定性大大增强。
实施例6：
将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂，70℃搅拌过夜获得前驱体溶液。碘化铅与有机溶剂的配比为700毫克:1毫升；碘化铅:碘化亚锡(摩尔比)为6:4；碘化铅:稳定剂(摩尔比)为1:0.8。其中，稳定剂为硫氰酸铵；有机溶剂为二甲基亚砜。分别用储存不同时间的添加、未添稳定剂前驱体溶液制备得到的Pb/Sn复合钙钛矿太阳电池，考察电池效率随前驱体溶液储存时间的变化，得到的曲线形状与图1相类似，表明加入稳定剂后，前驱体溶液的储存稳定性大大增强。
实施例7：
将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂，70℃搅拌过夜获得前驱体溶液。碘化铅与有机溶剂的配比为300毫克:1毫升；碘化铅:碘化亚锡(摩尔比)为4:6；碘化铅:稳定剂(摩尔比)为1:0.8。其中，稳定剂为硫氰酸甲胺；有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜和甲酰胺的混合溶液，比例为8:1:1(体积比)。分别用储存不同时间的添加、未添稳定剂前驱体溶液制备得到的Pb/Sn复合钙钛矿太阳电池，考察电池效率随前驱体溶液储存时间的变化，得到的曲线形状与图1相类似，表明加入稳定剂后，前驱体溶液的储存稳定性大大增强。

Claims (8)

  1. 一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液，其特征在于该前驱体溶液是将碘化铅、碘化亚锡、稳定剂混合溶解于有机溶剂中获得的。
  2. 根据权利要求1所述的一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液，其特征在于所述的稳定剂为硫氰酸铵、硫氰酸甲胺、硫氰酸或硫氰酸铅。
  3. 根据权利要求1所述的一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液，其特征在于所述的有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜、甲酰胺中的一种或其混合物。
  4. 根据权利要求1所述的一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液，其特征在于前驱体溶液中，碘化铅与有机溶剂的配比为100-800毫克:1毫升。
  5. 根据权利要求1所述的一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液，其特征在于前驱体溶液中，以摩尔比计，碘化铅:碘化亚锡为1:9～9:1。
  6. 根据权利要求1所述的一种可稳定储存的Pb/Sn复合钙钛矿用前驱体溶液，其特征在于前驱体溶液中，以摩尔比计，碘化铅:稳定剂为1:0.1～1:1。
  7. 一种由权利要求1～6任一所述前驱体溶液制备的Pb/Sn复合钙钛矿材料。
  8. 一种以权利要求7所述Pb/Sn复合钙钛矿材料层作为光吸收层的太阳电池。
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