CN110590647B - 一种水稳定锑碘基杂化钙钛矿及其合成与应用 - Google Patents

一种水稳定锑碘基杂化钙钛矿及其合成与应用 Download PDF

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CN110590647B
CN110590647B CN201910957509.8A CN201910957509A CN110590647B CN 110590647 B CN110590647 B CN 110590647B CN 201910957509 A CN201910957509 A CN 201910957509A CN 110590647 B CN110590647 B CN 110590647B
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et4ppi
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赵若愚
刘广宁
许让栋
牛鹏飞
王子菡
李村成
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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Abstract

本发明公开了一种水稳定锑碘基无机‑有机杂化钙钛矿及其制备方法与应用。所述的杂化钙钛矿分子结构式为Et4ppi‑SbI4，式中的Et4ppi是带有一个单位正电荷的4‑苯基吡啶阳离子，由4‑苯基吡啶中的N原子乙基化形成；该材料中的SbI4阴离子则是三价锑离子和碘离子配位形成的一维阴离子链。通过选择三氯化锑，4‑苯基吡啶，丙酮和氢碘酸为反应原料，通过溶剂热反应获得了Et4ppi‑SbI4的单晶，该材料作为一种环境友好型材料，同时具有优异的水稳定性和光电转换性能，在光电子器件领域具有重要应用价值。

Description

一种水稳定锑碘基杂化钙钛矿及其合成与应用
技术领域
本发明涉及无机-有机杂化钙钛矿领域，尤其涉及一种水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4的制备方法与其光电转换应用，Et4ppi为乙基化4-苯基吡啶阳离子。
背景技术
由于近年来化石能源消耗以及空气环境恶化日益严重，迫切需要一种新型的为人类提供清洁的可再生能源的方法，因此，人们将目光投向了取之不尽用之不竭的太阳能，在太阳能转换方式备选方案当中，将太阳能直接转换成电能的光伏技术拥有广阔的发展前景。
以明星材料甲铵铅碘钙钛矿（MAPbI3，其中MA = CH3NH3 +）为例，尽管其作为太阳能光吸收剂的认证效率已经突破23%，已逐渐趋近于硅基的太阳能电池，也被认为是光伏领域中最具有发展前景的材料，但是始终未达到真正的商业化应用，主要原因有二，其一来自于重金属铅的毒性，其二便是暴露于水中甚至是潮湿空气中的自分解特性。一般而言，杂化材料中的有机组分可以大大影响该材料与水分子的氢键结合能力，最终将会直接影响材料的水稳定性。因而MAPbI3极差的水稳定性主要归因于甲胺阳离子上存在强亲水基团-NH3 +。但是目前针对提升杂化钙钛矿水稳定的许多研究仅仅是将较长或较大的烷基链取代甲基，并未消除亲水胺基，因此并不能从根本上解决他们的亲水特性。
设计不含强亲水基团胺基的结构导向剂，是构筑强稳定性杂化材料的关键环节。烷基作为典型的疏水基团，通过设计对应的烷基化反应将芳香杂环上的N原子封闭，可以从根本上杜绝其与水分子形成强氢键的可能，因此我们推测具有N-烷基化有机阳离子作为结构导向剂合成的杂化钙钛矿比具有含亲水基团的杂化物水稳定性更高。基于锑、碘反应原料合成无铅杂化钙钛矿光吸收材料，既保持了杂化钙钛矿直接带隙的特点，使材料具有吸收系数高、载流子迁移率高和易于成膜的优势，又从根本上避免了重金属铅对于环境的污染。该类材料具有优异的光电转换性能，在光电探测及太阳能电池领域具有重要的研究价值。
发明内容
本发明的目的在于以“无强氢键”策略构筑水稳定锑碘基杂化钙钛矿材料，通过将芳香杂环结构导向剂的N原子用烷基封闭，从根本上杜绝材料与外界水分子形成强N–H…O强氢键的可能，克服了现阶段锑基杂化钙钛矿材料在水稳定性方面的不足；合成的材料具有良好的水稳定性，且在300-550 纳米范围内表现出了较强的光学吸收能力，光暗电流比值较高，可应用在光电器件领域。
本发明的技术方案包括以下内容：
1. 一种水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4，式中的Et4ppi表示带有一个单位正电荷4-苯基吡啶阳离子，由4-苯基吡啶中的N原子乙基化形成。该化合物为单斜晶系，结晶于P21/n空间群，单胞参数为a = 7.69埃，b = 19.94埃，c = 13.04埃，α = 90度，β =100.59度，γ = 90度。材料的晶体颜色为橙黄色，表现为离子型有机无机杂化类型的结构。具体结构特征为结构中阳离子为带一个单位正电荷的4-苯基吡啶阳离子，而阴离子则是由三价锑离子和碘离子配位构成的一维阴离子链，该链用于平衡4-苯基吡啶阳离子的正电荷，使整个结构达到电中性；该阴离子链中的锑离子都采用SbI6八面体型配位模式，碘离子采用端基配位或µ2桥基配位模式连接相邻的锑离子；分子内阴阳离子间通过C–H…I弱氢键和库仑相互作用结合在一起，阳离子与外界水分子不形成强氢键。
2. 如项1所述的无机-有机杂化锑碘钙钛矿的用途，其特征在于：该化合物具有亲水性甲胺阳离子钙钛矿不可企及的水稳定性，且具有优异的光电转换性能，作为一种光电探测器的备选材料。
本发明的有益效果为提出一种新颖的合成策略构筑水稳定锑碘基杂化钙钛矿材料，该策略简单、有效，在该策略的指导下，本发明制备的锑碘基杂化钙钛矿，不仅具有优异的光电转换性能还具有增强的水稳定性，可用作光电器件的制作。
附图说明
图1a和图1b分别为水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4的不对称单元和SbI6结构单元图。
图2为水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4分子在单胞内沿a轴的空间堆积图。
图3a和图3b分别为水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4和亲水胺型阳离子钙钛矿(MA)3Sb2I9 (MA = CH3NH3 +)在相同条件下的粉末衍射花样。由图可知，亲水胺型阳离子钙钛矿(MA)3Sb2I9 无法在相对湿度为75%的环境下承受三天，稳定性明显逊于Et4ppi-SbI4。
图4为水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4在光照和黑暗下的电流-电压曲线，材料的光暗电流比值接近2。
图5为水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4刚合成以及75%相对湿度处理三天后的的I-T曲线；在75%相对湿度处理三天后，材料仍然保持较高的光电流响应度，并且在五个循环后未发生明显的电流衰减，证明该材料具有稳定性非常好的光电流响应。
图6为水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4在不同光功率密度光源照射下的电流-电压曲线，随着照射光源光功率密度的增强，该材料的光响应强度逐渐升高。
图7为水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4在不同波长单色光照射下的电流-电压曲线，随着照射光波长的蓝移，材料的光响应电流值逐渐增大，在波长为365纳米的光源照射下，达到最大值，即材料的光电流值与照射光源的波长呈负相关。
图8a为水稳定的锑碘基杂化钙钛矿Et4ppi-SbI4在200到900纳米区间的吸收光谱，在紫外及可见光区均具有较强吸收，图8b为该材料在恒定偏压为5伏特条件下的光电流-波长曲线，与图7具有相同的趋势，即该材料具有优异的光吸收和光电转换性能。
具体实施方式
（1）化合物Et4ppi-SbI4的合成
将0.059克SbCl3和0.031克4-苯基吡啶放入内套玻璃小瓶的25毫升的聚四氟乙烯内胆中，加入0.3毫升HI，1毫升乙醇和5毫升丙酮，然后将聚四氟乙烯内胆放入不锈钢反应釜中，旋紧后放在140摄氏度烘箱中加热，并在此温度下恒温三天，然后冷却至室温，经过处理得到橙黄色晶体，即为化合物Et4ppi-SbI4。
（2）光电化学测试
将5毫克充分研磨的Et4ppi-SbI4粉末分散在0.3毫升乙醇中，球磨三十分钟混匀，然后将3.5微升分散液滴涂在1×1平方厘米的叉指电极上，重复五次，40摄氏度真空干燥四小时后得到薄膜光电极，以滤光片可调节的氙灯为光源，进行线性伏安扫描和计时电位扫描。线性伏安扫描电压范围-5-5伏特，扫速为50毫伏特/秒，计时电位扫描电位为2伏特，快门时间设置为5秒。

Claims (2)

1.一种水稳定锑碘基杂化钙钛矿材料Et4ppi-SbI4，式中的Et4ppi表示带有一个单位正电荷的4-苯基吡啶阳离子，由4-苯基吡啶中的N原子乙基化形成，该化合物为单斜晶系，结晶于P21/n空间群，单胞参数为a = 7.69埃，b = 19.94埃，c = 13.04埃，α = γ = 90度，β= 100.59度，材料的晶体颜色为橙黄色，表现为阴阳离子型有机-无机杂化结构，特征为阳离子为带一个单位正电荷的4-苯基吡啶阳离子，阴离子由三价锑离子和碘离子配位构成的一维阴离子链，整个结构呈电中性，阴阳离子间通过C-H…I弱氢键和库仑相互作用结合在一起，阳离子与外界水分子不形成强氢键。
2.一种权利要求1所述的水稳定锑碘基杂化钙钛矿材料Et4ppi-SbI4的用途，其特征在于：该材料具有增强的水稳定性和优异的光电转换性能，用于光电器件的制作。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109755393A (zh) * 2019-01-16 2019-05-14 济南大学 一种锑碘杂化钙钛矿的溶液法制备与应用
CN110054628A (zh) * 2019-03-25 2019-07-26 济南大学 一种水稳定杂化铅碘钙钛矿材料及其应用
CN110054638A (zh) * 2019-04-26 2019-07-26 济南大学 一种铜碘杂化半导体材料及其光电应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109755393A (zh) * 2019-01-16 2019-05-14 济南大学 一种锑碘杂化钙钛矿的溶液法制备与应用
CN110054628A (zh) * 2019-03-25 2019-07-26 济南大学 一种水稳定杂化铅碘钙钛矿材料及其应用
CN110054638A (zh) * 2019-04-26 2019-07-26 济南大学 一种铜碘杂化半导体材料及其光电应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
The structures, water stabilities and photoluminescence properties of two types of iodocuprate(I)-based hybrids;Xu, Z. Wang et al.;《Dalton Trans.》;20181231;2306-2317 *
以疏水有机阳离子构筑水稳定性增强铅碘杂化晶态材料的研究;刘广宁等;《第三届新型太阳能电池学术研讨会》;20160522;64 *

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