Ramirez Daniel, Suto Yusaku, Rosero-Navarro Nataly Carolina, Miura Akira, Tadanaga Kiyoharu, Jaramillo Franklin
Centro de Investigación, Innovación y Desarrollo de Materiales - CIDEMAT, Facultad de Ingeniería , Universidad de Antioquia UdeA , Calle 70 No. 52-21 , Medellín , Colombia.
Inorg Chem. 2018 Apr 2;57(7):4181-4188. doi: 10.1021/acs.inorgchem.8b00397. Epub 2018 Mar 21.
Organic-inorganic hybrid perovskite materials have recently been investigated in a variety of applications, including solar cells, light emitting devices (LEDs), and lasers because of their impressive semiconductor properties. Nevertheless, the perovskite structure has the ability to host extrinsic elements, making its application in the battery field possible. During the present study, we fabricated and investigated the electrochemical properties of three-dimensional (3D) methylammonium lead mixed-halide CHNHPbIBr and two-dimensional (2D) propylammonium-methlylammonium lead bromide (CHNH)(CH(CH)NH)PbBr hybrid perovskite thin films as electrode materials for Li-ion batteries. These electrodes were obtained by solution processing at 100 °C. CHNHPbBr achieved high discharge/charge capacities of ∼500 mA h g /160 mA h g that could account also for other processes taking place during the Li intercalation. It was also found that bromine plays an important role for lithium intercalation, while the new 2D (CHNH)(CH(CH)NH)PbBr with a layered structure allowed reversibility of the lithium insertion-extraction of 100% with capacities of ∼375 mA h g in the form of a thin film. Results suggest that tuning the composition of these materials can be used to improve intercalation capacities, while modification from 3D to 2D layered structures contributes to improving lithium extraction. The mechanism of the lithium insertion-extraction may consist of an intercalation mechanism in the hybrid material accompanying the alloying-dealloying process of the Li Pb intermetallic compounds. This work contributes to revealing the relevance of both composition and structure of potential hybrid perovskite materials as future thin film electrode materials with high capacity and compositional versatility.
有机-无机杂化钙钛矿材料因其令人印象深刻的半导体特性，最近在包括太阳能电池、发光器件（LED）和激光器在内的各种应用中得到了研究。然而，钙钛矿结构能够容纳外来元素，这使得其在电池领域的应用成为可能。在本研究中，我们制备并研究了三维（3D）甲基铵铅混合卤化物CH₃NH₃PbIₓBr₃₋ₓ和二维（2D）丙基铵-甲基铵溴化铅（CH₃NH₃）（CH₃（CH₂）₃NH₃）PbBr₂杂化钙钛矿薄膜作为锂离子电池电极材料的电化学性能。这些电极是通过在100℃下溶液处理获得的。CH₃NH₃PbBr₂实现了约500 mA h g⁻¹/160 mA h g⁻¹的高充放电容量，这也可以解释锂嵌入过程中发生的其他过程。还发现溴在锂嵌入中起重要作用，而具有层状结构的新型二维（CH₃NH₃）（CH₃（CH₂）₃NH₃）PbBr₂以薄膜形式实现了锂插入-脱出的100%可逆性，容量约为375 mA h g⁻¹。结果表明，调整这些材料的组成可用于提高嵌入容量，而从3D到2D层状结构的改性有助于提高锂脱出。锂插入-脱出的机制可能包括混合材料中的嵌入机制以及Li-Pb金属间化合物的合金化-脱合金化过程。这项工作有助于揭示潜在的杂化钙钛矿材料的组成和结构与未来具有高容量和组成多功能性的薄膜电极材料的相关性。
