Mo Hongsheng, Yin Yi-Chen, Luo Jin-Da, Yang Jing-Tian, Li Feng, Huang Dong-Mei, Zhang Hongjun, Ye Bangjiao, Tian Te, Yao Hong-Bin
Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, China.
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, Anhui, China.
ACS Appl Mater Interfaces. 2022 Apr 20;14(15):17479-17485. doi: 10.1021/acsami.2c02078. Epub 2022 Apr 7.
Exploring new solid electrolytes (SEs) for lithium-ion conduction is significant for the development of rechargeable all-solid-state lithium batteries. Here, a lead-free organic-inorganic halide perovskite, MASrLiCl (MA = methylammonium, CHNH in formula), is reported as a new SE for Li-ion conduction due to its highly symmetric crystal structure, inherent soft lattice, and good tolerance for composition tunability. Via density functional theory calculations, we demonstrate that the hybrid perovskite framework can allow fast Li-ion migration without the collapse of the crystal structure. The influence of the lithium content in MASrLiCl ( = 0.1, 0.2, 0.3, or 0.4) on Li migration is systematically investigated. At the lithium content of = 0.2, the MASrLiCl achieves the room-temperature lithium ionic conductivity of 7.0 × 10 S cm with a migration energy barrier of ∼0.47 eV. The lithium-tin alloy (Li-Sn) symmetric cell exhibits stable electrochemical lithium plating/stripping for nearly 100 cycles, indicating the alloy anode compatibility of the MASrLiCl SE. This lead-free organic-inorganic halide perovskite SE will open a new avenue for exploring new SEs.
探索用于锂离子传导的新型固体电解质(SEs)对于可充电全固态锂电池的发展具有重要意义。在此,报道了一种无铅有机-无机卤化物钙钛矿MASrLiCl(MA = 甲铵,化学式中的CH₃NH₃)作为一种新型锂离子传导SE,这归因于其高度对称的晶体结构、固有的软晶格以及对成分可调性的良好耐受性。通过密度泛函理论计算,我们证明了混合钙钛矿框架能够允许锂离子快速迁移而不会导致晶体结构崩塌。系统研究了MASrLiCl中锂含量(x = 0.1、0.2、0.3或0.4)对锂迁移的影响。在锂含量x = 0.2时,MASrLiCl实现了室温下7.0×10⁻⁴ S cm⁻¹的锂离子电导率,迁移能垒约为0.47 eV。锂-锡合金(Li-Sn)对称电池在近100个循环中表现出稳定的电化学锂沉积/剥离,表明MASrLiCl SE与合金阳极具有兼容性。这种无铅有机-无机卤化物钙钛矿SE将为探索新型SEs开辟一条新途径。