A Series of Ternary Metal Chloride Superionic Conductors for High‐Performance All‐Solid‐State Lithium Batteries

作者：Liang Jianwen; Maas Eveline; Luo Jing; Li Xiaona; Chen Ning; Adair Keegan R.; Li Weihan; Li Junjie; Hu Yongfeng; Liu Jue; Zhang Li; Zhao Shangqian; Lu Shigang; Wang Jiantao; Huang Huan; Zhao Wenxuan; Parnell Steven; Smith Ronald I.; Ganapathy Swapna; Wagemaker Marnix; Sun Xueliang

来源：Advanced Energy Materials, 2022, 12(21).

DOI：10.1002/AENM.202103921

• all‐solid‐state Li batteries
• energy storage
• halides
• solid‐state electrolytes
• superionic conductors

Understanding the relationship between structure, ionic conductivity, and synthesis is the key to the development of superionic conductors. Here, a series of Li3‐3xM1+xCl6 (−0.14 < x ≤ 0.5, M = Tb, Dy, Ho, Y, Er, Tm) solid electrolytes with orthorhombic and trigonal structures are reported. The orthorhombic phase of Li–M–Cl shows an approximately one order of magnitude increase in ionic conductivities when compared to their trigonal phase. Using the Li–Ho–Cl components as an example, their structures, phase transition, ionic conductivity, and electrochemical stability are studied. Molecular dynamics simulations reveal the facile diffusion in the z‐direction in the orthorhombic structure, rationalizing the improved ionic conductivities. All‐solid‐state batteries of NMC811/Li2.73Ho1.09Cl6/In demonstrate excellent electrochemical performance at both 25 and −10 °C. As relevant to the vast number of isostructural halide electro...