Amorphous Chloride Solid Electrolytes with High Li-Ion Conductivity for Stable Cycling of All-Solid-State High-Nickel Cathodes

Solid electrolytes (SEs) are central components that enable high-performance, all-solid-state lithium batteries (ASSLBs). Amorphous SEs hold great potential for ASSLBs because their grain-boundary-free characteristics facilitate intact solid–solid contact and uniform Li-ion conduction for high-performance cathodes. However, amorphous oxide SEs with limited ionic conductivities and glassy sulfide SEs with narrow electrochemical windows cannot sustain high-nickel cathodes. Herein, we report a class of amorphous Li–Ta–Cl-based chloride SEs possessing high Li-ion conductivity (up to 7.16 mS cm^–1) and low Young’s modulus (approximately 3 GPa) to enable excellent Li-ion conduction and intact physical contact among rigid components in ASSLBs. We reveal that the amorphous Li–Ta–Cl matrix is composed of LiCl₄^3–, LiCl₅^4–, LiCl₆^5– polyhedra, and TaCl₆^– octahedra via machine-learning simulation, solid-state ⁷Li nuclear magnetic resonance, and X-ray absorption analysis. Attractively, our amorphous chloride SEs exhibit excellent compatibility with high-nickel cathodes. We demonstrate that ASSLBs comprising amorphous chloride SEs and high-nickel single-crystal cathodes (LiNi_0.88Co_0.07Mn_0.05O₂) exhibit ∼99% capacity retention after 800 cycles at ∼3 C under 1 mA h cm^–2 and ∼80% capacity retention after 75 cycles at 0.2 C under a high areal capacity of 5 mA h cm^–2. Most importantly, a stable operation of up to 9800 cycles with a capacity retention of ∼77% at a high rate of 3.4 C can be achieved in a freezing environment of −10 °C. Our amorphous chloride SEs will pave the way to realize high-performance high-nickel cathodes for high-energy-density ASSLBs.