Kim, Se Young Bak, Seong-Min Jun, Kyujung Ceder, Gerbrand Chen, Guoying 2024-05-16T09:00:04Z 2024-05-16T09:00:04Z 2024-05-16 2024-07 1614-6832 https://pubs.kist.re.kr/handle/201004/149844 All-solid-state-batteries (ASSBs) based on a halide solid electrolyte (SE) and a lithium-metal based anode typically have poor cyclability without a buffer layer (such as Li3PS4 or Li6PS5Cl) to prevent the degradation reactions. Here excellent cycling stability of ASSB consisting of an uncoated single-crystal LiNi0.8Co0.1Mn0.1O2 cathode and a Li3YCl6 (LYC) SE separator in direct contact with a Li-In anode are demonstrated. Through a combination of electrochemical measurements, synchrotron micro-X-ray absorption and diffraction analyses, and density functional theory calculations, reveal for the first time that along with the standard Li+ transport during charge/discharge, indium in the Li-In anode also participates in the redox reactions. The in-situ generated In3+ preferentially occupies the vacant Li sites in the trigonal LYC lattice, leading to the formation, growth, and eventual stabilization of an anode-electrolyte interphase (AEI) layer consisting of an In-doped Li3-xInxYCl6 (x = approximate to 0.2) phase. It is discussed how the presence of such an AEI layer prevents LYC decomposition and suppresses dendrite formation and propagation, enabling stable cycling of ASSB with approximate to 90% capacity retention over 1000 cycles. This work sheds light on the dynamic evolution of the halide SE and alloy anode interphase, and opens new avenues in the future design of long-lasting high-energy all-solid-state-batteries. This study reveals In redox reactions at the interface between a halide solid-electrolyte and a Li-In alloy anode. The migration of the in situ generated In3+ leads to the formation, growth, and eventual stabilization of a Li3-xInxYCl6 anode-electrolyte interphase over cycling. Such dynamic evolution enables the excellent performance of high-energy NMC811 all-solid-state-battery cells, with approximate to 90% capacity retention after 1000 cycles. image English Wiley-VCH Verlag Revealing Dynamic Evolution of the Anode-Electrolyte Interphase in All-Solid-State Batteries with Excellent Cyclability Article 10.1002/aenm.202401299 1 Advanced Energy Materials, v.14, no.27 Advanced Energy Materials 14 27 N scie scopus 001210963600001 2-s2.0-85191768311 Chemistry, Physical Energy & Fuels Materials Science, Multidisciplinary Physics, Applied Physics, Condensed Matter Chemistry Energy & Fuels Materials Science Physics Article COVALENCY GROWTH RAY-ABSORPTION SPECTROSCOPY CHLORINE K-EDGE LITHIUM-ION STABILITY CONDUCTIVITY halide solid electrolyte Li-In anode NMC cathode all-solid-state batteries anode-electrolyte interface