Promising performance of sulfide catholytes compared to halide alternatives in NMC811 cathodes for sheet-type sulfide solid-state batteries

Li, Yuanshun; Kim, Chanho; Cho, Yukio; Musgrove, Amanda L.; Parker, Gabriel D.; Su, Yi-Feng; Sacci, Robert L.; Yu, Xiao-Ying; Zawodzinski, Thomas; Nanda, Jagjit; Yang, Guang

doi:10.1016/j.ensm.2025.104385

Promising performance of sulfide catholytes compared to halide alternatives in NMC811 cathodes for sheet-type sulfide solid-state batteries

Journal Article · Sun Jun 08 04:00:00 EDT 2025 · Energy Storage Materials

DOI:https://doi.org/10.1016/j.ensm.2025.104385· OSTI ID:3002087

^[1]; ^[2]; Cho, Yukio ^[3]; Musgrove, Amanda L. ^[2]; ^[2]; Su, Yi-Feng ^[2]; ^[2]; ^[2]; Zawodzinski, Thomas ^[1]; Nanda, Jagjit ^[3]; ^[4]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Graduate Education

Sulfide-based solid-state batteries (SSBs) show promise in achieving energy densities over 350 Wh/kg, yet challenges persist with their incorporation of high-voltage, nickel-rich layered oxide cathodes, such as LiNi₀.₈Mn₀.₁Co₀.₁O₂ (NMC811), due to the poor oxidation stability of sulfide solid-state electrolytes (SSEs) like Li₆PS₅Cl (LPSCl). Although halide SSEs such as Li₃InCl₆ (LIC) and Li₃YCl₆ (LYC) have previously shown promise in stabilizing high-voltage NMC cathodes, our research reveals that sulfide SSE catholytes, particularly when combined with surface-coated NMC cathodes, deliver superior performance. Here, this investigation assesses the cycling stability of various catholytes—LPSCl, LIC, Li₁₀GeP₂S₁₂ (LGPS), combined LIC-LPSCl, and LYC-LPSCl—in SSBs with LiNbO₃-coated NMC811 cathodes against sheet-type LPSCl separators. Findings indicate that while LGPS-based cathodes maintain higher capacity retention, they yield lower deliverable capacity, and LIC cathodes experience significant electrochemical degradation. Importantly, our results underscore that sulfide SSE catholytes, in conjunction with LiNbO₃-coated cathodes, optimize the cathode-electrolyte interphase (CEI), enhancing both kinetics and mass transport. These insights provide a strategic direction for optimizing catholyte composition in the development of sheet-type sulfide-based SSBs.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO). Advanced Battery Materials Research Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; AC02-76SF00515

OSTI ID:: 3002087

Journal Information:: Energy Storage Materials, Journal Name: Energy Storage Materials Vol. 80; ISSN 2405-8297

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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