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

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

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

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

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

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. 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.

Original language	English
Article number	104385
Journal	Energy Storage Materials
Volume	80
DOIs	https://doi.org/10.1016/j.ensm.2025.104385
State	Published - Jul 2025

Funding

This research was conducted at the Oak Ridge National Laboratory, managed by UT Battelle, LLC for the U.S. Department of Energy (DOE) and is sponsored by the Office of Energy Efficiency and Renewable Energy (EERE) in the Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program, managed by Dr. Simon Thompson and Mr. Tien Duong. This manuscript has been authored by UT- Battelle, LLC under Contract No DE-AC05\u201300OR22725 with the U.S. Department of Energy. SEM and TOF-SIMS research were conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. XPS was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-2026822. The use of the Stanford Synchrotron Radiation Lightsource at SLAC National Accelerator Laboratory is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No DE-AC02\u201376SF00515. Y. C. was supported by the Japan Society for the Promotion of Science (JSPS) overseas research fellowship and the Stanford Energy Postdoctoral Fellowship and the Precourt Institute for Energy.

Keywords

Catholyte
Composite cathode
Sulfide solid-state batteries

Access to Document

10.1016/j.ensm.2025.104385

Cite this

Li, Y., Kim, C., Cho, Y., Musgrove, A. L., Parker, G. D., Su, Y. F., Sacci, R. L., Yu, X.-Y., Zawodzinski, T., Nanda, J., & Yang, G. (2025). Promising performance of sulfide catholytes compared to halide alternatives in NMC811 cathodes for sheet-type sulfide solid-state batteries. Energy Storage Materials, 80, Article 104385. https://doi.org/10.1016/j.ensm.2025.104385

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

abstract = "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. 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.",

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author = "Yuanshun Li and Chanho Kim and Yukio Cho and Musgrove, \{Amanda L.\} and Parker, \{Gabriel D.\} and Su, \{Yi Feng\} and Sacci, \{Robert L.\} and Xiao-Ying Yu and Thomas Zawodzinski and Jagjit Nanda and Guang Yang",

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AU - Li, Yuanshun

AU - Kim, Chanho

AU - Cho, Yukio

AU - Musgrove, Amanda L.

AU - Parker, Gabriel D.

AU - Su, Yi Feng

AU - Sacci, Robert L.

AU - Yu, Xiao-Ying

AU - Zawodzinski, Thomas

AU - Nanda, Jagjit

AU - Yang, Guang

PY - 2025/7

Y1 - 2025/7

N2 - 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. 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.

AB - 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. 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.

KW - Catholyte

KW - Composite cathode

KW - Sulfide solid-state batteries

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DO - 10.1016/j.ensm.2025.104385

M3 - Article

AN - SCOPUS:105007989744

SN - 2405-8297

VL - 80

JO - Energy Storage Materials

JF - Energy Storage Materials

M1 - 104385

ER -

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

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