Virtual electrode XPS experiments on Li 3−x Sc 1−x Zr x Cl ₆ (x ∼ 0.2): Oxygen-mediated interface passivation on metallic lithium anodes
- 1Department of Chemistry
- 2Colorado School of Mines
- 3National Laboratory of the Rockies
Abstract
Lithium metal chlorides are a promising class of solid-state electrolyte (SSE) materials that may enable the use of lithium anodes for next-generation electrochemical energy storage. Zr-substituted Li 3 ScCl 6 (Li 3-x Sc 1-x Zr x Cl 6 ), combines the high ionic conductivities of Li 3 ScCl 6 with the moisture resistance of Li 2 ZrCl 6 that facilitates processing and manufacturing. However, little is known about the solid electrolyte interphase (SEI) formation and composition at the Li 3-x Sc 1-x Zr x Cl 6 and Li metal anode interfacial region. Elucidating the relevant (electro)chemical processes is crucial for engineering Li 3-x Sc 1-x Zr x Cl 6 | Li 0 interfaces with low interfacial impedances and long-term cycling stability. Here, we utilize the virtual-electrode X-ray photoelectron spectroscopy (VE-XPS) technique study the formation and early-stage evolution of the SEI. Additionally, we investigate the long-term effects of galvanostatic cycling on the ion transport properties and how SEI evolution impacts the overall electrochemical impedance of Li 2.8 Sc 0.8 Zr 0.2 Cl 6 -based cells. Our results show the initial SEI formation diverges from thermodynamic phase decomposition predictions due to the presence of oxygen, leading to formation of a novel Li-Sc-Zr-oxide (LSZO) phase that is compositionally similar to Li 7 La 3 Zr 2 O 12 (LLZO). For the early-stage SEI, this oxygen-mediated decomposition pathway appears to mitigate reduction of the metal cations and prevent the formation of metallic phases (e.g., metallic Zr, Sc, and Sc-Zr alloys). We find that LSZO phase formation effectively passivates the Li 2.8 Sc 0.8 Zr 0.2 Cl 6 | Li 0 interface and enables plating and stripping of metallic lithium.
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BibTeX
@misc{combs2026virtual,
title = {{Virtual electrode XPS experiments on Li 3−x Sc 1−x Zr x Cl ₆ (x ∼ 0.2): Oxygen-mediated interface passivation on metallic lithium anodes}},
author = {Sinclair R. Combs and Zachary J. Berquist and Annalise E. Maughan and Glenn Teeter},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15011105/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011105/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Virtual electrode XPS experiments on Li 3−x Sc 1−x Zr x Cl ₆ (x ∼ 0.2): Oxygen-mediated interface passivation on metallic lithium anodes
AU - Sinclair R. Combs
AU - Zachary J. Berquist
AU - Annalise E. Maughan
AU - Glenn Teeter
PY - 2026
DA - 2026/10/27
PB - ChemRxiv
DO - 10.26434/chemrxiv.15011105/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011105/v1
AB - Lithium metal chlorides are a promising class of solid-state electrolyte (SSE) materials that may enable the use of lithium anodes for next-generation electrochemical energy storage. Zr-substituted Li 3 ScCl 6 (Li 3-x Sc 1-x Zr x Cl 6 ), combines the high ionic conductivities of Li 3 ScCl 6 with the moisture resistance of Li 2 ZrCl 6 that facilitates processing and manufacturing. However, little is known about the solid electrolyte interphase (SEI) formation and composition at the Li 3-x Sc 1-x Zr x Cl 6 and Li metal anode interfacial region. Elucidating the relevant (electro)chemical processes is crucial for engineering Li 3-x Sc 1-x Zr x Cl 6 | Li 0 interfaces with low interfacial impedances and long-term cycling stability. Here, we utilize the virtual-electrode X-ray photoelectron spectroscopy (VE-XPS) technique study the formation and early-stage evolution of the SEI. Additionally, we investigate the long-term effects of galvanostatic cycling on the ion transport properties and how SEI evolution impacts the overall electrochemical impedance of Li 2.8 Sc 0.8 Zr 0.2 Cl 6 -based cells. Our results show the initial SEI formation diverges from thermodynamic phase decomposition predictions due to the presence of oxygen, leading to formation of a novel Li-Sc-Zr-oxide (LSZO) phase that is compositionally similar to Li 7 La 3 Zr 2 O 12 (LLZO). For the early-stage SEI, this oxygen-mediated decomposition pathway appears to mitigate reduction of the metal cations and prevent the formation of metallic phases (e.g., metallic Zr, Sc, and Sc-Zr alloys). We find that LSZO phase formation effectively passivates the Li 2.8 Sc 0.8 Zr 0.2 Cl 6 | Li 0 interface and enables plating and stripping of metallic lithium.
ER -