Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

Kochetkov, Ivan; Zuo, Tong-Tong; Ruess, Raffael; Singh, Baltej; Zhou, Laidong; Kaup, Kavish; Janek, Jürgen; Nazar, Linda

doi:10.1039/d2ee00803c

Title: Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

Journal Article · Fri Jul 29 00:00:00 EDT 2022 · Energy & Environmental Science

DOI:https://doi.org/10.1039/d2ee00803c· OSTI ID:1982246

Kochetkov, Ivan ^[1]; Zuo, Tong-Tong ^[2]; Ruess, Raffael ^[2]; Singh, Baltej ^[3];

^[3]; Kaup, Kavish ^[3];

^[2];

^[3]

University of Waterloo, Ontario (Canada)
Justus Liebig University, Giessen (Germany)
University of Waterloo, Ontario (Canada); Argonne National Laboratory (ANL), Argonne, IL (United States)

A deep understanding of the interaction of the surface of cathode materials with solid electrolytes is crucial to design advanced solid-state batteries (SSBs). This is especially true for the new class of lithium metal chloride (Li-M-Cl) solid electrolytes which are receiving rapidly growing attention due to their very high oxidative stability (>4 V) in combination with good ionic conductivity that can enable long cell cycle life. While Li-M-Cl electrolytes typically contain resource-limited metals (M) such as indium or rare earths, work has focused on substituting M with more abundant elements such as zirconium. Via operando resistance measurements using intermittent current interruption we explore the dynamic evolution of the interphase at the surface of Ni-rich NCM85 or NCM111 cathode particles inside a working SSB with three different Li-(M₁,M₂)-Cl catholytes (Li₃InCl₆, Li₂Sc_1/3In_1/3Cl₄ and Li_5/2Y_1/2Zr_1/2Cl₆) to reveal the impact of the cationic metal substitution on the interfacial chemistry. We show that the metal plays a critical role in determining high voltage stability, contrary to prior assumptions. Using a combination of cyclic voltammetry and ultraviolet photoelectron spectroscopy measurements of the electronic band structure to assess oxidative stability; coupled with DFT calculations and ToF-SIMS to evaluate products formed at the interface at different upper cutoff potentials and degrees of delithiation, we are able to differentiate between electrochemical and chemical degradation. We find that Li₂Sc_1/3In_1/3Cl₄ yields the highest (and Li₃InCl₆ the lowest) stability against electrochemical oxidation, while Li_5/2Y_1/2Zr_1/2Cl₆ undergoes a detrimental chemical reaction with oxygen released from Ni-rich NCM85 at high potentials, resulting in fast capacity fading. Altogether, our work establishes a platform for the metrics and an approach that can be utilized to efficiently evaluate the stability of new halide SEs in SSB cells.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1982246

Alternate ID(s):: OSTI ID: 1880398

Journal Information:: Energy & Environmental Science, Vol. 15, Issue 9; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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