In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

Tremolet de Villers, Bertrand J.; Bak, Seong‐Min; Yang, Junghoon; Han, Sang‐Don

doi:10.1002/batt.202000259

Title: In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

Journal Article · Thu Jan 28 00:00:00 EST 2021 · Batteries & Supercaps

DOI:https://doi.org/10.1002/batt.202000259· OSTI ID:1767415

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National Renewable Energy Lab. (NREL), Golden, CO (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

We present a study of the lithium nickel manganese cobalt oxide (LiNi_0.6Mn_0.2Co_0.2O₂, NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Furthermore, our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; AC36-08GO2830

OSTI ID:: 1767415

Report Number(s):: BNL-221077-2021-JAAM

Journal Information:: Batteries & Supercaps, Vol. 4; ISSN 2566-6223

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
in situ ATR FTIR
cathode electrolyte interphase
electrolyte solution structure
transition metal redox
surface layer evolution

Title: In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

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