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

Journal Article · · Batteries & Supercaps
 [1];  [2];  [1];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
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We present a study of the lithium nickel manganese cobalt oxide (LiNi0.6Mn0.2Co0.2O2, 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.
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
OSTI ID:
1767415
Alternate ID(s):
OSTI ID: 1774885
Report Number(s):
BNL--221077-2021-JAAM
Journal Information:
Batteries & Supercaps, Journal Name: Batteries & Supercaps Vol. 4; ISSN 2566-6223
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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