On the Decomposition of Carbonate-Based Lithium-Ion Battery Electrolytes Studied Using Operando Infrared Spectroscopy


Infrared diagnostic, Electrolyte decomposition, SEI formation, Thermal degradation, Li-ion battery


A novel infrared diagnostic for operando measurements of electrolyte decomposition is reported. The diagnostic was used to study the decomposition of LiPF6/EC/DEC electrolyte in LCO/graphite Li-ion cells. During formative cycles spectra revealed electrochemical reduction of the EC carbonyl group, which corresponded to simultaneous SEI formation on the graphite anode. This observation supplements current theories of EC decomposition during SEI formation. Operating LCO half-cells at voltages above 4.2 V caused permanent battery capacity loss but no observable electrolyte degradation, indicating the LCO electrode is degraded at high voltage. Infrared thermometry was used to measure the temperature of the electrolyte during heated tests. Operating cells at temperatures above 70◦C resulted in SEI and electrolyte decomposition. Operando spectra collected during heating revealed EC ring-opening as the mechanism of thermal degradation, which resulted in permanent capacity loss. EC thermal decomposition was identical in all cells tested, indicating a homogeneous decomposition reaction independent of electrode material or potential. Thermal stability decreased with increased salt concentration indicating that decomposition is likely catalyzed by LiPF6 decomposition products. Thus, thermal decomposition is not caused by continued reduction reactions on the anode due to SEI failure, as EC reduction and EC thermal decomposition have different mechanisms.

Original Publication Citation

N Saqib, CM Ganim, AE Shelton, JM Porter, On the Decomposition of Carbonate-Based Lithium-Ion Battery Electrolytes Studied Using Operando Infrared Spectroscopy, Journal of The Electrochemical Society (2019) 165 (16), A4051-A4057.

Document Type

Peer-Reviewed Article

Publication Date



The Electrochemical Society




Ira A. Fulton College of Engineering and Technology


Mechanical Engineering

University Standing at Time of Publication

Associate Professor