For achieving higher energy density lithium-ion batteries, the improvement of cathode active materials is crucial. The most promising cathode materials are nickel-rich layered oxides LiNixCoyMnzO2 (NCM) and over lithiated NCM (often called HE-NCM). Unfortunately, the full capacity of NCM cannot be utilized due to its limited cycle-life at high state-of-charge (SOC), while HE-NCM requires high voltages. By operando emission spectroscopy, we show for the first time that highly reactive singlet oxygen is released when charging NCM and HE-NCM to an SOC beyond ˜80%. In addition, on-line mass-spectrometry reveals the evolution of CO and CO2 once singlet oxygen is detected, providing significant evidence for the reaction between singlet oxygen and electrolyte to be a chemical reaction. It is controlled by the SOC rather than by potential, as would be the case for a purely electrochemical electrolyte oxidation. Singlet oxygen formation therefore imposes a severe challenge to the development of high-energy batteries based on layered oxide cathodes, shifting the focus of research from electrochemically stable 5?V-electrolytes to chemical stability toward singlet oxygen.

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DOI: 10.1016/j.mattod.2018.03.037