Contribution of Electrolyte Decomposition Products and the Effect of Temperature on the Dissolution of Transition...

A fundamental understanding of aging processes in lithium-ion batteries (LIBs) is imperative in the development of future battery architectures for widespread electrification. Herein, dissolution of transition metals from cathode active materials of LIBs is among the most important degradation processes. Research has demonstrated that elevated operating temperatures accelerate battery degradation. However, the exact mechanism of transition-metal dissolution at elevated temperatures has still to be clarified. Current literature suggests that the reaction rate of dissolution increases with increasing temperature; moreover, the decomposition of electrolytes results in products that also accelerate dissolution processes. Most studies focus on ex situ analyses of thermally treated full cells. This approach is not appropriate to get detailed insights and to distinguish between different contributions. In this work, with the help of real-time dissolution analysis using an electroanalytical flow cell (EFC) coupled to an inductively coupled plasma mass spectrometer (ICP-MS), we present novel details of the temperature effects on in situ dissolution at the cathode electrolyte interface. With fresh electrolytes, we find increased Mn dissolution even at open-circuit conditions as well as with constant voltage polarization when the electrode sample is heated at constant temperatures between 50 and 80 °C. The release of transition metals also responds in a nuanced manner when applying temperature transients. Utilizing electrolytes preheated at 60 and 100 °C, we demonstrate that decomposition products in the bulk electrolyte have no influence on transition-metal (TM) dissolution when constantly flushing the cell with the thermally aged electrolyte samples. Only when keeping the cathode temperature at 60 °C, the dissolution increases by a factor of 2-3. Our findings highlight the interplay between the cathode and electrolyte and provide new insights into the dissolution mechanism of cathode materials.