Tuning Interfacial Processes in Mn-Based Li-Ion Systems Though Vapor Phase Modification

Abstract

Among the different rechargeable battery technologies available, Co/Ni/Mn-based Li-ion systems appear to be a leading contender for automotive applications as a result of their high specific energy. However, the high operating potential of this system is outside the thermodynamic stability window of standard organic carbonate-based electrolytes. This results in electrolyte oxidation with transition metal dissolution and gas formation at the electrode/electrolyte interface during cycling, which leads to severe loss of electrochemical performance. To address these challenges, many strategies are currently being investigated, ranging from the development of new electrodes and electrolytes to the improvement of commercial Li-ion systems by surface engineering of the interfaces.In this work, we mitigate parasitic interfacial processes in start/stop batteries by atomic layer deposition (ALD). We develop an Al2O3 or LiPON conformal artificial SEI layer on LMO and LTO electrodes and study its effect on the Li-ion batteries failure modes with differential electrochemical mass spectroscopy (DEMS), X-ray Photoelectron Spectroscopy (XPS) and ICP measurements. The beneficial impact of the protection layer on the kinetics of the gassing, metal dissolution and associated chemical cross-talk was clearly identified. The presence of a protection layer at the LMO surface, in particular of a 10 nm LiPON conformal layer, mitigate the electrolyte oxidation at high voltage at 60°C with a significant reduction of the amount of H2 produced. The formation of metal complexes and subsequent poisoning of the SEI is also attenuated. Interestingly, counter intuitively, the ratio of the inorganic to organic components of the SEI is lowered by the presence of an inorganic protection layer. The correlation between the nature of the electrode protection layer, the electrode’s surface activity, and associated organic electrolyte oxidation pathways will be presented and discussed. Acknowledgement This work was supported by SAFT and as part of the Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science.