Characterization of the surface of positive electrodes for Li-ion batteries using 7Li MAS NMR

The growth and evolution of the interphase, due to contact with the ambient atmosphere or electrolyte, are followed using 7Li magic-angle spinning nuclear magnetic resonance (MAS NMR) in the case of two materials amongst the most promising candidates for positive electrodes for lithium batteries: LiFePO4 and LiMn0.5Ni0.5O2. The use of appropriate experimental conditions to acquire the NMR signal allows observing only the «diamagnetic» lithium species at the surface of the grains of active material. The reaction of LiMn0.5Ni0.5O2 with the ambient atmosphere or LiPF6 (1 M in Ethylene Carbonated/DiMéthyl Carbonate (EC/DMC)) electrolyte is extremely fast and leads to an important amount of lithium-containing diamagnetic species compared to what can be observed in the case of LiFePO4. The two studied materials display a completely different surface chemistry in terms of reactivity and/or kinetics of the surface towards electrolyte. Moreover, these results show that MAS NMR is a very promising tool to monitor phenomena taking place at the interface between electrode and electrolyte.

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