RESUMEN
Lithium-ion batteries (LiBs) with graphite as an anode and lithiated transition metal oxide as a cathode are approaching their specific energy and power theoretical values. To overcome the limitations of LiBs, lithium metal anode with high specific capacity and low negative redox potential is necessary. However, practical application in rechargeable cells is hindered by uncontrolled lithium deposition manifesting, for instance, as Li dendrite growth which can cause formation of dead Li, short circuits and cell failure. The electrochemical behaviour of a protic additive (NH4PF6) in a carbonate-based electrolyte has been investigated by operando confocal Raman spectroscopy, in situ optical microscopy, and X-ray photoelectron spectroscopy, elucidating its functional mechanism. The ammonium cation promotes a chemical modification of the lithium metal anode-electrolyte interphase by producing an N-rich solid electrolyte interphase and chemically modifying the lithium surface morphology by electrochemical pitting. This novel method results in stable lithium deposition and stripping by a decreasing the local current density on the electrode, thus limiting dendritic deposition.