Revising the pathways of Li reaction with organic carbonates
Metallic lithium electrode has major concerns such as extremely high reactivity and nonuniform needle-like electrodeposition limiting its wide application as a negative electrode in secondary batteries. Its reactions with electrolyte leading to solid electrolyte interphase (SEI) formation play an important role, and controlling its composition and properties can help to overcome both difficulties. Even though solid electrolyte interphase chemistry and properties seem to be well known, many surface chemistry experiments reported are not perfect with respect purity needed for Li studies and can be interpreted alternatively. Here, we studied reactions between lithium and propylene carbonate and ethylene carbonate in model reactions realized in ultra-high vacuum. In addition to already reported reaction pathway yielding lithium carbonate and semicarbonate, our theoretical (DFT) modeling confirms thе preference of alternative routes. Along with the most beneficial final lithium carbonates, dilithium 1,2-dialkoxide (DD) can form barierlessly as a final product by two-electron transfer. Experimental XPS/NEXAFS studies of model reactions in the gas phase and solid-gas reaction revealed that in both cases, DD is the main reaction product. Understanding of the discovered reaction pathway can also be essential for reactions in liquid electrolytes, although low electric conductivity of SEI makes it less probable.