Molecular Understanding of Li Metal Anode

Developing new liquid electrolyte is a promising approach to enable the next-generation high-energy Li metal battery for wide-ranging application such as electric vehicles (EV). However, the high reactivity of Li metal interface renders it crucial to form favorable solid-electrolyte interphase (SEI), via active electrolyte decomposition, for highly reversible operation of Li-metal anode (LMA). Therefore, deeply understanding how the molecular structures of electrolyte species precisely control both the interfacial reactivity and the operational reversibility of LMA, can further guide and inspire new electrolyte systems with progressively improved battery performance. Herein, we systematically investigated the impact of Li salts with different imide anions dissolved in ether-based solvent, on the resulting Coulombic efficiencies (CE) of LMA, whereas beneficial and detrimental molecular motifs were first identified. By leveraging the non-washing XPS protocol newly developed at Stanford, we managed to uncover the distinct molecular reactivity leading to reductive bond cleavage as well as new bond formation at Li-metal potential. Such nanoscale reactivity of SEI-forming reactions was discovered to profoundly govern the macroscopic performance of LMA, which simultaneously emphasized the significance of electric double layer (EDL). Importantly, aided by gas-titration experiments to quantify the by-products in SEI, we revealed the critical molecular origins of irreversible capacity loss of LMA during continuous Li-metal plating and stripping. These new insights allow us to formulate rational strategies of molecular engineering to design LMA interface with high reversibility and minimal side reactivity.