Entropy‐Driven 60 mol% Li Electrolyte for Li Metal‐Free Batteries

Highly Li-concentrated electrolytes are acknowledged for their compatibility with Li metal negative electrodes and high voltage positive electrodes to achieve high-energy Li metal batteries, showcasing stable and facile interfaces for Li deposition/dissolution and high anodic stability. This study aims to explore a highly concentrated electrolyte by adopting entropy-driven chemistry for Li metal-free (so-called anode-free) batteries. The combination of lithium bis(fluorosulfonyl)amide (LiFSA) and lithium trifluoromethanesulfonate (LiOTf) salts in a pyrrolidinium-based ionic liquid is found to significantly modify the coordination structure, resulting in an unprecedented 60 mol% Li concentration and a low solvent-to-salt ratio of 0.67:1 in the electrolyte system. This novel 60 mol% Li electrolyte demonstrates unique coordination stricture, featuring a high ratio of monodentate-anion structures and aggregates, which facilitates an enhanced Li⁺ transference number and improved anodic stability. Moreover, the developed electrolyte provides a facile de-coordination process and leads to the formation of an anion-based solid electrolyte interface, which enables stable Li deposition/dissolution properties and demonstrates excellent cycling stability in the Li metal-free full cell with a Li[Ni_0.8Co_0.1Mn_0.1]O₂ (NCM811) positive electrode.