A nonsolvolytic fluorine/LiNO₃-containing electrolyte for stabilizing dynamic interfaces in Li||LiMn₂O₄ batteries

Mn-based high voltage cathodes, e.g., spinel LiMn₂O₄, are considered among the most promising materials for cost-effective, next generation energy storage. When paired with a Li metal anode, secondary batteries based on Li||LiMn₂O₄ in principle offer a straightforward, scalable approach for achieving cost-effective and high energy density storage demanded in applications. In practice, however, such batteries fail to live up to their promise. Rapid capacity fading caused by irreversible Mn dissolution at the cathode coupled with mossy/dendritic Li deposition at the anode limit their useful life. In this study, we report on the design of electrolytes based on a binary blend of two widely available salts, LiNO₃ and LiTFSI, in ethylene carbonate (EC), which simultaneously overcome failure modes at both the cathode and anode of Li||LiMn₂O₄ batteries. The electrolyte design is motivated by a recent finding that compared with their linear counterparts (e.g., dimethyl carbonate), cyclic carbonates like EC dissolve considerably larger amount of LiNO₃, which markedly improves anode reversibility. On the other hand, it is known that nonsolvolytic fluorine-containing Li salts like LiTFSI, lowers the electrolyte's susceptibility to solvolysis, which generates HF species responsible for Mn leaching at the cathode. In particular, we report instead that fluorine groups in the TFSI salt, promote formation of a favorable, fluorine-rich interphase on the Li metal anode. Electrochemical measurements show that the electrolytes enable remarkably improved charge-discharge cycling stability (>1000 charge-discharge cycles) of Li||LiMn₂O₄ batteries. In-depth atomic-resolution electron microscopy and X-ray/synchrotron diffraction experiments reveal the fundamental source of the improvements. The measurements show that crystallographic degradation of Mn-based cathodes (e.g., surface Mn leaching and bulk defect generation) upon cycling in conventional electrolytes is dramatically lowered in the LiNO₃ + LiTFSI/EC electrolyte system. It is shown further that the reduction of Mn dissolution not only improves the cathode stability but improves the reversibility of the Li metal anode via a unique re-deposition mechanism in which Li and Mn co-deposit on the anode. Taken together, our findings show that the LiNO₃ + LiTFSI/EC electrolyte system holds promise for accelerating progress towards practical Li||LiMn₂O₄ batteries because it stabilizes the dynamic interfaces required for long-term stability at both the Li anode and the LiMn₂O₄ cathode.