Five Volts Lithium Batteries with Advanced Carbonate‐Based Electrolytes: A Rational Design via a Trio‐Functional Addon Materials

Abstract Lithium metal batteries paired with high‐voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) cathodes are a promising energy storage source for achieving enhanced high energy density. Forming durable and robust solid‐electrolyte interphase (SEI) and cathode‐electrolyte interface (CEI) and the ability to withstand oxidation at high potentials are essential for long‐lasting performance. Herein, advanced electrolytes are designed via trio‐functional additives to carbonate‐based electrolytes for 5 V Li||LNMO and graphite||LNMO cells achieving 88.3% capacity retention after 500 charge–discharge cycles. Theoretical calculations reveal that adding adiponitrile facilitates the presence of more hierarchical DFOB − and PF 6 − dual anion structure in the solvation sheath, leading to a faster de‐solvation of the Li cation. By combining both fluorine and nitrile additives, an efficient synergistic effect is obtained, generating robust thin inorganic SEI and CEI films, respectively. These films enhance microstructural stability; Li dendrite growth on the Li electrode is being suppressed at the anode side and transition‐metals dissolution from the cathode is being mitigated, as evidenced by cryo‐transmission electron microscopy and synchrotron studies.