Hybrid High‐Voltage LiNi_0.5Mn_1.5O₄/Graphite Cathodes Enabling Rechargeable Batteries with Simultaneous Anion‐ and Cation Storage

Abstract A hybrid cathode concept that targets combining the specific advantages of Li‐ion batteries and dual‐ion batteries is proposed. LiNi_0.5Mn_1.5O₄ (LNMO), (de)inserting Li⁺, and graphite, capable to (de)intercalate PF₆⁻ present in the electrolyte, are combined in one cathode, aiming for synergy effects due to the presence of two electrochemically active species to overcome rate limitations caused by electrolyte depletion. Hybrid cathodes of different compositions and designs are prepared and investigated regarding their properties and the storage mechanism using electrochemical analyses combined with operando XRD and extensive materials characterization, including scanning electron microscopy and energy‐dispersive X‐ray spectroscopy. Finally, hybrid cathodes with higher areal capacity are prepared and investigated regarding rate performance. Model‐based analysis of the results reveals design criteria and material properties required to achieve synergistic effects between the components in hybrid cathodes. These insights lay the foundation for a new type of battery with advantageous properties in terms of cost, environmental friendliness, and electrochemical performance.