Cation Co-Intercalation with Anions: The Origin of Low Capacities of Graphite Cathodes in Multivalent Electrolytes

Dual-ion batteries involving anion intercalation into graphite cathodes represent promising battery technologies for low-cost and high-power energy storage. However, the fundamental origins regarding much lower capacities of graphite cathodes in earth abundant and inexpensive multivalent electrolytes than in Li-ion electrolytes remain elusive. Herein, we reveal that the limited anion-storage capacity of a graphite cathode in multivalent electrolytes is rooted in the abnormal multivalent-cation co-intercalation with anions in the form of large-sized anionic complexes. This cation co-intercalation behavior persists throughout the stage evolution of graphite intercalation compounds and leads to a significant decrease of sites practically viable for capacity contribution inside graphite galleries. Further systematic studies illustrate that the phenomenon of cation co-intercalation into graphite is closely related to the high energy penalty of interfacial anion desolvation due to the strong cation-anion association prevalent in multivalent electrolytes. Leveraging this understanding, we verify that promoting ionic dissociation in multivalent electrolytes by employing high-permittivity and oxidation-tolerant co-solvents is effective in suppressing multivalent-cation co-intercalation and thus achieving increased capacity of graphite cathodes. For instance, introducing adiponitrile as a co-solvent to a Mg²⁺-based carbonate electrolyte leads to 83% less Mg²⁺ co-intercalation and a ∼29.5% increase in delivered capacity of the graphite cathode.