Chloroaluminate Anion Intercalation in Graphene and Graphite: From Two-Dimensional Devices to Aluminum-Ion Batteries

A rechargeable aluminum-ion battery based on chloroaluminate electrolytes has received intense attention due to the high abundance and chemical stability of aluminum. However, the fundamental intercalation processes and dynamics in these battery systems remain unresolved. Here, the energetics and dynamics of chloroaluminate ion intercalation in atomically thin single crystal graphite are investigated by fabricating mesoscopic devices for charge transport and operando optical microscopy. These mesoscopic measurements are compared to the high-performance rechargeable Al-based battery consisting of a few-layer graphene-multiwall carbon nanotube composite cathode. These composites exhibit a 60% capacity enhancement over pyrolytic graphite, while an ∼3-fold improvement in overall ion diffusivity is also obtained exhibiting ∼1% of those in atomically thin single crystals. Our results thus establish the distinction between intrinsic and ensemble electrochemical behavior in Al-based batteries and show that engineering ion transport in these devices can yet lead to vast improvements in battery performance.