We introduce an intermediate-temperature (350 °C) dry molten sodium hydroxide-mediated binder-free electrodeposition process to grow the previously electrochemically inaccessible air- and moisture-sensitive layered sodium transition metal oxides, NaxMO2 (M = Co, Mn, Ni, Fe), in both thin and thick film form, compounds which are conventionally synthesized in powder form by solid-state reactions at temperatures ≥700 °C. As a key motivation for this work, several of these oxides are of interest as cathode materials for emerging sodium-ion–based electrochemical energy storage systems. Despite the low synthesis temperature and short reaction times, our electrodeposited oxides retain the key structural and electrochemical performance observed in high-temperature bulk synthesized materials. We demonstrate that tens of micrometers thick >75% dense NaxCoO2 and NaxMnO2 can be deposited in under 1 h. When used as cathodes for sodium-ion batteries, these materials exhibit near theoretical gravimetric capacities, chemical diffusion coefficients of Na+ ions (∼10−12 cm2⋅s−1), and high reversible areal capacities in the range ∼0.25 to 0.76 mA⋅h⋅cm−2, values significantly higher than those reported for binder-free sodium cathodes deposited by other techniques. The method described here resolves longstanding intrinsic challenges associated with traditional aqueous solution-based electrodeposition of ceramic oxides and opens a general solution chemistry approach for electrochemical processing of hitherto unexplored air- and moisture-sensitive high valent multinary structures with extended frameworks.
Transition Metal Oxide Anodes for Electrochemical Energy Storage in Lithium‐ and Sodium‐Ion Batteries