Fast-Charging Capability of Thin-Film Prussian Blue Analogue Electrodes for Aqueous Sodium-Ion Batteries

Prussian blue analogues are considered as promising candidates for aqueous sodium-ion batteries providing a decently high energy density for stationary energy storage. However, suppose the operation of such materials under high-power conditions could be facilitated. In that case, their application might involve fast-response power grid stabilization and enable short-distance urban mobility due to fast re-charging. In this work, sodium nickel hexacyanoferrate thin-film electrodes are synthesized via a facile electrochemical deposition approach to form a model system for a robust investigation. Their fast-charging capability is systematically elaborated with regard to the electroactive material thickness in comparison to a ″traditional″ composite-type electrode. It is found that quasi-equilibrium kinetics allow extremely fast (dis)charging within a few seconds for sub-micron film thicknesses. Specifically, for a thickness below ≈ 500 nm, 90% of the capacity can be retained at a rate of 60C (1 min for full (dis)charge). A transition toward mass transport control is observed when further increasing the rate, with thicker films being dominated by this mode earlier than thinner films. This can be entirely attributed to the limiting effects of solid-state diffusion of Na⁺ within the electrode material. By presenting a PBA model cell yielding 25 Wh kg^-1 at up to 10 kW kg^-1, this work highlights a possible pathway toward the guided design of hybrid battery-supercapacitor systems. Furthermore, open challenges associated with thin-film electrodes are discussed, such as the role of parasitic side reactions, as well as increasing the mass loading.