Synthetic control of manganese birnessite: Impact of crystallite size on Li, Na, and Mg based electrochemistry

The synthesis and characterization of Mg-birnessite (Mg_xMnO₂) with different crystallite sizes, prepared though low temperature precipitation and ion exchange was demonstrated. The influence of crystallite size on electrochemical performance of Mg-birnessite was studied for the first time, where material with smaller crystallite size was demonstrated to have enhanced capacity and rate capability in Li ion, Na ion, and Mg ion based electrolytes. Cation diffusion using GITT type testing demonstrated the ion diffusion coefficient of Mg²⁺was ∼10× lower compared with Li⁺and Na⁺. This work illustrates that tuning of inorganic materials properties can lead to significant enhancement of electrochemical performance in lithium, sodium as well as magnesium based batteries for materials such as Mg-birnessite and provides a deliberate approach to improve electrochemical performance.