Tuning the Porous Structure in PMMA-Templated Mesoporous MoO2 for Pseudocapacitive Li-Ion Electrodes

MoO2 is an exciting candidate for next-generation energy storage. It can be used for fast-charging applications in nanoscale form, but its kinetic performance is often limited by insulating MoO3 surface oxide layers. Here, we developed methods to produce polymer-templated porous MoO2 powders where electrical conductivity was well-maintained throughout the structure, even in the presence of some surface oxidation. Porosity, pore size, and crystallite size were controlled by varying the amount and size of the colloidal templates and through calcination temperature. The electrochemical performance was correlated with nanoscale structure: samples with high porosity, medium pore sizes, and good crystallinity display optimal rate capabilities, with over 100 mAh g–1 delivered in 3 min and 93% capacity retention after 1000 cycles. Kinetic studies were performed on samples with the largest and smallest crystallite sizes to understand the charge storage mechanism. In the sample with the smallest crystallite size, 85% of the total stored charge was capacitive, compared to 60% for the largest crystallite size. Sloping voltage profiles in materials with smaller domain sizes further suggest suppression of intercalation-induced phase transitions. This work thus provides insights into the mechanisms of charge storage in nanoscale MoO2 and design parameters for the production of fast charging materials.