Pseudocapacitance is commonly associated with surface or near-surface reversible redox reactions, as observed with RuO2·xH2O in an acidic electrolyte. However, we recently demonstrated that a pseudocapacitive mechanism occurs when lithium ions are inserted into mesoporous and nanocrystal films of orthorhombic Nb2O5 (T-Nb2O5; refs 1,2). Here, we quantify the kinetics of charge storage in T-Nb2O5: currents that vary inversely with time, charge-storage capacity that is mostly independent of rate, and redox peaks that exhibit small voltage offsets even at high rates. We also define the structural characteristics necessary for this process, termed intercalation pseudocapacitance, which are a crystalline network that offers two-dimensional transport pathways and little structural change on intercalation. The principal benefit realized from intercalation pseudocapacitance is that high levels of charge storage are achieved within short periods of time because there are no limitations from solid-state diffusion. Thick electrodes (up to 40 μm thick) prepared with T-Nb2O5 offer the promise of exploiting intercalation pseudocapacitance to obtain high-rate charge-storage devices.

Carbon supercapacitors, which are energy storage devices that use ion adsorption on the surface of highly porous materials to store charge, have numerous advantages over other power-source technologies, but could realize further gains if their electrodes were properly optimized. Studying the effect of the pore size on capacitance could potentially improve performance by maximizing the electrode surface area accessible to electrolyte ions, but until recently, no studies had addressed the lower size limit of accessible pores. Using carbide-derived carbon, we generated pores with average sizes from 0.6 to 2.25 nanometer and studied double-layer capacitance in an organic electrolyte. The results challenge the long-held axiom that pores smaller than the size of solvated electrolyte ions are incapable of contributing to charge storage.