Composite structures for electrochemical energy storage are prepared on the basis of using the high-rate lithium ion insertion properties of Nb2O5. The Nb2O5 is anchored on reduced graphene oxide (rGO) by hydrothermal synthesis to improve the charge-transfer properties, and by controlling the surface charge, the resulting Nb2O5-rGO particles are attached to a high-surface-area carbide-derived carbon scaffold without blocking its exfoliated layers. The electrochemical results are analyzed using a recently published multiscale physics model that provides significant insights regarding charge storage kinetics. In particular, the composite electrode exhibits surface-confined charge storage at potentials of <1.7 V (vs Li/Li+), where faradaic processes dominate, and electrical double layer charge storage at potentials of >2.2 V. A hybrid device composed of the composite electrode with activated carbon as the demonstrates increased energy density at power densities comparable to an activated carbon device, provided the hybrid device operates in the faradaic potential range.