Electrochemical characterization was carried out using 2032 type coin cells (Hohsen), which were assembled in an argon-filled glovebox (MBraun, O2 & H2O < 0.1 ppm). They contained a stack composed of the V2O5 electrodes on aluminum current collectors, a glass fiber separator (19 mm diameter, GF/A, Whatman), a 12 mm diameter lithium disc (500 μm thickness, Honjo), a stainless-steel spacer and a spring. As electrolyte, 90 μL of 1.0 M LiPF6 in ethylene carbonate/diethyl carbonate is used (EC:DEC, 3:7 volume ratio, Powerlyte). All electrochemical experiments were performed in climatic chambers (Binder) at 20 °C with potentiostats from Biologic (VMP3, VMP-3e, VMP-300). Cyclic voltammetry (CV) and galvanostatic cycling were conducted in the potential window of 2.0 -4.0 V vs. the Li + /Li. For long-term cycling, a specific current of 500 mA/g was employed. To test the rate capability, specific currents of 20, 50, 100, 200, 500, 1000, 5000 mA/g were applied for 5 cycles each and the last 5 cycles were again run at 20 mA/g. All normalizations are with respect to combined mass of V2O5 with molecular pillar, unless explicitly stated otherwise.