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3D lithium vanadium phosphate/reduced graphene oxide porous structures are prepared using a facile lyophilization process. The 3D porous nature of these lyophilized electrodes along with their high surface area lead to high rate capability and specific capacity. A high specific discharge capacity of ≈192 mAh g−1 is observed at 0.5 C. The cycling performance is noteworthy, as these lyophilized samples at 0.5 and 1 C do not show any fading, even after 1000 and 5000 cycles, respectively. Capacity retention of ≈96.2% is observed at the end of 10 000 cycles at 20 C. This remarkable cycling performance is attributed to the structural stability of the 3D porous network and is confirmed using scanning electron microscopy and selected area electron diffraction after 10 000 cycles of consecutive charging and discharging at 20 C. [ABSTRACT FROM AUTHOR]