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Electrochemical energy storage devices, which typically include lithium-ion batteries and supercapacitors,[1-4] have drawn worldwide interests since the realization of the energy crisis.Among all the targeted electrode materials for Li-ion batteries, peapod-like nanostructures with nanoscale active materials encapsulated in carbon fibers are considered as the promising candidates due to their synergic effect in electrochemical energy storage derived from the unique conformation.[4]