The lithium-sulfur (Li-S) batteries have high theoretical energy density, exceeding that of the lithium-ion batteries. However, their practical applications are hindered by the capacity decay due to lithium polysulfide shuttle effect and sulfur volume expansion. Here, we design a S@hollow carbon with porous shell/MnOx (S@HCS/MnOx) cathode to accommodate and immobilize sulfur and polysulfides, and develop a non-destructive technique X-ray computed tomography (X-ray CT) to in situ visualize the volume expansion of Li-S cathode. The designed cathode achieves a specific capacity of ∼1100 mAh g-1 at 0.2 C with a fade rate of 0.18% per cycle over 300 cycles. The X-ray CT shows that only 16% volume expansion and 70% volume fraction of solid sulfur remaining in the S@HCS/MnOx cathode, superior to the commercial cathode with 40% volume expansion and 5% volume remaining of solid sulfur particles. This is the first reported visualization evidence for the effectiveness of hollow carbon structure in accommodating cathode volume expansion and immobilizing sulfur shuttling. X-ray CT can serve as a powerful in situ tool to trace the active materials and then feedback to the structure design, which helps develop efficient and reliable energy storage systems
