Polyoxomolybdate‐Based Metal–Organic Framework‐Derived Cu‐Embedded Molybdenum Dioxide Hybrid Nanoparticles as Highly Efficient Electrocatalysts for Al−S Batteries

High‐performance rechargeable aluminum‐sulfur batteries (RASB) have great potential for various applications owing to their high theoretical capacity, abundant sulfur resources, and good safety. Nevertheless, the practical application of RASB still faces several challenges, including the polysulfide shuttle phenomenon and low sulfur utilization efficiency. Here, we first developed a synergistic copper heterogeneous metal oxide MoO2 derived from polymolybdate‐based metal‐organic framework as an efficient catalyst for mitigating polysulfide diffusion. This composite enhances sulfur utilization and electrical conductivity of the cathode. DFT calculations and experimental results reveal the catalyst Cu/MoO2@C not only effectively anchors aluminum polysulfides (AlPSs) to mitigate the shuttle effect, but also significantly promotes the catalytic conversion of AlPSs on the sulfur cathode side during charging and discharging. The unique nanostructure contains abundant electrocatalytic active sites of oxide nanoparticles and Cu clusters, resulting in excellent electrochemical performance. Consequently, the established RASB exhibits an initial capacity of 875 mAh g−1 at 500 mA g−1 and maintains a capacity of 967 mAh g−1 even at a high temperature of 50 °C. A Polyoxomolybdate‐based metal‐organic framework‐derived Cu‐embedded molybdenum dioxide hybrid nanoparticles was first applied as sulfur host in aluminum‐sulfur batteries to resolve remaining critical challenge of polysulfide shuttle effect. The pouch cell with Cu/MoO2@C cathode cycled at 100 mA g−1 exhibits an initial discharge capacity of 150 mAh g−1 and maintains 100 cycles.