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The practical application of Li‐S batteries is still severely restricted by poor cyclic performance caused by the intrinsic polysulfides shuttle effect, which is even more severe under the high‐temperature condition owing to the inevitable increase of polysulfides’ solubility and diffusion rate. Herein, tungsten‐doped vanadium dioxide (W‐VO2) micro‐flowers are employed with first‐order metal‐insulator...