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Metal chalcogenides with structural pulverization/degradation and intrinsic low electrical conductivity trigger the challenging issues of serious capacity fading and inferior rate capability upon repeated de-/sodiation cycling. Multiple electroactive heterostructures can integrate the inherent advantages of a strong synergistic coupling effect to improve their electrochemical Na+-storage behavior and structural durability, showing robust mechanical features, fast Na+ immigration and abundant active insertion sites at intriguing heteroi