Anion‐repulsive polyoxometalate@MOF‐modified separators for dendrite‐free and high‐rate lithium batteries

Abstract Commercial polyolefin separators in lithium batteries encounter issues of uncontrolled lithium‐dendrite growth and safety incidents due to their low Li + transference numbers () and low melting points. To address these challenges, this study proposes an innovative approach by upgrading conventional separators through the incorporation of metal‐organic framework (MOF)‐confined polyoxometalate (POM). The presence of POM restricts anion diffusion through electrostatic repulsion while facilitating Li + transport within MOF nanochannels through their affinity for lithium ions. Moreover, MOF confinement effectively mitigates the acidification of electrolytes induced by POM. As a proof‐of‐concept, the polypropylene separators decorated with phosphotungstic acid@UIO66 (denoted as PW 12 @UIO66‐PP) exhibit remarkable lithium‐ion conductivity of 0.78 mS cm −1 with a high of 0.75 at room temperature. The modified separators also display excellent thermal stability, preventing significant shrinkage even at 150°C. Furthermore, Li symmetric cells employing PW 12 @UIO66‐PP separators exhibit stable cycling for 1000 h, benefiting from rapid Li‐ion transport and uniform deposition. Additionally, the modified separator shows promising adaptability to industrial manufacturing of lithium‐ion batteries, as evidenced by the assembly of a 4 Ah NCM811/graphite pouch cell that retains 97% capacity after 350 cycles at C/3, thus highlighting its potential for practical applications.