Functional Separators Regulating Ion Transport Enabled by Metal‐Organic Frameworks for Dendrite‐Free Lithium Metal Anodes

Developing high energy density lithium secondary batteries is pivotal for satisfying the increasing demand in advanced energy storage systems. Lithium metal batteries (LMBs) have attracted growing attention due to their high theoretical capacity, but the lithium dendrites issue severely fetter their real‐world applications. It is found that reducing anion migration near lithium metal prolongs the nucleation time of dendrites, meanwhile, promoting homogeneous lithium deposition suppresses the dendritic growth. Thus, regulating ion transport in LMBs is a feasible and effective strategy for addressing the issues. Based on this, a functional separator is developed to regulate ion transport by utilizing a well‐designed metal‐organic frameworks (MOFs) coating to functionalize polypropylene (PP) separator. The well‐defined intrinsic nanochannels in MOFs and the negatively charged gap channels both restricts the free migration of anions, contributing to a high Li+ transference number of 0.68. Meanwhile, the MOFs coating with uniform porous structure promotes homogeneous lithium deposition. Consequently, a highly‐stable Li plating/stripping cycling for over 150 h is achieved. Furthermore, implementation of the separator enables LMBs with high discharge capacity, prominent rate performance and good capacity retention. This work is anticipated to aid developement of dendrite‐free LMBs by utilizing advanced separators with ion transport management. A functional separator based on metal‐organic frameworks is developed to achieve ion regulation. Based on highly efficient lithium ion selectivity transport and homogeneous lithium deposition, the separator significantly improves the electrochemical performance of lithium metal batteries. This provides new insight into regulating ion transport in next generation high energy battery technologies.