A “Blockchain” Synergy in Conductive Polymer‐Filled Metal–Organic Frameworks for Dendrite‐Free Li Plating/Stripping with High Coulombic Efficiency

Abstract The performance of lithium‐metal batteries is severely hampered by uncontrollable dendrite growth and volume expansion on the metal anodes. Inspired by the “blockchain” concept in data mining, here we utilize a conductive polymer‐filled metal–organic framework (MOF) as the lithium host, in which polypyrrole (PPy) serves as the “chain” to interlink Li “blocks” stored in the MOF pores. While the N‐rich PPy guides fast Li + infiltration/extrusion and serves as the nucleation sites for isotropic Li growth, the MOF pores compartmentalize bulk Li deposition for 3D matrix Li storage, leading to low‐barrier and dendrite‐free Li plating/stripping with superb Coulombic efficiency. The as‐fabricated lithium‐metal anodes operate over 700 cycles at 5 mA cm −2 in symmetric cells, and 800 cycles at 1 C in full cells with a per‐cycle capacity loss of only 0.017 %. This work might open a new chapter for Li‐metal anode construction by introducing the concept of “blockchain” management of Li plating/stripping.