Self‐Assembled Nanochains with Synchronous Anchor‐Transport Effect Reinforced All‐Solid‐State Lithium‐Metal Batteries

Polymer‐based solid‐state electrolytes (PSEs) hold great potential for constructing all‐solid‐state lithium‐metal batteries (ASSLMBs) with higher energy density and longer cycling life. However, PSEs encounter some challenges, including low ionic conductivity and poor interface compatibility. Here, this is aimed to address these challenges by applying a rationally designed nanochains with synchronous anchor‐transport effect as fillers for PSEs. The nanochains are self‐assembled via intermolecular hydrogen bonding of MgF 2 (MF) nanoparticles and bacterial cellulose (BC) (denoted as BCMF). Theoretical calculations and characterizations demonstrate that BCMF chains exert an important role in assisting dissociating LiTFSI and transporting Li + , in which the MF of BCMF anchors TFSI − while the OH group of BCMF providing fast transport paths for Li + , thus achieving a remarkable room‐temperature ionic conductivity (8.75 × 10 −4 S cm −1 ). In addition, the superior SEI derived from in situ conversion reactions of MF improves the interface compatibility between electrolytes and the lithium anode. As a result, the Li||Li cell demonstrates an ultra‐long plating/stripping time of over 10,000 h. Notably, the LFP||Li and NCM811||Li batteries even maintain remarkable cycle stability at room temperature, revealing the great potential of the BCMF chains at room temperature for ASSLMBs.