Multifunctional and Near Zero‐Strain Li‐Rich In‐Li Intermetallic Anodes for Stable Cycling of Li‐S Batteries

ABSTRACT Li‐S batteries (LSBs) are emerging as formidable contenders in the field of energy storage systems, owing to their cost‐effectiveness and ultrahigh energy density that surpasses that of conventional Li‐ion batteries. Nonetheless, unresolved issues, such as Li dendrite growth and parasitic chemical reactions between the Li metal and dissolved polysulfides, pose significant safety concerns and remain major hurdles to their commercial viability. Herein, we propose a Li‐rich In 3 Li 13 intermetallic alloy anode (In‐Li IMA) fabricated via a simple roll‐pressing and pressure‐holding process. Unlike previous studies that focused primarily on stabilized interfaces for dendrite suppression, the in situ‐formed In‐Li IMA demonstrates not only significantly inhibited dendritic Li growth but also minimized volume change during cycling, owing to its ionically and electronically conductive 3D framework. Furthermore, simulation studies reveal that the In‐Li IMA suppresses polysulfide‐induced side reactions due to its hole‐dominated conduction and weaker polysulfide adsorption energy relative to Li. In contrast to the control Li cell that exhibits significant capacity fading, the In‐Li IMA cell achieves 87.4% capacity retention over 600 cycles and exhibits improved cyclability even in large‐area pouch‐cell configurations. Based on this accessible approach for fabricating large‐scale multifunctional anodes, this study provides critical design insights for developing practical anodes for LSBs.