A Triple Crosslinked Binder with Hierarchical Stress Dissipation and High Ionic Conductivity for Advanced Silicon Anodes in Lithium‐ion Batteries

Abstract Silicon (Si) is a promising anode material for high‐energy‐density lithium‐ion batteries, but the significant volume change of Si particles during alloying/dealloying with lithium (Li) undermines the mechanical integrity of Si anode, causing electrode fracture, delamination and rapid capacity decay. Herein, a robust triple crosslinked network (TCN) binder with high ionic conductivity and hierarchical stress dissipation is reported for Si anodes, which is prepared by in situ chemical crosslinking polyacrylic acid (PAA) and melamine (MA). The triple interactions of hydrogen bonds, electrostatic interactions, and covalent amide bonds enhance the adhesion of binder to Si and synergistically promote stress dissipation within Si anodes, thus strengthening the dynamic structural stability of Si anodes during cycling. Moreover, the rapid coupling/decoupling of Li + with the TCN binder enables an impressive Li + transference number of 0.63 and high ionic conductivity of 1.2 × 10 −4 S cm −1 . Consequently, the Si‐TCN anode delivers specific capacity of 2268 mAh g −1 with a high mass loading of 2 mg cm −2 , high‐rate performance of 1673 mAh g −1 at 5 A g −1 , and stable cycling for 250 cycles at 1 A g −1 , thus showing great prospects for high‐energy‐density Si‐based batteries.