Tailoring Three-Dimensional Cross-Linked Networks Based on Water-Soluble Polymeric Materials for Stable Silicon Anode

For stable battery operation of silicon (Si)-based anodes, utilizing cross-linked three-dimensional (3D) network binders has emerged as an effective strategy to mitigate significant volume fluctuations of Si particles. In the design of cross-linked network binders, careful selection of appropriate cross-linking agents is crucial to maintaining a balance between the robustness and functionality of the network. Herein, we strategically design and optimize a 3D cross-linked network binder through a comprehensive analysis of cross-linking agents. The proposed network is composed of poly(vinyl alcohol) grafted poly(acrylic acid) (PVA-g-PAA, PVgA) and aromatic diamines. PVgA is chosen as the polymer backbone owing to its high flexibility and facile synthesis using an ecofriendly water solvent. Subsequently, an aromatic diamine is employed as a cross-linker to construct a robust amide network that features a resonance-stabilized high modulus and enhanced adhesion. Comparative investigations of three cross-linkers, 2,2′-bis(trifluoromethyl)benzidine, 3,3′-oxidianiline, and 4,4′-oxybis[3-(trifluoromethyl)aniline] (TFODA), highlight the roles of the trifluoromethyl group (−CF3) and the ether linkage. Consequently, PVgA cross-linked with TFODA (PVgA-TFODA), featuring both −CF3 and −O–, establishes a well-balanced 3D network characterized by heightened elasticity and improved binding forces. The optimized Si and SiOx/graphite composite electrodes with the PVgA-TFODA binder demonstrate impressive structural stability and stable cycling. This study offers a novel perspective on designing cross-linked network binders, showcasing the benefits of a multidimensional approach considering chemical and physical interactions.