Supramolecular self-assembly in solid-state lithium batteries: Bulk electrolyte design and interface engineering

The development of solid-state lithium batteries (SSLBs) is pivotal to addressing the escalating global demand for advanced electrochemical energy storage systems, driven notably by electric vehicles and portable electronics. Recently, supramolecular chemistry has demonstrated significant potential in enhancing the performance and stability of SSLBs through precisely controlled molecular interactions and self-assembly processes. This review systematically analyzes recent advancements in supramolecular self-assembly applied to solid-state-electrolyte materials and solid electrode-solid electrolyte interface engineering within SSLBs. Various supramolecular interactions, such as hydrogen bonding, halogen bonding, charge transfer interactions, host-guest interactions, π–π stacking, and dynamic covalent bonding, are comprehensively examined for their roles in constructing electrolytes characterized by superior ionic conductivity, electrochemical stability, mechanical robustness, and self-healing functionality. In addition, we discuss supramolecular strategies for engineering functional interfaces of effectively mitigating lithium dendrite formation, reducing interfacial impedance, and significantly enhancing cycle stability. And the detailed mechanistic insights into how these supramolecular interactions foster optimized ionic conduction pathways, structural integrity, and dynamic adaptability are elucidated. This review underscores the transformative potential of supramolecular chemistry in realizing practical and highly efficient next-generation SSLBs.