Supramolecular chemistry of cellulose-based electrolytes

Cellulose has garnered significant attention in material science and energy storage due to its unique supramolecular structure and excellent mechanical properties. In particular, cellulose-based electrolytes have emerged as promising candidates for next-generation energy devices. However, the fundamental supramolecular interactions governing their structural evolution and ion-transport dynamics remain unclear. This review provides a comprehensive overview of the supramolecular chemistry of cellulose-based electrolytes, emphasizing the synergistic roles of hydrogen bonding, electrostatic coordination, van der Waals forces, and π–π interactions in directing molecular self-assembly, solvation regulation, and dynamic ion migration. The discussion integrates molecular conformations within crystalline–amorphous domains with the hierarchical organization of supramolecular networks, thereby linking interfacial chemistry with macroscopic functionality such as ionic conductivity, interfacial stability, and mechanical robustness. We also critically analyze the cooperative supramolecular effects between cellulose matrices and functional additives to reveal structure–property correlations. The review closes by proposing rational design strategies for cellulose-based electrolytes and offering insights into their potential applications in the field of energy storage.