Dynamic Networks of Cellulose Nanofibrils Enable Highly Conductive and Strong Polymer Gel Electrolytes for Lithium‐Ion Batteries

Abstract Tunable dynamic networks of cellulose nanofibrils (CNFs) are utilized to prepare high‐performance polymer gel electrolytes. By swelling an anisotropically dewatered, but never dried, CNF gel in acidic salt solutions, a highly sparse network is constructed with a fraction of CNFs as low as 0.9%, taking advantage of the very high aspect ratio and the ultra‐thin thickness of the CNFs (micrometers long and 2–4 nm thick). These CNF networks expose high interfacial areas and can accommodate massive amounts of the ionic conductive liquid polyethylene glycol‐based electrolyte into strong homogeneous gel electrolytes. In addition to the reinforced mechanical properties, the presence of the CNFs simultaneously enhances the ionic conductivity due to their excellent strong water‐binding capacity according to computational simulations. This strategy renders the electrolyte a room‐temperature ionic conductivity of 0.61 ± 0.12 mS cm −1 which is one of the highest among polymer gel electrolytes. The electrolyte shows superior performances as a separator for lithium iron phosphate half‐cells in high specific capacity (161 mAh g −1 at 0.1C), excellent rate capability (5C), and cycling stability (94% capacity retention after 300 cycles at 1C) at 60 °C, as well as stable room temperature cycling performance and considerably improved safety compared with commercial liquid electrolyte systems.