Nanoengineered Functional Cellulose Ionic Conductor Toward High‐ Performance All‐Solid‐State Zinc‐Ion Battery

• Published in: Advanced functional materials 2024-06, Vol.34 (25), p.n/a
• Main Authors: Tu, Wen‐Bin, Liang, Shuang, Song, Li‐Na, Wang, Xiao‐Xue, Ji, Gui‐Juan, Xu, Ji‐Jing
• Format: Article
• Language: English
• Subjects: Cellulose; cellulose nanofibrils; Conductors; Density functional theory; Energy of dissociation; Energy storage; Free energy; Functional groups; functionalization; Heat of formation; Hydrogen evolution reactions; Ion currents; nano‐engineering; Rechargeable batteries; solid‐state electrolyte; solid‐state zinc‐ion battery; Zinc
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202316137

The rechargeable zinc‐ion battery is regarded as a promising candidate for the next‐generation energy storage system, however, zinc dendrite growth and hydrogen evolution reaction (HER) have greatly hindered the practical application of the battery. Herein, a functionalized, nano‐engineering Zn2+ coordinated carboxylate cellulose solid‐state electrolyte (denoted as Zn‐CCNF@XG) for zinc‐ion battery is constructed through a straightforward approach. According to the experimental and density functional theory (DFT) results of dissociation energy, the notably decreased dissociation energy by −COOH is favorable to Zn2+ de‐coordinating and rapid ion‐hopping in Zn‐CCNF@XG to achieve high ionic conductivity and transference number. More importantly, the engineered molecular channels are beneficial to enlarging the distance between the nanofibril chains, providing a larger space for the movement of Zn2+. Benefiting from the coordination of Zn2+ with −OH in carboxylate cellulose nanofibrils, Zn‐CCNF@XG as a good ionic conductor displays a high ionic conductivity of 1.17 × 10−4 S cm−1 and transference number of 0.78. The Zn||NaV3O8·1.5H2O full cell with Zn‐CCNF@XG maintains a capacity retention of 83.46% with a coulombic efficiency of 99.99% after 3000 cycles (1 A g−1). The proposed strategy by introducing a functional group to cellulose nanofibrils effectively avoids the dendrite and HER, providing valuable guidelines for the practical application of zinc‐ion batteries. Functionalizing and nano‐engineering strategies are utilized to explore cellulose as a novel solid‐state Zn2+ conductor (Zn‐CCNF@XG). The introduction of −COOH is favorable to Zn2+  rapid ion‐hopping with low energy barrier and high ionic conductivity (1.17 × 10−4 S cm−1), showing an efficient and instructive strategy for high ionic conductivity, ionic transference number, and stability of SSEs.