RESUMEN
Polyethylene oxide (PEO)-based solid-state batteries hold great promise as the next-generation batteries with high energy density and high safety. However, PEO-based electrolytes encounter certain limitations, including inferior ionic conductivity, low Li+ transference number, and poor mechanical strength. Herein, we aim to simultaneously address these issues by utilizing one-dimensional zwitterionic cellulose nanofiber (ZCNF) as fillers for PEO-based electrolytes using a simple aqueous solution casting method. Multiple characterizations and theoretical calculations demonstrate that the unique zwitterionic structure imparts ZCNF with various functions, such as disrupting PEO crystallization, dissociating lithium salts, anchoring anions through cationic groups, accelerating Li+ migration by anionic groups, as well as its inherent reinforcement effect. As a result, the prepared PL-ZCNF electrolyte exhibits remarkable ionic conductivity (5.37×10-4â S cm-1) and Li+ transference number (0.62) at 60 °C without sacrificing mechanical strength (9.2â MPa), together with high critical current density of 1.1â mA cm-2. Attributed to these merits of PL-ZCNF, the LiFePO4|PL-ZCNF|Li solid-state full-cell delivers exceptional rate capability and cycling performance (900â cycles at 5â C). Notably, the assembled pouch-cell can maintain steady operation over 1000â cycles with an impressive 93.7 % capacity retention at 0.5â C and 60 °C, highlighting the great potential of PL-ZCNF for practical applications.
RESUMEN
A simplified procedure to synthesize zwitterionic cellulose by means of N-protected aspartic anhydride under mild conditions was developed. The preparation of modified cellulose samples was carried out under heterogeneous, aqueous conditions by reacting NH4OH-activated cellulose with aspartic anhydrides N-protected with trifluoroacetyl (TFAc) and carbobenzyloxy (Cbz). Modified cellulose samples Cel-Asp-N-TFAc and Cel-Asp-N-Cbz were characterized by Fourier Transform Infrared (FTIR) and 13C solid state Nuclear Magnetic Resonance (NMR) spectroscopy. The functionalization degree of each cellulose sample was determined by the 13C NMR signal integration values corresponding to the cellulose C1 vs. the Cα of the aspartate residue and corroborated by elemental analysis. In agreement, both analytical methods averaged a grafting degree of 20% for Cel-Asp-N-TFAc and 16% for Cel-Asp-N-Cbz. Conveniently, Cel-Asp-N-TFAc was concomitantly partially N-deprotected (65%) as determined by the ninhydrin method. The zwitterion character of this sample was confirmed by a potentiometric titration curve and the availability of these amino acid residues on the cellulose was inspected by adsorption kinetics method with a 100 mg L-1 cotton blue dye solution. In addition, the synthesis reported in the present work involves environmentally related advantages over previous methodologies developed in our group concerning to zwitterionic cellulose preparation.