Stable and Highly Ion Selective Membrane Made from Cellulose Nanocrystal for Aqueous Redox Flow Batteries.
NANO LETTERS(2019)
Abstract
The design of chemically stable ion-exchange membranes with high selectivity for applications in an aqueous redox flow battery (RFB) at high acid concentrations remains a significant challenge. Herein, this study designed a stable and highly ion-selective membrane by utilizing proton conductive cellulose nanocrystals (CNCs) incorporated in a semicrystalline hydrophobic poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix. The high hydrophobicity of the PVDF-HFP matrix mitigates crossover of the electrolytes, whereas the abundant and low-cost CNCs derived from wood provide high proton conductivity. The fundamental contributors for CNCs' excellent proton conductivity are the hydroxyl (OH) functional groups, highly acidic sulfonate (SO3H) functional groups, and the extensive intramolecular hydrogen bonding network. In addition, CNCs exhibit a mechanically and chemically stable structure in the harsh acidic electrolyte attributed to the high crystallinity (crystalline index of similar to 86%). Therefore, because of the high proton conductivity, excellent ion selectivity, high chemical stability, and structural robustness, the vanadium redox flow battery (VRFB) assembled with the homogeneous CNCs and PVDF-HFP (CNC/PVDF-HFP) membrane achieved a Coulombic efficiency (CE) of 98.2%, energy efficiency (EE) of 88.2%, and a stable cycling performance for more than 650 cycles at a current density of 100 mA cm(-2). The obtained membrane possesses excellent flexibility, high mechanical tensile strength, and superior selectivity. Meanwhile, the applied casting method is scalable for large-scale manufacturing.
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Key words
Ion-exchange membrane,redox flow battery,cellulose nanocrystal,proton conductivity,vanadium,hydrogen bonding
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