In this study, we developed eco-friendly biopolymer electrolytes by blending nanocrystalline cellulose (NCC) with polyvinyl alcohol (PVA) and crosslinking them using glutaraldehyde. These membranes, denoted as NCC-x/PVA-y, were fabricated via the solution casting method. We thoroughly investigated the effects of different NCC to PVA ratios on various properties, including water uptake, swelling ratio, thermal and mechanical characteristics, proton conductivity, hydrogen permeation, and single Proton Exchange Membrane Fuel Cell (PEMFC) performances. Increasing the NCC concentration (ranging from 20 % to 60 %) led to enhanced surface roughness and compactness of ionic domains, resulting in improved dimensional stability and reduced hydrogen permeability across the membranes. Among the tested ratios, NCC-50/PVA-50 exhibited the highest proton conductivity, measuring 0.3 × 10−2 S cm−1. Notably, this ratio demonstrated a 60 % lower swelling ratio and lower hydrogen permeability (0.76 × 10−13 cm2/scmHg) compared to Nafion 117 (514 × 10−13 cm2/scmHg), indicating its superior performance. Furthermore, the NCC-50/PVA-50 membrane consistently maintained open-circuit voltages exceeding 0.9 V under all conditions, highlighting its effective proton transport capabilities and minimal fuel penetration. Density Functional Theory (DFT) analysis confirmed the successful cross-linking of NCC/PVA with glutaraldehyde, emphasizing its compatibility and potential for proton conductivity in PEMFC applications.
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