Tailored proton conductive membranes of PVdF-co-HFP: Investigating the synergistic effects of ammonium tetrafluoroborate and phosphoric acid dopants on dielectric characteristics

• Published in: Process safety and environmental protection 2024-11, Vol.191, p.1994-2006
• Main Authors: Yılmazoğlu, Mesut, Abaci, Ufuk, Erdemi, Hamit, Coban, Ozan
• Format: Article
• Language: English
• Subjects: Ammonium salt; Dielectric; Ionic conductivity; Phosphoric acid; PVdF-co-HFP
• ISSN: 0957-5820
• DOI: 10.1016/j.psep.2024.09.112

This study investigates the structural, thermal, and dielectric properties of pure PVdF-co-HFP matrix and its composite electrolytes, PVdF-co-HFP/NH4BF4[x], both before and after PA doping, using FTIR, SEM, TGA, and dielectric analyses. FTIR spectra reveal characteristic vibrational bands, confirming the presence of various functional groups and phases. SEM images display a smooth and homogeneous surface morphology for pure PVdF-co-HFP, while the composite electrolytes exhibit irregular dispersion of NH4BF4 salt and rougher surfaces upon PA doping. TGA analysis shows that the onset of thermal degradation occurs at approximately 370 ℃ for pure PVdF-co-HFP, while PA-doped samples demonstrate higher decomposition temperatures, exceeding 400 ℃ due to hydrogen bonding and ionic complex formation. The presence of NH4BF4 and PA doping also affects the crystallinity of the PVdF-co-HFP matrix, notably shifting the transition temperatures of the alpha and beta phases. Ionic conductivity measurements indicate that PA doping significantly enhances conductivity by increasing charge carrier concentration and facilitating ion transport. PA-doped PVdF-co-HFP/NH4BF4[10] showed the highest conductivity reaching 1.68 × 10−3 S.cm−1 at 1 MHz and 400 K. Dielectric studies reveal frequency-dependent behavior, with dielectric constant (ε') and loss (ε") showing distinct trends influenced by salt concentration and PA doping. The dielectric tangent loss (tanδ) of PA-doped PVdF-co-HFP/NH4BF4 composite membranes exhibits frequency and temperature dependence. At higher temperatures, tanδ increases with frequency, showing a resonance peak that shifts towards higher frequencies. The study elucidates the impact of PA doping on the structural, thermal, and electrochemical performance of PVdF-co-HFP/NH4BF4 composites, providing insights for their potential applications in advanced electrolyte systems.