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<p>Composite polymer electrolytes based on a PEO/PVDF (90:10) matrix containing NaClO<sub>4</sub> and Mn–Prussian Blue analogue (Mn-PBA, Na<sub>2</sub>MnFe(CN)<sub>6</sub>) nanoparticles were investigated to elucidate the role of electroactive fillers on sodium-ion transport in solid polymer electrolytes. Structural and thermal analyses show that Mn-PBA incorporation modifies the polymer microstructure by reducing PEO crystallinity and enhancing segmental mobility at intermediate filler loadings. An optimal Mn-PBA content of 7 wt.% leads to the highest ionic conductivity within the studied range (~ 2.5 × 10<sup>–6</sup> S cm⁻<sup>1</sup> at room temperature) and increases the Na⁺ transference number from 0.23 to 0.28. The temperature dependence of ionic conductivity follows a Vogel–Tammann–Fulcher behavior, indicating that ion transport is strongly coupled to polymer segmental dynamics. X-ray diffraction and differential thermal analysis reveal that low filler contents disrupt long-range crystalline order, whereas higher loadings promote partial structural reorganization due to filler aggregation. Electrochemical stability measurements indicate stability within the voltage range relevant for sodium-ion battery studies. While the absolute room-temperature conductivity remains limited, a clear relationship between structural evolution and sodium-ion transport is observed in the composite electrolyte.</p>

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Ion transport and structural effects of Mn–Prussian blue analogue fillers in PEO/PVDF-based polymer electrolytes

  • 期刊论文

  • 发表日期：

    2026年7月2日

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  • Ivan Morales-Cruz,
  • Arian Espinosa-Roa,
  • Alfredo Romero-Contreras,
  • Eduardo M. Sanchez-Cervantes

摘要

Composite polymer electrolytes based on a PEO/PVDF (90:10) matrix containing NaClO4 and Mn–Prussian Blue analogue (Mn-PBA, Na2MnFe(CN)6) nanoparticles were investigated to elucidate the role of electroactive fillers on sodium-ion transport in solid polymer electrolytes. Structural and thermal analyses show that Mn-PBA incorporation modifies the polymer microstructure by reducing PEO crystallinity and enhancing segmental mobility at intermediate filler loadings. An optimal Mn-PBA content of 7 wt.% leads to the highest ionic conductivity within the studied range (~ 2.5 × 10–6 S cm⁻1 at room temperature) and increases the Na⁺ transference number from 0.23 to 0.28. The temperature dependence of ionic conductivity follows a Vogel–Tammann–Fulcher behavior, indicating that ion transport is strongly coupled to polymer segmental dynamics. X-ray diffraction and differential thermal analysis reveal that low filler contents disrupt long-range crystalline order, whereas higher loadings promote partial structural reorganization due to filler aggregation. Electrochemical stability measurements indicate stability within the voltage range relevant for sodium-ion battery studies. While the absolute room-temperature conductivity remains limited, a clear relationship between structural evolution and sodium-ion transport is observed in the composite electrolyte.