Raman, Dilatometric, and Dielectric Insights into Pr3+-Doped Pb–Sb Silicate Glasses toward Ion-Conducting Glass Electrolytes

Rao, Yeti Dana; Ravi Kumar, Vandana; Pavić, Luka; Bafti, Arijeta; Jiménez, José A.; Venkata Sekhar, Ayyagari; Kapuśniak, Paulina; Brągiel, Piotr; Piasecki, Michal; Veeraiah, Nalluri (2025) Raman, Dilatometric, and Dielectric Insights into Pr3+-Doped Pb–Sb Silicate Glasses toward Ion-Conducting Glass Electrolytes. The Journal of Physical Chemistry B, 129 (39). pp. 10193-10205. ISSN 1520-6106

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Abstract

This work reports new physical insights concerning the effect of red lead (Pb3O4) addition (10–35 mol %) on the structural, dilatometric, dielectric, and conductivity properties of Sb2O3–SiO2:Pr2O3 glasses for potential solid-state electrolyte applications. The melt-quenched glasses were scrutinized via Raman spectroscopy including a temperature-dependent evaluation revealing progressive polymerization of the glass network up to 30 mol % Pb3O4, followed by depolymerization at 35 mol %. Harmonizing with the structural evolution, thermal analysis by dilatometry showed that the thermal expansion coefficients/softening temperatures first decreased/increased from 10 to 30 mol % Pb3O4 and then increased/decreased for 35 mol % Pb3O4. The dielectric properties and ac conductivity were measured over 0.02–1 MHz and 20–240 °C. An increase in Pb3O4 from 10 to 30 mol % led to reduced dielectric constant and conductivity, which is attributed to a more compact and polymerized structure that limits ion mobility. Here, conduction is primarily polaronic, supported by mixed-valence Pb2+/Pb4+ and Sb3+/Sb5+ ions. At 35 mol % Pb3O4, network depolymerization introduced nonbridging oxygens and structural disorder, enhancing the free volume and ion migration pathways. Consequently, ionic conduction, particularly of Pb2+, becomes dominant, significantly boosting the conductivity. Although Pb2+ ions are relatively immobile compared to Li+ or Na+, the insights gained offer a foundational understanding and guide the development of similar glass systems doped with lighter and more mobile alkali ions for practical battery applications.

Item Type:	Article
Uncontrolled Keywords:	Amorphous materials; Electrical conductivity; Electrical properties; Insulators; Ions
Subjects:	NATURAL SCIENCES > Physics NATURAL SCIENCES > Chemistry
Divisions:	Division of Materials Chemistry
Depositing User:	Lorena Palameta
Date Deposited:	31 Oct 2025 09:33
URI:	http://fulir.irb.hr/id/eprint/10118
DOI:	10.1021/acs.jpcb.5c05304

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