Tailoring structure for improved sodium mobility and electrical properties in V2O5–Nb2O5–P2O5 Glass(es)-(Ceramics)

Marijan, Sara; Razum, Marta; Klaser, Teodoro; Mošner, Petr; Koudelka, Ladislav; Skoko, Željko; Pisk, Jana; Pavić, Luka

doi:10.1016/j.jpcs.2023.111461

Cited by 8 publications

(20 citation statements)

References 44 publications

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“…Here, it is worth noting the correlation between the scaling outcomes for the investigated glasses and their σ DC and E DC values. Specifically, the shape of the master curves is observed to change concurrently with the changes in σ DC , mirroring phenomena observed in our previous study on another series within the Na-V-P-Nb system [27]. Furthermore, these alterations in the master curves coincide with the transition of the conductivity mechanism from mixed conductive in glasses with x < 10 to predominantly ionic in glasses with x ≥ 10.…”

Section: Scaling Properties Of Conductivity Spectrasupporting

confidence: 84%

“…Similar to V M , the T g trend follows a non-monotonic pattern, gradually decreasing until reaching a minimum for the 25V-20Nb glass, after which it begins to rise. These findings diverge from the anticipated thermal behaviour observed in similar glass systems, where T g typically increases nearly linearly with the addition of Nb 2 O 5 [27,[29][30][31][32][33][34]. In contrast to the anticipated rise in T g with the incorporation of Nb 2 O 5 , the 25V series displays a minimum, and T g values exhibit only small changes upon the introduction of Nb 2 O 5 .…”

Section: General Properties and Thermal Behaviourcontrasting

confidence: 83%

“…Variations in T g typically arise from the same factors influencing ρ and V M , such as the replacement of weaker P-O bonds with stronger Nb-O bonds and the formation of a more condensed mixed niobate-phosphate (Nb-P) network, leading to an increase in T g in previously reported series [27,[29][30][31][32][33][34]. However, the non-monotonic trend in T g within the 25V series indicates the unfavourable influence of Nb 2 O 5 on T g .…”

Section: General Properties and Thermal Behaviourmentioning

confidence: 97%

“…Building upon the aforementioned discoveries regarding both crystalline and glassy Na-V-P-based materials, and drawing on our proficiency in exploring the electrical properties of diverse alkali-TMO-containing phosphate-based systems manifesting distinct electrical conductivity mechanisms (ionic [22], polaronic [23], mixed ionic-polaronic [24][25][26]), we extended our research scope to encompass Na-V-P-based glass-(ceramic) systems incorporating Nb 2 O 5 . In our prior research, we examined the influence of Nb 2 O 5 addition on the thermal, (micro)structural, and electrical characteristics of 35Na 2 O-10V 2 O 5 -(55 − x)P 2 O 5 − xNb 2 O 5 (x = 0-40, mol%) glass and glass-ceramic series [27]. Solid-state impedance spectroscopy (SS-IS) measurements unveiled a purely ionic mechanism of electrical conductivity, despite the presence of 10 mol% of V 2 O 5 .…”

Section: Introductionmentioning

confidence: 99%

“…Using the model-free Summerfield scaling procedure, mixed ionic-polaronic conductivity is observed for x < 10 mol%, while for x ≥ 10 mol%, ionic conductivity prevails. A comparative analysis of two analogue Na-Nb-P series, with 10 mol% V 2 O 5 [27] and 25 mol% V 2 O 5 , evaluates the impact of V 2 O 5 content on the electrical transport mechanism and the extent of its polaronic contribution.…”

Section: Introductionmentioning

confidence: 99%

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Exploring the Effect of V2O5 and Nb2O5 Content on the Structural, Thermal, and Electrical Characteristics of Sodium Phosphate Glasses and Glass–Ceramics

Marijan,

Klaser,

Mirosavljević

et al. 2024

IJMS

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Na-V-P-Nb-based materials have gained substantial recognition as cathode materials in high-rate sodium-ion batteries due to their unique properties and compositions, comprising both alkali and transition metal ions, which allow them to exhibit a mixed ionic–polaronic conduction mechanism. In this study, the impact of introducing two transition metal oxides, V2O5 and Nb2O5, on the thermal, (micro)structural, and electrical properties of the 35Na2O-25V2O5-(40 − x)P2O5 − xNb2O5 system is examined. The starting glass shows the highest values of DC conductivity, σDC, reaching 1.45 × 10−8 Ω−1 cm−1 at 303 K, along with a glass transition temperature, Tg, of 371 °C. The incorporation of Nb2O5 influences both σDC and Tg, resulting in non-linear trends, with the lowest values observed for the glass with x = 20 mol%. Electron paramagnetic resonance measurements and vibrational spectroscopy results suggest that the observed non-monotonic trend in σDC arises from a diminishing contribution of polaronic conductivity due to the decrease in the relative number of V4+ ions and the introduction of Nb2O5, which disrupts the predominantly mixed vanadate–phosphate network within the starting glasses, consequently impeding polaronic transport. The mechanism of electrical transport is investigated using the model-free Summerfield scaling procedure, revealing the presence of mixed ionic–polaronic conductivity in glasses where x < 10 mol%, whereas for x ≥ 10 mol%, the ionic conductivity mechanism becomes prominent. To assess the impact of the V2O5 content on the electrical transport mechanism, a comparative analysis of two analogue series with varying V2O5 content (10 and 25 mol%) is conducted to evaluate the extent of its polaronic contribution.

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Section: Scaling Properties Of Conductivity Spectrasupporting

confidence: 84%