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

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.

The Crystallization Behavior of a Na2O-GeO2-P2O5 Glass System: A (Micro)Structural, Electrical, and Dielectric Study.

Sodium-phosphate-based glass-ceramics (GCs) are promising materials for a wide range of applications, including solid-state sodium-ion batteries, microelectronic packaging substrates, and humidity sensors. This study investigated the impact of 24 h heat-treatments (HT) at varying temperatures on Na-Ge-P glass, with a focus on (micro)structural, electrical, and dielectric properties of prepared GCs. Various techniques such as powder X-ray diffraction (PXRD), infrared spectroscopy-attenuated total reflection (IR-ATR), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) were employed. With the elevation of HT temperature, crystallinity progressively rose; at 450 °C, the microstructure retained amorphous traits featuring nanometric grains, whereas at 550 °C, HT resulted in fully crystallized structures characterized by square-shaped micron-scale grains of NaPO3. The insight into the evaluation of electrical and dielectric properties was provided by Solid-State Impedance Spectroscopy (SS-IS), revealing a strong correlation with the conditions of controlled crystallization and observed (micro)structure. Compared to the initial glass, which showed DC conductivity (σDC) on the order of magnitude 10-7 Ω-1 cm-1 at 393 K, the obtained GCs exhibited a lower σDC ranging from 10-8 to 10-10 Ω-1 cm-1. With the rise in HT temperature, σDC further decreased due to the crystallization of the NaPO3 phase, depleting the glass matrix of mobile Na+ ions. The prepared GCs showed improved dielectric parameters in comparison to the initial glass, with a noticeable increase in dielectric constant values (~20) followed by a decline in dielectric loss (~10-3) values as the HT temperatures rise. Particularly, the GC obtained at @450 stood out as the optimal sample, showcasing an elevated dielectric constant and low dielectric loss value, along with moderate ionic conductivity. This research uncovers the intricate relationship between heat-treatment conditions and material properties, emphasizing that controlled crystallization allows for precise modifications to microstructure and phase composition within the remaining glassy phase, ultimately facilitating the fine-tuning of material properties.

Sodium-Ion Conductivity and Humidity-Sensing Properties of Na2O-MoO3-P2O5 Glass-Ceramics.

A series of glass-ceramics were prepared by heat-treatments of 40Na2O-30MoO3-30P2O5 (in mol%) glass in a temperature range from 380 (Tg) to 490 °C (Tc) and for 1-24 h. The prepared glass-ceramics contain from 2 to 25 wt.% of crystalline NaMoO2PO4. The sodium-ion conductivity in these materials decreases up to one order of magnitude with an increase in the degree of crystallization due to the immobilization of sodium ions in crystalline NaMoO2PO4. The transport of sodium ions in these materials occurs primarily through the dominant continuous glassy phase, and it is weakly affected by the sporadically distributed crystalline grains. However, the prepared glass-ceramics exhibit high proton conductivity in a humid atmosphere and remarkable humidity-sensing properties; this could be related to crystalline NaMoO2PO4, which provides sites for water adsorption. The glass-ceramic prepared at 450 °C for 24 h shows the best humidity-sensing performance among all samples, showing an increase in proton conductivity for more than seven orders of magnitude with the increase in relative humidity from 0% to 95%. Under a highly humid atmosphere (95% relative humidity and 25 °C), the proton conductivity of this glass-ceramic reaches 5.2 × 10-3 (Ω cm)-1. Moreover, the electrical response of these materials on the change in the relative humidity is linear and reversible in the entire range of the relative humidity, which indicates that they are novel promising candidates for application as humidity sensors.

A significant enhancement of sodium ion conductivity in phosphate glasses by addition of WO3 and MoO3: the effect of mixed conventional-conditional glass-forming oxides.

Ion conducting oxide glasses are attractive materials for application in various electrochemical devices and an understanding of the structure-transport properties relationship is crucial for their development. An interesting effect of glass structure on the dynamics of mobile ions is the mixed glass-former effect which causes a non-linear change of ionic conductivity when glass-forming oxides get gradually substituted. Here, we report a strong, positive effect of structural changes on the conductivity of sodium ions in two glass systems 40Na2O-xMoO3-(60-x)P2O5 and 40Na2O-xWO3-(60-x)P2O5; x = 0-50 mol% where a conventional glass-forming oxide (P2O5) is gradually replaced by WO3/MoO3 which are conditional ones. In both glass systems, the compositional change in DC conductivity is non-linear, with the maximal increase of four orders of magnitude in the case of WO3 and three orders of magnitude in the case of MoO3. This significant enhancement of ionic conductivity is related to the formation of mixed phosphate-tungstate and phosphate-molybdate units in the glass network. The facilitating effect of these structural units on sodium ion dynamics is also observed in the changes of the shape of frequency-dependent conductivity and in the values of typical spatial extent of diffusion of sodium ions known as the Sidebottom length.

Lithium-Ion Mobility in Quaternary Boro-Germano-Phosphate Glasses.

Effect of the structural changes, electrical conductivity, and dielectric properties on the addition of a third glass-former, GeO2, to the borophosphate glasses, 40Li2O-10B2O3-(50 - x)P2O5-xGeO2, x = 0-25 mol %, has been studied. Introduction of GeO2 causes the structural modifications in the glass network, which results in a continuous increase in electrical conductivity. Glasses with low GeO2 content, up to 10 mol %, show a rapid increase in dc conductivity as a result of the interlinkage of slightly depolymerized phosphate chains and negatively charged [GeO4](-) units, which enhances the migration of Li(+) ions. The Li(+) ions compensate these delocalized charges connecting both phosphate and germanium units, which results in reduction of both bond effectiveness and binding energy of Li(+) ions and therefore enables their hop to the next charge-compensating site. For higher GeO2 content, the dc conductivity increases slightly, tending to approach a maximum in Li(+) ion mobility caused by the incorporation of GeO2 units into phosphate network combined with conversion of GeO4 to GeO6 units. The strong cross-linkage of germanium and phosphate units creates heteroatomic P-O-Ge bonds responsible for more effectively trapped Li(+) ions. A close correspondence between dielectric and conductivity parameters at high frequencies indicates that the increase in conductivity indeed is controlled by the modification of structure as a function of GeO2 addition.

Electrical mobility of silver ion in Ag2O-B2O3-P2O5-TeO2 glasses.

The effect of adding TeO(2) into (100 - x)[0.5Ag(2)O - 0.1B(2)O(3) - 0.4P(2)O(5)] - xTeO(2), with 0-80 mol % TeO(2) glass, on the structural changes and electrical properties has been investigated. DSC and thermodilatomery were used to study their thermal behavior, structure was studied by Raman spectroscopy, and electrical properties have been studied by impedance spectroscopy over a wide temperature and frequency range. The introduction of TeO(2) as a third glass former to the glass network causes the structural transformation from TeO(3) (tp) to TeO(4) (tbp) which contributes to the changes in conductivity. The glasses with low TeO(2) content show only a slow decrease in dc conductivity with addition of TeO(2) due to the increase of the number of nonbridging oxygens, which increases the mobility of Ag(+) ions. The steep decrease in conductivity for glasses containing more than 40 mol % TeO(2) is a result of decrease of the Ag(2)O content and stronger cross-linkage in glass network through the formation of more Te-(eq)O(ax)-Te bonds in TeO(4) tbp units. The glasses obey ac conductivity scaling with respect to temperature, implying that the dynamic process is not temperature dependent. On the other hand, the scaling of the spectra for different glass compositions showed the deviations from the Summerfield scaling because of the local structural disorder which occurs as a result of the structural modifications in the tellurite glass network.

Site connectivities in silver borophosphate glasses: new results from 11B{31P} and 31P{11B} rotational echo double resonance NMR spectroscopy.

Local and medium range order in the glass system 50Ag2O-50[(B2O3)x-(P2O5)(1-x)] (x=0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6) have been investigated by high-resolution solid state nuclear magnetic resonance (NMR) techniques. The detailed local site distribution has been derived from deconvolution analysis of the 11B and 31P magic-angle spinning (MAS) NMR signals. Quantitative information regarding the extent of boron-oxygen-phosphorus connectivity has been obtained on the basis of 11B[31P} and 31P{11B} rotational echo double resonance experiments. Incorporation of borate into silver metaphosphate glasses produces four-coordinate BO4/2- sites, which crosslink the metaphosphate chains, resulting in a significant increase in the glass transition temperature. Furthermore, the presence of borate favors the disproportionation of P(2) chain-like units into P(1) and P(3) sites, an effect not observed in binary alkali phosphate glasses. Finally, borate incorporation beyond x=0.3 results in the formation of neutral BO3/2 units, indicating some net charge transfer from the borate to the phosphate network former species. This latter result corresponds to the general metal ion scavenging effect observed for phosphate species in other mixed network former glass systems. In the present system, the effect is relatively moderate, however, suggesting that anionic BO4/2- groups are stabilized by the interaction with the phosphate groups.