Solid-state impedance spectroscopy studies of dielectric properties and relaxation processes in Na₂O-V₂O₅-Nb₂O₅-P₂O₅ glass system

Abstract

Solid-state impedance spectroscopy (SS-IS) was used to investigate the influence of structural modifications resulting from the addition of Nb₂O₅ on the dielectric properties and relaxation processes in the quaternary mixed glass former (MGF) system 35Na₂O-10V₂O₅-(55−x)P₂O₅−xNb₂O₅ (x = 0–40, mol%). The dielectric parameters, including the dielectric strength and dielectric loss, are determined from the frequency and temperature-dependent complex permittivity data, revealing a significant dependence on the Nb₂O₅ content. The transition from a predominantly phosphate glass network (x < 10, region I) to a mixed niobate-phosphate glass network (10 ≤ x ≤ 20, region II) leads to an increase in the dielectric parameters, which correlates with the observed trend in the direct-current (DC) conductivity. In the predominantly niobate network (x ≥ 25, region III), the highly polarizable nature of Nb⁵⁺ ions leads to a further increase in the dielectric permittivity and dielectric strength. This is particularly evident in Nb-40 glass-ceramic, which contains Na₁₃Nb₃₅O₉₄ crystalline phase with a tungsten bronze structure and exhibits the highest dielectric permittivity of 61.81 and the lowest loss factor of 0.032 at 303 K and 10 kHz. The relaxation studies, analyzed through modulus formalism and complex impedance data, show that DC conductivity and relaxation processes are governed by the same mechanism, attributed to ionic conductivity. In contrast to glasses with a single peak in frequency dependence of imaginary part of electrical modulus, M″(ω), Nb-40 glass-ceramic exhibits two distinct contributions with similar relaxation times. The high-frequency peak indicates bulk ionic conductivity, while the additional low-frequency peak is associated with the grain boundary effect, confirmed by the electrical equivalent circuit (EEC) modelling. The scaling characteristics of permittivity and conductivity spectra, along with the electrical modulus, validate time-temperature superposition and demonstrate a strong correlation with composition and modification of the glass structure upon Nb₂O₅ incorporation.

Keywords

phosphate glasses / glass-ceramics / impedance spectroscopy / dielectric properties / relaxation processes / permittivity scaling / conductivity scaling / modulus formalism

References

[[1]] Q.B. Yuan, M. Chen, S.L. Zhan, Y.X. Li, Y. Lin, and H.B. Yang, Ceramic-based dielectrics for electrostatic energy storage applications: Fundamental aspects, recent progress, and remaining challenges, Chem. Eng. J., 446(2022), art. No. 136315.

[[2]] Z.H. Yao, Z. Song, H. Hao, et al., Homogeneous/inhomogeneous-structured dielectrics and their energy-storage performances, Adv. Mater., 29(2017), No. 20, art. No. 1601727.

[[3]] Smirnova A, Numan-Al-Mobin A, Inamuddin. . Green Sustainable Process for Chemical and Environmental Engineering and Science: Solid-State Energy Storage - A Path to Environmental Sustainability, 2023 Amsterdam Elsevier

[[4]] S. Gandi, V.S.C.S. Vaddadi, S.S.S. Panda, et al., Recent progress in the development of glass and glass-ceramic cathode/solid electrolyte materials for next-generation high capacity all-solid-state sodium-ion batteries: A review, J. Power Sources, 521(2022), art. No. 230930.

[[5]] Chen C, Zheng YX, Li B. Achieving ultrafast discharge speed and excellent energy storage efficiency in environmentally friendly niobate-based glass ceramics. J. Eur. Ceram. Soc., 2022, 42(15): 6977,

[[6]] T.T. Fu, S.F. Xie, C.S. Liu, H.R. Bai, B. Shen, and J.W. Zhai, High discharge energy density and ultralow dielectric loss in alkali-free niobate-based glass-ceramics by composition optimization, Scripta Mater., 221(2022), art. No. 114993.

[[7]] Luo F, Qin YY, Shang F, Chen GH. Crystallization temperature dependence of structure, electrical and energy storage properties in BaO-Na₂O-Nb₂O₅-Al₂O₃-B₂O₃ glass ceramics. Ceram. Int., 2022, 48(20): 30661,

[[8]] Liu CS, Xie SF, Chen KK, Song BJ, Shen B, Zhai JW. High breakdown strength and enhanced energy storage performance of niobate-based glass-ceramics via glass phase structure optimization. Ceram. Int., 2021, 47(22): 31229,

[[9]] T. Komatsu, T. Honma, T. Tasheva, and V. Dimitrov, Structural role of Nb₂O₅ in glass-forming ability, electronic polarizability and nanocrystallization in glasses: A review, J. Non-Cryst. Solids, 581(2022), art. No. 121414.

[[10]] Wang SJ, Tian J, Yang K, Liu JR, Zhai JW, Shen B. Crystallization kinetics behavior and dielectric energy storage properties of strontium potassium niobate glass-ceramics with different nucleating agents. Ceram. Int., 2018, 44(7): 8528,

[[11]] Graça MPF, da Silva MGF, Sombra ASB, Valente MA. Electric and dielectric properties of a SiO₂-Na₂O-Nb₂O₅ glass subject to a controlled heat-treatment process. Physica B, 2007, 396(1–2): 62,

[[12]] X. Peng, Y.P. Pu, Z.X. Sun, et al., Achieving high electrical homogeneity in (Na₂O, K₂O)-Nb₂O₅-SiO₂-MO (M = Ca²⁺, Sr²⁺, Ba²⁺) glass-ceramics for energy storage by composition design, Composites Part B, 260(2023), art. No. 110765.

[[13]] Liu XY, Zhao K, Jiao H. Stabilizing the anti-ferroelectric phase in NaO-Nb₂O₅-CaO-B₂O₃-SiO₂-ZrO₂ glass-ceramics using the modification of K⁺ ion. Ceram. Int., 2023, 49(12): 21078,

[[14]] Graça MPF, da Silva MGF, Valente MA. NaNbO₃ crystals dispersed in a B₂O₃ glass matrix–Structural characteristics versus electrical and dielectrical properties. Solid State Sci., 2009, 11(2): 570,

[[15]] Benyounoussy S, Bih L, Muñoz F, Rubio-Marcos F, Naji M, El Bouari A. Structure, dielectric, and energy storage behaviors of the lossy glass-ceramics obtained from Na₂O-Nb₂O₅-P₂O₅ glassy-system. Phase Transitions, 2021, 94(9): 634,

[[16]] S. Benyounoussy, L. Bih, F. Muñoz, F. Rubio-Marcos, and A. El Bouari, Effect of the Na₂O-Nb₂O₅-P₂O₅ glass additive on the structure, dielectric and energy storage performances of sodium niobate ceramics, Heliyon, 7(2021), No. 5, art. No. e07113.

[[17]] A. Ihyadn, A. Lahmar, D. Mezzane, et al., Structural, electrical and energy storage properties of BaO-Na₂O-Nb₂O₅-WO₃-P₂O₅ glass-ceramics system, Mater. Res. Express, 6(2019), No. 11, art. No. 115203.

[[18]] A. Ihyadn, S. Merselmiz, D. Mezzane, et al., Dielectric and energy storage properties of Ba_0.85Ca_0.15Zr_0.1Ti_0.90O₃ ceramics with BaO-Na₂O-Nb₂O₅-WO₃-P₂O₅ glass addition, J. Mater. Sci. Mater. Electron., 34(2023), No. 12, art. No. 1051.

[[19]] M. Maraj, W.W. Wei, B.L. Peng, and W.H. Sun, Dielectric and energy storage properties of Ba(_1−x)Ca_xZr_yTi(_1−y)O₃ (BCZT): A review, Materials, 12(2019), No. 21, art. No. 3641.

[[20]] L. Zhang, Y.P. Pu, and M. Chen, Complex impedance spectroscopy for capacitive energy-storage ceramics: A review and prospects, Mater. Today Chem., 28(2023), art. No. 101353.

[[21]] Sanghi S, Sheoran A, Agarwal A, Khasa S. Conductivity and dielectric relaxation in niobium alkali borate glasses. Physica B, 2010, 405(24): 4919,

[[22]] Graça MPF, Melo BMG, Prezas PR, Valente MA, Freire FNA, Bih L. Electrical and dielectric analysis of phosphate based glasses doped with alkali oxides. Mater. Des., 2015, 86: 427,

[[23]] Attafi Y, Liu SQ. Conductivity and dielectric properties of Na₂O-K₂O-Nb₂O₅-P₂O₅ glasses with varying amounts of Nb₂O₅. J. Non-Cryst. Solids, 2016, 447: 74,

[[24]] Gerace KS, Lanagan MT, Mauro JC. Dielectric polarizability of SiO₂ in niobiosilicate glasses. J. Am. Ceram. Soc., 2023, 106(8): 4546,

[[25]] S. Marijan, M. Razum, T. Klaser, et al., Tailoring structure for improved sodium mobility and electrical properties in V₂O₅-Nb₂O₅-P₂O₅ glass(es)-(ceramics), J. Phys. Chem. Solids, 181(2023), art. No. 111461.

[[26]] Moguš-Milanković A, Sklepić K, Blažanović H, Mošner P, Vorokhta M, Koudelka L. Influence of germanium oxide addition on the electrical properties of Li₂O-B₂O₃-P₂O₅ glasses. J. Power Sources, 2013, 242: 91,

[[27]] Prasad V, Pavić L, Moguš-Milanković A, et al.. Influence of silver ion concentration on dielectric characteristics of Li₂O-Nb₂O₅-P₂O₅ glasses. J. Alloys Compd., 2019, 773: 654,

[[28]] Pavić L, Skoko Ž, Gajović A, Su DS, Moguš-Milanković A. Electrical transport in iron phosphate glass-ceramics. J. Non-Cryst. Solids, 2018, 502: 44,

[[29]] Pavić L, Sklepić K, Skoko Ž, et al.. Ionic conductivity of lithium germanium phosphate glass-ceramics. J. Phys. Chem. C, 2019, 123(38): 23312,

[[30]] Pavić L, Nikolić J, Graça MPF, et al.. Effect of controlled crystallization on polaronic transport in phosphate-based glass-ceramics. Int. J. Appl. Glass Sci., 2020, 11(1): 97,

[[31]] A. Bafti, S. Kubuki, H. Ertap, et al., Electrical transport in iron phosphate-based glass-(ceramics): Insights into the role of B₂O₃ and HfO₂ from model-free scaling procedures, Nanomaterials, 12(2022), No. 4, art. No. 639.

[[32]] Kremer F, Schönhals A. . Broadband Dielectric Spectroscopy, 2003 Heidelberg Springer Berlin,

[[33]] Sidebottom DL. Universal approach for scaling the ac conductivity in ionic glasses. Phys. Rev. Lett., 1999, 82(18): 3653,

[[34]] D.L. Sidebottom, B. Roling, and K. Funke, Ionic conduction in solids: Comparing conductivity and modulus representations with regard to scaling properties, Phys. Rev. B, 63(2000), No. 2, art. No. 024301.

[[35]] Mohan NK, Reddy MR, Jayasankar CK, Veeraiah N. Spectroscopic and dielectric studies on MnO doped PbO-Nb₂O₅-P₂O₅ glass system. J. Alloys Compd., 2008, 458(1–2): 66,

[[36]] Roling B. Scaling properties of the conductivity spectra of glasses and supercooled melts. Solid State Ionics, 1998, 105(1–4): 185,

[[37]] Bakry M, Klinkenbusch L. Using the Kramers-Kronig transforms to retrieve the conductivity from the effective complex permittivity. Adv. Radio Sci., 2018, 16: 23,

[[38]] Macedo PB, Moynihan CT, Bose R. Role of ionic diffusion in polarization in vitreous ionic conductors. Phys. Chem. Glasses, 1972, 13(6): 171

[[39]] Sinclair DC. Characterization of electro-materials using ac impedance spectroscopy. Bol. Soc. Esp. Ceram. Vidrio, 1995, 34(2): 55