Electrical conductivity of BaM 2 O 4  (M = Nd, Sm) with a spinel structure

Nataliia Tarasova; Daniil Pyankov; Viktoria Zaviralova; Vladislava Gnatyuk; Ksenia Belova

doi:10.15826/chimtech.9038

Electrical conductivity of BaM₂O₄ (M = Nd, Sm) with a spinel structure

Nataliia Tarasova, Daniil Pyankov, Viktoria Zaviralova, Vladislava Gnatyuk, Ksenia Belova

Abstract

Complex oxides with a spinel structure can be considered as promising electrolyte materials for electrochemical devices to be used in energy generation. In this paper, complex oxides with a spinel structure were obtained, and their electrical conductivity properties at various pH₂O and pO₂ were investigated for the first time. These compositions are unstable in a humid atmosphere and decompose to barium hydroxide and metal oxide. The electrical conductivity values of BaNd₂O₄ and BaSm₂O₄ spinels must be measured strictly in an atmosphere with controlled humidity. The nature of their conductivity is mixed ionic-hole. The conductivity value of the BaNd₂O₄ composition is higher than that of the BaSm₂O₄ composition. The greatest values of the ionic conductivity were recorded for the BaSm₂O₄ composition, in which the share of oxygen ionic transport reaches up to 85% at low temperatures. The values of electrical conductivity at 700 ^oC are –3.2 and –3.6 S/cm for the BaNd₂O₄ and BaSm₂O₄ compositions; the values of ionic conductivity are –3.7 and –4.2 S/cm, correspondingly.

Keywords

spinel; layered perovskite; BaGd2O4; BaGd2O4; ionic conductivity

Full Text:

PDF

References

Ahmed HEH, Soylak M. Spinel nanomaterials and their composites as extractors and sensors for heavy metals and other pollutants. TrAC Trend Anal Chem. 2025;118159. doi:10.1016/j.trac.2025.118159

Korek H, Habanjar K, Elsharkawy SG, Awad R. Synthesis, characterization, and gas-sensing application of Cd0.5Zn0.5NdxFe2–xO4 nanoparticles. Mater Res Express. 2024;11(8):085008. doi:10.1088/2053-1591/ad6ef0

Chandu B, Mosali VSS, Kasturi S, Kumar VR, Bollikolla HB. Gas-sensing characteristics of AB2O4 (spinel ferrites)-structured metal oxides. In Complex and Composite Metal Oxides for Gas, VOC and Humidity Sensors. Elsevier. 2024:405–439. doi:10.1016/B978-0-323-95476-1.00007-1

Raturi P, Khan I, Joshi G, Kumar S, Gupta S. Ferrite nanoparticles for sensing applications. In Engineered ferrites and their applications (pp. 151–187). Singapore: Springer Nature; 2025.

Vatsalya VLS, Sundari GS, Laxmi KSM, Supraja S, Lakshmi CS. Elastic behaviour and gas sensing properties of substituted Ni–Zn nano crystalline ferrites. J Mater Sci Mater Electron. 2025;36(6):372. doi:10.1007/s10854-025-14329-6

Laobuthee A, Wongkasemjit S, Traversa E, Laine RM. MgAl2O4 spinel powders from oxide one pot synthesis (OOPS) process for ceramic humidity sensors. J Eur Ceram Soc. 2000;20(2):91-97. doi:10.1016/S0955-2219(99)00153-3

Oprea O, Gingasu D, Culita DC, Calderon Moreno JM, Marinescu G, Preda S. A sustainable approach for the synthesis of magnesium aluminate spinel towards photocatalytic applications. J Mater Sci. 2025;1–21. doi:10.1007/s10853-025-10946-y

Klym H, Hadzaman I, Vasylchyshyn I, Kushnir O. Sintering and exploitation properties of humidity-sensitive nanostructured ceramics and thick films based on MgAl2O4 spinel. Molecular Crystals and Liquid Crystals. 2024;768(16):840–848.

Nakane T, Naka T, Nakayama M, Uchikoshi T. Humidity sensitivity of chemically synthesized ZnAl2O4/Al. Sensors. 2022;22(16):6194. doi:10.3390/s22166194

Anchieta CG, Sallet D, Foletto EL, da Silva SS, Chiavone-Filho O, do Nascimento CA Synthesis of ternary zinc spinel oxides and their application in the photodegradation of organic pollutant. Ceramics International. 2014;40(3):4173–4178. doi:10.1016/j.ceramint.2013.08.074

Battiston S, Rigo C, Severo EDC, Mazutti MA, Kuhn RC, Gündel A, Foletto EL Synthesis of zinc aluminate (ZnAl2O4) spinel and its application as photocatalyst. Mater Res. 2024;17:734–738. doi:10.1590/S1516-14392014005000073

Gharibeh S. The high efficiency of ZnAl2O4/ZSM-5 in the removal of carbon monoxide contaminants during photocatalytic oxidation process. Microporous Mesoporous Mater. 2022;335:111797. doi:10.1016/j.micromeso.2022.111797

Li S, Zhou X, Fang G, Xie G, Liu X, Lin X, Qiu HJ Multicomponent spinel metal oxide nanocomposites as high-performance bifunctional catalysts in Zn–Air batteries. ACS Appl Energy Mater. 2020;3(8):7710–7718. doi:10.1021/acs.energyfuels.1c00275

Xu H, An Z, Wan Z, Zhao Y, Ma Z, Wang X. Dealloying-induced Mn-enhancing nanoporous Fe-based spinel oxides as stable electrocatalysts for oxygen reduction reaction and rechargeable zinc-air battery. Chem Engin J. 2024;502:158056. doi:10.1016/j.cej.2024.158056

Carrillo AJ, Chinchilla LE, Iglesias‐Juez A, Gutiérrez‐Rubio S, Sastre D, Pizarro P, Coronado JM Determining the Role of Fe‐Doping on Promoting the Thermochemical Energy Storage Performance of (Mn1−xFex)3O4 Spinels. Small Methods. 2021;5(10):2100550. doi:10.1002/smtd.202100550

Zhu X. Recent advances of transition metal oxides and chalcogenides in pseudo-capacitors and hybrid capacitors: A review of structures, synthetic strategies, and mechanism studies. J Energy Storage. 2022;49:104148. doi:10.1016/j.est.2022.104148

Ganesan M, Alagar S, Bagchi V, Piraman S. Surface oxygen engineered ZnCo2O4 planar hybrid supercapacitor electrode for high energy applications. J Energy Storage. 2024;98:112954. doi:10.1016/j.est.2024.112954

Ranjithkumar A, Balachandran S, Muruganandhan P, Girimurugan R. Electrochemical performance of MWCNT nanowires-decorated ZnCo2O4 sphere nanocomposite for an asymmetric capacitor. Diamond Related Mater. 2025;151:111808. doi:10.1016/j.diamond.2024.111808

Thaheem I, Ali S, Waqas M, Hussain A, Soomro AM, Bhutto Z, Shah J. Electrochemical performance of NiCo2O4 spinel cathodes for intermediate temperature solid oxide fuel cells. Phys Status Solidi. 2024;219(1): 2100542. doi:10.1002/pssa.202100542

Lin Z, Ma B, Chen Z, Cheng L, Zhou Y. Exploring B-site high-entropy configuration of spinel oxides for improved cathode performance in solid oxide fuel cells. J Eur Ceram Soc. 2024;44(4):2233-2241. doi:10.1016/j.jeurceramsoc.2023.11.004

Margoni MM, Akbari-Fakhrabadi A, Mangalaraja RV Recent advances in cobalt-based cathode materials for intermediate solid oxide fuel cells. Mater Technol Energy Environment Nexus. 2023;2:6–10.

Xu R, Liu S, Yang M, Yang G, Luo Z, Ran, R, Shao Z.Advancements and prospects of perovskite-based fuel electrodes in solid oxide cells for CO2 electrolysis to CO. Chem Sci. 2024;15(29);11166–11187. doi:10.1039/D4SC03306J

Sharma SK, Bessiere A, Gourier D, Sraiki G, Viana B, Dereń PJ, Richard C. Optical properties and storage capabilities of AB2O4:Cr3+ (A= Zn, Mg, B= Ga, Al). In Oxide-based. Mater Devices V. 2014;8987:102–108. doi:10.1117/12.2048836

Yu X, Yang XX, Huan J, Tong J, Qiao Y, Xing JJ, Zhao JT. Intense NIR mechanoluminescence from Al3+-regulated MgGa2O4:Cr3+. Chem Engin J. 2024;491:152155. doi:10.1016/j.cej.2024.152155

Chen G, Jin Y, Yuan L, Wang B, Huo J, Suo H, Wang F. Unlocking Cr3+–Cr3+ coupling in spinel: ultrabroadband near-infrared emission beyond 900 nm with high efficiency and thermal stability. ACS Appl Mater Interfaces. 202;16(23):30185–30195.

Zentefis NP, Fiore A, Yang Y. Recent Advancements of Spinel Oxide Materials in Energy and Fuel Applications. Energy Fuels. 2025;39(15):7167–7181.

Deng W, Xu Y, Zhang X, Xia J, Xu K, Gao H, Chen Y. Achieving active and durable oxygen reduction/evolution reactions on protonic ceramic electrochemical cells with spinel-based air electrodes. J Mater Chem A. 2025;13(21):15636–15644.

Wu Z, Zhu P, Huang Y, Yao J, Yang F, Zhang Z, Ni M, A comprehensive review of modeling of solid oxide fuel cells: From large systems to fine electrodes. Chem Rev. 2025;125:2184–2268. doi:10.1021/acs.chemrev.4c00614

Tang C, Yao Y, Wang N, Zhang X, Zheng F, Du L, Ye S, Green hydrogen production by intermediate-temperature protonic solid oxide electrolysis cells: Advances, challenges, and perspectives. InfoMat 6. 2024;e12515. doi:10.1002/inf2.12515

Duggan E, Recent progress in sustainable energy systems development: Investment, operations, and decarbonization. Curr Sustain Energy Rep. 2025;12:1–9. doi:10.1007/s40518-024-00248-3

Garcia-Vallejo MC, Alzate CAC, Sustainability of hydrogen production considering alternative technologies towards a neutral carbon society. Int J Hydrog Energy 2024;64:853–863. doi:10.1016/j.ijhydene.2024.03.328

Tarasova NA, Animitsa IE, Galisheva AO, Medvedev DA. Layered and hexagonal perovskites as novel classes of proton-conducting solid electrolytes. A focus review. Electrochem Mater Technol. 2022;1(1):20221004. doi:10.15826/elmattech.2022.1.004

Pan X, Wu W, Zhou X, Wu S. Enhanced protonic and oxygen-ionic conductivity in Ga-doped Nd₂Ce₂O₇ electrolytes for intermediate-temperature solid oxide fuel cell. Electrochim. Acta. 2024:507;145142. doi:10.1016/j.electacta.2024.145142

Tarasova NA, Filinkova YV, Animitsa IE. Hydration and forms of oxygen-hydrogen groups in oxyfluorides Ba2-0.5xIn2O5-xFx. Russ. J Phys Chem A 2012;86:1208–1211. doi:10.1134/S0036024412080134

Tarasova N, Animitsa I. Protonic transport in oxyfluorides Ba2InO3F and Ba3In2O5F2 with Ruddlesden-Popper structure. Solid State Ionics. 2015;275:53-57. doi:10.1016/j.ssi.2015.03.025

Animitsa IE, Korona DV, Bushueva AV, Andreev RD, Gilev AR. The effect of Zn-doping on electrical properties, hydration, sintering and chemical resistance of hexagonal perovskite Ba7In6Al2O19. Ceram Int. 2024;50:45851–45861. doi:10.1016/j.ceramint.2024.08.426

Baratov A, Filonova E, Ivanova I, Hanif MB, Irshad M, Khan MZ, Motola M, Rauf S, Medvedev D. Current and further trajectories in designing functional materials for solid oxide electrochemical cells: A review of other reviews. J. Energy Chem. 2024;94:302-331. doi:10.1016/j.jechem.2024.02.045

Medvedev D. Doping design strategies of proton-conducting perovskite oxides: A brief compositional map. Int J Hydrog Energy. 2025;161:150689. doi:10.1016/j.ijhydene.2025.150689

Kato S, Ogasawara M, Sugai M, Nakata S. Synthesis and oxide ion conductivity of new layered perovskite La1-xSr1+xInO4-d. Solid State Ionics. 2002;149:53–57. doi:10.1016/S0167-2738(02)00138-8

Fujii K, Esaki Y, Omoto K, Yashima M, Hoshikawa A, Ishigaki T, Hester JR. New perovskite-related structure family of oxide-ion conducting materials NdBaInO4. Chem Mater. 2014;26:2488−2491. doi:10.1021/cm500776x

Troncoso L, Alonso JA, Aguadero A, Low activation energies for interstitial oxygen conduction in the layered perovskites La1+xSr1-xInO4+d. J Mater Chem A. 2015;3:17797–17803. doi:10.1039/c5ta03185k

Troncoso LJA, Alonso MT, Fernández-Díaz A. Introduction of interstitial oxygen atoms in the layered perovskite LaSrIn1-xBxO4+δ system (B=Zr, Ti). Solid State Ionics 282 (2015) 82˗87. doi:10.1016/j.ssi.2015.09.014

Ishihara T, Yan Yu, Sakai T, Ida S. Oxide ion conductivity in doped NdBaInO4. Solid State Ion. 2016;288:262 doi:10.1016/j.ssi.2016.01.011

Yang X, Liu S, Lu F, Xu J, Kuan, X. Acceptor doping and oxygen vacancy migration in layered perovskite NdBaInO4-based mixed conductors. J Phys Chem C. 2016;120:6416–6426.

Fijii K, Yashima M. Discovery and development of BaNdInO4 – A brief review. J Ceram Soc Jpn. 2018;126:852–859.

Vasin D, Lakiza N, Animitsa I. Layered perovskite SrLaAlO4 as a proton-conducting material for intermediate-temperature solid oxide fuel cells: synthesis, hydration, and electrical properties. Ionics. 2025;31:8173–8183. doi:10.1007/s11581-025-06434-7

Tarasova N, Animitsa I, Galisheva A, Korona D. Incorporation and conduction of protons in Ca, Sr, Ba-doped BaLaInO4 with Ruddlesden-Popper structure. Mater. 2019;12:1668. doi:10.3390/ma12101668

Troncoso L, Arce MD, Fernández-Díaz MT, Mogni LV, Alonso JA. Water insertion and combined interstitial-vacancy oxygen conduction in the layered perovskites La1.2Sr0.8-xBaxInO4+δ. New J Chem. 2019;43:6087–6094. doi:10.1039/C8NJ05320K

Zhou Y, Shiraiwa M, Nagao M, Fujii K, Tanaka I, Yashima M, Baque L, Basbus JF, Mogni LV, Skinner SJ. Protonic conduction in the BaNdInO4 structure achieved by acceptor doping. Chem Mater. 2021;33:2139–2146. doi:10.1021/acs.chemmater.0c04828

Tarasova N, Galisheva A, Animitsa I, Anokhina I, Gilev A, Cheremisina P. Novel mid-temperature Y3+ → In3+ doped proton conductors based on the layered perovskite BaLaInO4. Ceram Int. 2022;48:15677–15685. doi:10.1016/j.ceramint.2022.02.102

Abakumova E, Kuznetsova T, Zaviralova V, Gnatyuk V, Pyankov D, Tarasova N, Ionic conductivity in the novel complex oxide Ba0.95La1.05InO4.025 with Ruddlesden-Popper structure. Ionics. 2025;31:7125˗7134. doi:10.1007/s11581-025-06383-1

Abakumova E, Tarasova N, Proton transport in the novel samarium-doped layered perovskite based on BaLaInO4. Ceram Int. 2024;50:40298˗40305. doi:10.1016/j.ceramint.2024.05.479

Abakumova E, Kuznetsova T, Gnatyuk V, Pyankov D, Zaviralova V, Tarasova N, Oxygen ion and proton transport in novel isovalent doped Ca2+/Sr2+ → Ba layered perovskites based on BaLaInO4, Int J Hydrog Energy. 225;164;150824. doi:10.1016/j.ijhydene.2025.150824

Murakami T, Avdeev M, Morikawa R, Hester JR, Yashima M, High Proton Conductivity in β-Ba2ScAlO5 Enabled by Octahedral and Intrinsically Oxygen‐Deficient Layers. Adv Function Mater. 2023;33:2206777. doi:10.1002/adfm.202206777

Ruddlesden SN, Popper P. New compounds of the K2NiF4 type. Acta Cryst. 1957;10:538–539. doi:10.1107/S0365110X57001929

Besara T, Lundberg MS, Sun J, Ramirez D, Dong L, Whalen JB, Siegrist T. Single crystal synthesis and magnetism of the BaLn2O4 family (Ln= lanthanide). Progr Solid State Chem. 2014;42(3):23–36. doi:10.1016/j.progsolidstchem.2014.05.001

小林秀彦, 荻野博幸, 中村和正, 森利之, 山村博, 三田村孝. BaCO 3-M2O3 混合粉末 (M: La, Nd, Sm, Gd, Ho, Y) から反応焼結により合成した BaM2O4 の秩序-無秩序転移. 日本セラミックス協会学術論文誌. 1994;102(1186):583–586. doi:10.2109/jcersj.102.583

Gao H, Liu S, Li Y, Conte E, Cao Y. A critical review of spinel structured iron cobalt oxides based materials for electrochemical energy storage and conversion. Energies. 1997;10:1787. doi:10.3390/en10111787

Xie H, Cui J, Yao Z, Ding X, Zhang Z, Luo D, Lin Z. Revealing the role of spinel phase on Li-rich layered oxides: A review. Chem Eng J. 2022;427:131978. doi:10.1016/j.cej.2021.131978

Kim H, Seo DH, Kim H, Park I, Hong J, Park KY, Kang K. Multicomponent effects on the crystal structures and electrochemical properties of spinel-structured M3O4 (M= Fe, Mn, Co) anodes in lithium rechargeable batteries. Chem Mater. 2012;24(4):720–725. doi:10.1021/cm2036794

DOI: https://doi.org/10.15826/chimtech.9038

Copyright (c) 2025 Nataliia Tarasova, Daniil Pyankov, Viktoria Zaviralova, Vladislava Gnatyuk, Ksenia Belova