Broad Applicability of Electrochemical Impedance Spectroscopy to the Measurement of Oxygen Nonstoichiometry in Mixed Ion and Electron Conductors

Huang, Ruiyun; Carr, Connor G.; Gopal, Chirranjeevi Balaji; Haile, Sossina M.

doi:10.1021/acsami.2c05417

Broad Applicability of Electrochemical Impedance Spectroscopy to the Measurement of Oxygen Nonstoichiometry in Mixed Ion and Electron Conductors

Journal Article · Mon Apr 25 00:00:00 EDT 2022 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.2c05417· OSTI ID:1985151

Huang, Ruiyun ^[1]; ^[2]; Gopal, Chirranjeevi Balaji ^[3]; ^[2]

Northwestern University, Evanston, IL (United States); Northwestern University
Northwestern University, Evanston, IL (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)

Oxygen non-stoichiometry is a fundamental feature of mixed ion and electron conductors (MIECs). In this work a general electrochemical method for determining non-stoichiometry in thin film MIECs, via measurement of the chemical capacitance, is demonstrated using ceria and ceria-zirconia (Ce_0.8Zr_0.2O_2-δ) as representative materials. A.C. impedance data are collected from both materials at high temperature (750-900 °C) under reducing conditions with oxygen partial pressure (pO₂) in the range 10-13 to 10-20 atm. Additional measurements of ceria-zirconia films are made under relatively oxidizing conditions with pO₂ in the range 0.2 to 10^-4 atm and temperatures of 800-900 °C. Under reducing conditions, the impedance spectra are described by a simple circuit in which a resistor is in series with a resistor and capacitor in parallel, and thickness dependent measurements are used to resolve the capacitance into interfacial and chemical terms. Under more oxidizing conditions, the impedance spectra (of Ce_0.8Zr_0.2O_2-δ) reveal an additional diffusional feature, which enables determination of the ionic resistance of the film in addition to the capacitance, and hence the transport properties. A generalized mathematical formalism is presented for recovering the non-stoichiometry from the chemical capacitance, without recourse to defect chemical models. The ceria non-stoichiometry values are in good agreement with literature values determined by thermogravimetric measurements but display considerably less scatter and are collected on considerably shorter timescales. Here, the thermodynamic analysis of Ce_0.8Zr_0.2O_2-δ corroborates earlier findings that introduction of Zr into ceria enhances its reducibility.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern University, Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0008089

OSTI ID:: 1985151

Alternate ID(s):: OSTI ID: 1978272

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 17 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

Non-stoichiometry in Oxide Thin Films: A Chemical Capacitance Study of the Praseodymium-Cerium Oxide System Chen, Di; Bishop, Sean R.; Tuller, Harry L. Advanced Functional Materials, Vol. 23, Issue 17 https://doi.org/10.1002/adfm.201202104	journal	November 2012
Voltage-Controlled Nonstoichiometry in Oxide Thin Films: Pr _0.1 Ce _0.9 O _2−δ Case Study Chen, Di; Tuller, Harry L. Advanced Functional Materials, Vol. 24, Issue 48 https://doi.org/10.1002/adfm.201402050	journal	October 2014
Origin and Tunability of Unusually Large Surface Capacitance in Doped Cerium Oxide Studied by Ambient-Pressure X-Ray Photoelectron Spectroscopy Gopal, Chirranjeevi Balaji; Gabaly, Farid El; McDaniel, Anthony H. Advanced Materials, Vol. 28, Issue 23 https://doi.org/10.1002/adma.201506333	journal	March 2016
Electrical conductivity of single crystal and polycrystalline yttria-stabilized zirconia Badwal, S. P. S. Journal of Materials Science, Vol. 19, Issue 6 https://doi.org/10.1007/BF00550246	journal	June 1984
Simple method to determine electronic and ionic components of the conductivity in mixed conductors a review Huggins, R. A. Ionics, Vol. 8, Issue 3-4 https://doi.org/10.1007/BF02376083	journal	May 2002
Investigation of reactive cerium-based oxides for H2 production by thermochemical two-step water-splitting Abanades, Stéphane; Legal, Alex; Cordier, Anne Journal of Materials Science, Vol. 45, Issue 15 https://doi.org/10.1007/s10853-010-4506-4	journal	April 2010
A thermodynamic study of nonstoichiometric cerium dioxide Panlener, R. J.; Blumenthal, R. N.; Garnier, J. E. Journal of Physics and Chemistry of Solids, Vol. 36, Issue 11, p. 1213-1222 https://doi.org/10.1016/0022-3697(75)90192-4	journal	November 1975
Measurements of electronic and ionic partial conductivities in mixed conductors, without the use of blocking electrodes Riess, I. Solid State Ionics, Vol. 44, Issue 3-4 https://doi.org/10.1016/0167-2738(91)90009-Z	journal	February 1991
Electrical conductivity and point defect behavior in ceria-stabilized zirconia Reidy, R.; Simkovich, G. Solid State Ionics, Vol. 62, Issue 1-2 https://doi.org/10.1016/0167-2738(93)90255-2	journal	July 1993
Electrical and oxygen storage/release properties of nanocrystalline ceriaâ€“zirconia solid solutions Boaro, M. Solid State Ionics, Vol. 147, Issue 1-2 https://doi.org/10.1016/S0167-2738(02)00004-8	journal	March 2002
The geometry dependence of the polarization resistance of Sr-doped LaMnO3 microelectrodes on yttria-stabilized zirconia Brichzin, V. Solid State Ionics, Vol. 152-153 https://doi.org/10.1016/S0167-2738(02)00379-X	journal	December 2002
Electrical properties of the ZrO2-CeO2 system Chiodelli, G. Solid State Ionics, Vol. 91, Issue 1-2 https://doi.org/10.1016/S0167-2738(96)00382-7	journal	October 1996
Nonstoichiometry of Ce0.9Gd0.1O1.95âˆ’x Wang, S. Solid State Ionics, Vol. 107, Issue 1-2 https://doi.org/10.1016/S0167-2738(97)00519-5	journal	March 1998
Fuel cell materials and components☆☆☆The Golden Jubilee Issue—Selected topics in Materials Science and Engineering: Past, Present and Future, edited by S. Suresh. Haile, Sossina M. Acta Materialia, Vol. 51, Issue 19 https://doi.org/10.1016/j.actamat.2003.08.004	journal	November 2003
Structural characterization and oxygen nonstoichiometry of ceria-zirconia (Ce1−xZrxO2−δ) solid solutions Kuhn, M.; Bishop, S. R.; Rupp, J. L. M. Acta Materialia, Vol. 61, Issue 11 https://doi.org/10.1016/j.actamat.2013.04.001	journal	June 2013
Synergy between gold and oxygen vacancies in gold supported on Zr-doped ceria catalysts for the CO oxidation Laguna, O. H.; Pérez, A.; Centeno, M. A. Applied Catalysis B: Environmental, Vol. 176-177 https://doi.org/10.1016/j.apcatb.2015.04.019	journal	October 2015
Defect equilibria and chemical expansion in non-stoichiometric undoped and gadolinium-doped cerium oxide Bishop, S. R.; Duncan, K. L.; Wachsman, E. D. Electrochimica Acta, Vol. 54, Issue 5 https://doi.org/10.1016/j.electacta.2008.09.026	journal	February 2009
Ion–electron transport in strontium ferrites: relationships with structural features and stability Patrakeev, M. V.; Leonidov, I. A.; Kozhevnikov, V. L. Solid State Sciences, Vol. 6, Issue 9 https://doi.org/10.1016/j.solidstatesciences.2004.05.002	journal	September 2004
Highly Enhanced Concentration and Stability of Reactive Ce ³⁺ on Doped CeO ₂ Surface Revealed In Operando Chueh, William C.; McDaniel, Anthony H.; Grass, Michael E. Chemistry of Materials, Vol. 24, Issue 10 https://doi.org/10.1021/cm300574v	journal	May 2012
Defect and Transport Model of Ceria–Zirconia Solid Solutions: Ce_0.8Zr_0.2O_2−δ—An Electrical Conductivity Study Chen, Di; Cao, Yidan; Weng, Duan Chemistry of Materials, Vol. 26, Issue 17 https://doi.org/10.1021/cm502565b	journal	August 2014
Ceria–Zirconia Solid Solutions (Ce _{1– x} Zr _x O _2−δ , x ≤ 0.2) for Solar Thermochemical Water Splitting: A Thermodynamic Study Hao, Yong; Yang, Chih-Kai; Haile, Sossina M. Chemistry of Materials, Vol. 26, Issue 20 https://doi.org/10.1021/cm503131p	journal	October 2014
Nonstoichiometry in Oxide Thin Films Operating under Anodic Conditions: A Chemical Capacitance Study of the Praseodymium–Cerium Oxide System Chen, Di; Bishop, Sean R.; Tuller, Harry L. Chemistry of Materials, Vol. 26, Issue 22 https://doi.org/10.1021/cm503440v	journal	November 2014
Materials for Solid Oxide Fuel Cells ^† Jacobson, Allan J. Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902640j	journal	February 2010
Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes ^† Adler, Stuart B. Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020724o	journal	October 2004
Thermodynamic Analysis of Cerium-Based Oxides for Solar Thermochemical Fuel Production Scheffe, Jonathan R.; Steinfeld, Aldo Energy & Fuels, Vol. 26, Issue 3 https://doi.org/10.1021/ef201875v	journal	February 2012
Oxygen nonstoichiometry and thermodynamic characterization of Zr doped ceria in the 1573–1773 K temperature range Takacs, M.; Scheffe, J. R.; Steinfeld, A. Physical Chemistry Chemical Physics, Vol. 17, Issue 12 https://doi.org/10.1039/C4CP04916K	journal	January 2015
Probing the reaction pathway in (La _0.8 Sr _0.2 ) _0.95 MnO _3+δ using libraries of thin film microelectrodes Usiskin, Robert E.; Maruyama, Shingo; Kucharczyk, Chris J. Journal of Materials Chemistry A, Vol. 3, Issue 38 https://doi.org/10.1039/C5TA02428E	journal	January 2015
Voltage and partial pressure dependent defect chemistry in (La,Sr)FeO _3−δ thin films investigated by chemical capacitance measurements Schmid, Alexander; Rupp, Ghislain M.; Fleig, Jürgen Physical Chemistry Chemical Physics, Vol. 20, Issue 17 https://doi.org/10.1039/C7CP07845E	journal	January 2018
Perovskite oxides – a review on a versatile material class for solar-to-fuel conversion processes Kubicek, Markus; Bork, Alexander H.; Rupp, Jennifer L. M. Journal of Materials Chemistry A, Vol. 5, Issue 24 https://doi.org/10.1039/C7TA00987A	journal	January 2017
A review of defect structure and chemistry in ceria and its solid solutions Schmitt, Rafael; Nenning, Andreas; Kraynis, Olga Chemical Society Reviews, Vol. 49, Issue 2 https://doi.org/10.1039/C9CS00588A	journal	January 2020
The favourable thermodynamic properties of Fe-doped CaMnO ₃ for thermochemical heat storage Mastronardo, Emanuela; Qian, Xin; Coronado, Juan M. Journal of Materials Chemistry A, Vol. 8, Issue 17 https://doi.org/10.1039/D0TA02031A	journal	January 2020
Unexpected trends in the enhanced Ce ³⁺ surface concentration in ceria–zirconia catalyst materials Yuan, Weizi; Ma, Qing; Liang, Yangang Journal of Materials Chemistry A, Vol. 8, Issue 19 https://doi.org/10.1039/D0TA02762F	journal	January 2020
Generalised equivalent circuits for mass and charge transport: chemical capacitance and its implications Jamnik, J.; Maier, J. Physical Chemistry Chemical Physics, Vol. 3, Issue 9 https://doi.org/10.1039/b100180i	journal	January 2001
Impedance studies of dense polycrystalline thin films of La2NiO4+? Kim, Gun Tae; Wang, Shuangyan; Jacobson, Allan J. Journal of Materials Chemistry, Vol. 17, Issue 13 https://doi.org/10.1039/b616101d	journal	January 2007
Electrochemical studies of capacitance in cerium oxide thin films and its relationship to anionic and electronic defect densities Chueh, William C.; Haile, Sossina M. Physical Chemistry Chemical Physics, Vol. 11, Issue 37 https://doi.org/10.1039/b910903j	journal	January 2009
The role of point defects in the physical properties of nonstoichiometric ceria Duncan, Keith L.; Wang, Yanli; Bishop, Sean R. Journal of Applied Physics, Vol. 101, Issue 4 https://doi.org/10.1063/1.2559601	journal	February 2007
Catalytic Properties of Ceria and CeO ₂ -Containing Materials Trovarelli, Alessandro Catalysis Reviews, Vol. 38, Issue 4 https://doi.org/10.1080/01614949608006464	journal	November 1996
Impedance Spectroscopy as a Tool for Chemical and Electrochemical Analysis of Mixed Conductors: A Case Study of Ceria Lai, Wei; Haile, Sossina M. Journal of the American Ceramic Society, Vol. 88, Issue 11 https://doi.org/10.1111/j.1551-2916.2005.00740.x	journal	November 2005
Nanograin Composite Model Studies of Nanocrystalline Gadolinia-Doped Ceria: Nanograin Composite Model Studies Yeh, Ted C.; Perry, Nicola H.; Mason, Thomas O. Journal of the American Ceramic Society, Vol. 94, Issue 4 https://doi.org/10.1111/j.1551-2916.2010.04200.x	journal	November 2010
High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria Chueh, W. C.; Falter, C.; Abbott, M. Science, Vol. 330, Issue 6012 https://doi.org/10.1126/science.1197834	journal	December 2010
Determination of Oxygen Vacancy Concentration in a Thin Film of La[sub 0.6]Sr[sub 0.4]CoO[sub 3−δ] by an Electrochemical Method Kawada, T.; Suzuki, J.; Sase, M. Journal of The Electrochemical Society, Vol. 149, Issue 7 https://doi.org/10.1149/1.1479728	journal	January 2002
Chemical resistance and chemical capacitance Maier, Joachim Zeitschrift für Naturforschung B, Vol. 75, Issue 1-2 https://doi.org/10.1515/znb-2019-0163	journal	December 2019

Similar Records

Electronic and reactivity changes in epitaxially grown Ce_1-xZr_xO_2-δ (111) thin films

Journal Article · Sun Mar 16 20:00:00 EDT 2025 · Surface Science · OSTI ID:2558982

Facile Interfacial Reduction Suppresses Redox Chemical Expansion and Promotes the Polaronic to Ionic Transition in Mixed Conducting (Pr,Ce)O_2−δ Nanoparticles

Journal Article · Sun Dec 15 19:00:00 EST 2024 · ACS Applied Materials and Interfaces · OSTI ID:3002605

High temperature steam separation membrane

Patent · Tue Apr 04 00:00:00 EDT 2023 · OSTI ID:1998250

Related Subjects

08 HYDROGEN
ceria ceria-zirconia
chemical capacitance
electrical properties
impedance spectroscopy
ionic conductivity
ions
mixed ion and electron conductor (MIEC)
oxides
oxygen
oxygen nonstoichiometry
thin films

Broad Applicability of Electrochemical Impedance Spectroscopy to the Measurement of Oxygen Nonstoichiometry in Mixed Ion and Electron Conductors

Citation Formats

References (42)

Similar Records

Related Subjects