Proton surface exchange kinetics of perovskite triple conducting thin films for protonic ceramic electrolysis cells: BaPr0.9Y0.1O3–δ (BPY) vs. Ba1–xCo0.4Fe0.4Zr0.1Y0.1O3–δ (BCFZY)

Lee, Jongmin; Buckner, Haley B.; Perry, Nicola H.

doi:10.1039/d3ta07534f

Proton surface exchange kinetics of perovskite triple conducting thin films for protonic ceramic electrolysis cells: BaPr_0.9Y_0.1O_3–δ (BPY) vs. Ba_1–xCo_0.4Fe_0.4Zr_0.1Y_0.1O_3–δ(BCFZY)

Journal Article · Thu May 16 00:00:00 EDT 2024 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d3ta07534f· OSTI ID:2382696

^[1]; Buckner, Haley B. ^[2]; ^[2]

University of Illinois Urbana-Champaign, IL (United States); University of Illinois Urbana-Champaign
University of Illinois Urbana-Champaign, IL (United States)

Protonic ceramic electrolysis cells (PCECs) are an attractive green H₂ production technology, given their intermediate-temperature operating range and ability to produce dry H₂. However, PCECs will benefit from development of more efficient and durable “triple conducting” anodes where steam is split, H incorporated, and oxygen evolved. In this work, we evaluated the kinetics of the steam-splitting/H incorporation reaction on BaPr_0.9Y_0.1O_3–δ (BPY) in comparison to the benchmark Ba_1–xCo_0.4Fe_0.4Z_r0.1Y_0.1O_3–δ(BCFZY) composition, replacing most of the transition metal elements (Co, Fe, Zr) with the lanthanide Pr. We prepared geometrically well-defined perovskite BPY and BCFZY thin films by pulsed laser deposition and performed simultaneous optical transmission relaxation and electrical conductivity relaxation measurements at 400–500 °C in 0.21 atm O₂ during switching of the steam partial pressure to isolate and compare their proton surface exchange coefficients (k). The k values of BPY were comparable to those of BCFZY and more stable over time. According to angle-resolved XPS and STEM-EDS mapping of FIB cross-sections, the surface of BPY exhibited Ba enrichment, Pr deficiency, and Si contamination. In contrast, BCFZY exhibited Ba deficiency throughout, no obvious surface segregation, and less Si contamination. The Ba segregation on the BPY film appears to have promoted steam splitting/H incorporation kinetics even though the more basic surface reacted with the acidic environmental SiO_xH_y. Faster kinetics observed on stoichiometric BCFZY vs. Ba-deficient BCFZY confirmed the benefit of a high A-site Ba concentration. This result contrasts with most work on perovskites applied in solid oxide electrolysis cell anodes, in which A-site segregation is considered deleterious for surface reaction kinetics.

View Accepted Manuscript (DOE)

Research Organization:: University of Illinois, Champaign, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018963

OSTI ID:: 2382696

Alternate ID(s):: OSTI ID: 2367413

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 25 Vol. 12; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Tuning Surface Acidity of Mixed Conducting Electrodes: Recovery of Si‐Induced Degradation of Oxygen Exchange Rate and Area Specific Resistance Seo, Han Gil; Staerz, Anna; Kim, Dennis S. Advanced Materials, Vol. 35, Issue 8 https://doi.org/10.1002/adma.202208182	journal	December 2022
In Situ Optical Absorption Studies of Point Defect Kinetics and Thermodynamics in Oxide Thin Films Buckner, Haley B.; Perry, Nicola H. Advanced Materials Interfaces, Vol. 6, Issue 15 https://doi.org/10.1002/admi.201900496	journal	June 2019
Electrokinetic Proton Transport in Triple (H ⁺ /O ²⁻ /e ⁻ ) Conducting Oxides as a Key Descriptor for Highly Efficient Protonic Ceramic Fuel Cells Seong, Arim; Kim, Junyoung; Jeong, Donghwi Advanced Science, Vol. 8, Issue 11 https://doi.org/10.1002/advs.202004099	journal	March 2021
Degradation issues and stabilization strategies of protonic ceramic electrolysis cells for steam electrolysis Su, Hanrui; Hu, Yun Hang Energy Science & Engineering, Vol. 10, Issue 5 https://doi.org/10.1002/ese3.1010	journal	November 2021
Protonic ceramic electrolysis cells for fuel production: a brief review Ji, Ho-Il; Lee, Jong-Ho; Son, Ji-Won Journal of the Korean Ceramic Society, Vol. 57, Issue 5 https://doi.org/10.1007/s43207-020-00059-4	journal	May 2020
Conductivity of BaPrO3 based perovskite oxides Fukui, Takehisa; Ohara, Satoshi; Kawatsu, Shigeyuki Journal of Power Sources, Vol. 71, Issue 1-2 https://doi.org/10.1016/S0378-7753(97)02813-9	journal	March 1998
The interplay and impact of strain and defect association on the conductivity of rare-earth substituted ceria Harrington, George F.; Sun, Lixin; Yildiz, Bilge Acta Materialia, Vol. 166 https://doi.org/10.1016/j.actamat.2018.12.058	journal	March 2019
Systematic and collaborative approach to problem solving using X-ray photoelectron spectroscopy Fairley, Neal; Fernandez, Vincent; Richard‐Plouet, Mireille Applied Surface Science Advances, Vol. 5 https://doi.org/10.1016/j.apsadv.2021.100112	journal	September 2021
X-Ray Spectroscopic Characterization of BaO, Ba(OH)2, BaCO3, and Ba(NO3)2 Karslıoğlu, Osman; Trotochaud, Lena; Zegkinoglou, Ioannis Journal of Electron Spectroscopy and Related Phenomena, Vol. 225 https://doi.org/10.1016/j.elspec.2018.03.008	journal	May 2018
Sr Segregation in Perovskite Oxides: Why It Happens and How It Exists Koo, Bonjae; Kim, Kyeounghak; Kim, Jun Kyu Joule, Vol. 2, Issue 8 https://doi.org/10.1016/j.joule.2018.07.016	journal	August 2018
Surface and interface behaviors of (La0.8Sr0.2)xMnO3 air electrode for solid oxide cells Jin, Tongan; Lu, Kathy Journal of Power Sources, Vol. 196, Issue 20 https://doi.org/10.1016/j.jpowsour.2011.06.052	journal	October 2011
Investigate the proton uptake process of proton/oxygen ion/hole triple conductor BaCo0.4Fe0.4Zr0.1Y0.1O3-δ by electrical conductivity relaxation Chen, Yang; Hong, Tao; Wang, Piaopiao Journal of Power Sources, Vol. 440 https://doi.org/10.1016/j.jpowsour.2019.227122	journal	November 2019
Impedance spectroscopic study on well-defined (La,Sr)(Co,Fe)O3−δ model electrodes Baumann, F.; Fleig, J.; Habermeier, H. Solid State Ionics, Vol. 177, Issue 11-12 https://doi.org/10.1016/j.ssi.2006.02.045	journal	April 2006
Proton incorporation and defect chemistry of Yb-doped BaPrO3 Mimuro, Shin; Shibako, Shuta; Oyama, Yukiko Solid State Ionics, Vol. 178, Issue 7-10 https://doi.org/10.1016/j.ssi.2007.02.006	journal	April 2007
Pulsed laser deposition of BaCo0.4Fe0.4Zr0.1Y0.1O3-δ cathode for solid oxide fuel cells Ryu, Sangbong; Lee, Sanghoon; Jeong, Wonyeop Surface and Coatings Technology, Vol. 369 https://doi.org/10.1016/j.surfcoat.2019.01.034	journal	July 2019
Toward Zero-Strain Mixed Conductors: Anomalously Low Redox Coefficients of Chemical Expansion in Praseodymium-Oxide Perovskites Anderson, Lawrence O.; Yong, Adrian Xiao Bin; Ertekin, Elif Chemistry of Materials, Vol. 33, Issue 21 https://doi.org/10.1021/acs.chemmater.1c02739	journal	October 2021
Improving the Si Impurity Tolerance of Pr _0.1 Ce _0.9 O _2−δ SOFC Electrodes with Reactive Surface Additives Zhao, Liang; Perry, Nicola H.; Daio, Takeshi Chemistry of Materials, Vol. 27, Issue 8 https://doi.org/10.1021/acs.chemmater.5b00501	journal	April 2015
Origins and Control of Optical Absorption in a Nondilute Oxide Solid Solution: Sr(Ti,Fe)O _{3– x} Perovskite Case Study Perry, Nicola H.; Kim, Namhoon; Ertekin, Elif Chemistry of Materials, Vol. 31, Issue 3 https://doi.org/10.1021/acs.chemmater.8b04580	journal	January 2019
Revealing the Impact of Steam Concentration on the Activity and Stability of Double-Perovskite Air Electrodes for Proton-Conducting Electrolysis Cells Pan, Junxian; Ye, Yongjian; Zhou, Mengzhen Energy & Fuels, Vol. 36, Issue 19 https://doi.org/10.1021/acs.energyfuels.2c02560	journal	September 2022
Effect of Surface Defect Engineering on Proton Conductivity in Yttrium-Doped Barium Zirconate Thin Films Wang, Yifan; Wang, Luyao; Chen, Yu The Journal of Physical Chemistry C, Vol. 127, Issue 19 https://doi.org/10.1021/acs.jpcc.3c00929	journal	May 2023
Simultaneous Electrical, Electrochemical, and Optical Relaxation Measurements of Oxygen Surface Exchange Coefficients: Sr(Ti,Fe)O _3−d Film Crystallization Case Study Skiba, Emily J.; Chen, Ting; Perry, Nicola H. ACS Applied Materials & Interfaces, Vol. 12, Issue 43 https://doi.org/10.1021/acsami.0c14265	journal	October 2020
High-Temperature 2D Optical Relaxation Visualizes Enhanced Oxygen Exchange Kinetics at Metal-Mixed Conducting Oxide Interfaces Skiba, Emily J.; Perry, Nicola H. ACS Applied Materials & Interfaces, Vol. 14, Issue 42 https://doi.org/10.1021/acsami.2c12184	journal	October 2022
Assessing Substitution Effects on Surface Chemistry by in Situ Ambient Pressure X-ray Photoelectron Spectroscopy on Perovskite Thin Films, BaCe _x Zr _{0.9– x} Y _0.1 O _2.95 ( x = 0; 0.2; 0.9) Jarry, Angelique; Ricote, Sandrine; Geller, Aaron ACS Applied Materials & Interfaces, Vol. 10, Issue 43 https://doi.org/10.1021/acsami.8b12546	journal	October 2018
Improving the Electrocatalytic Activity and Durability of the La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3−δ Cathode by Surface Modification Chen, Huijun; Guo, Zheng; Zhang, Lei A. ACS Applied Materials & Interfaces, Vol. 10, Issue 46 https://doi.org/10.1021/acsami.8b14693	journal	October 2018
Emergence of Rapid Oxygen Surface Exchange Kinetics during in Situ Crystallization of Mixed Conducting Thin Film Oxides Chen, Ting; Harrington, George F.; Masood, Juveria ACS Applied Materials & Interfaces, Vol. 11, Issue 9 https://doi.org/10.1021/acsami.8b21285	journal	January 2019
Self-sustainable protonic ceramic electrochemical cells using a triple conducting electrode for hydrogen and power production Ding, Hanping; Wu, Wei; Jiang, Chao Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15677-z	journal	April 2020
Exceptional power density and stability at intermediate temperatures in protonic ceramic fuel cells Choi, Sihyuk; Kucharczyk, Chris J.; Liang, Yangang Nature Energy, Vol. 3, Issue 3 https://doi.org/10.1038/s41560-017-0085-9	journal	February 2018
Mixed proton and electron conducting double perovskite anodes for stable and efficient tubular proton ceramic electrolysers Vøllestad, Einar; Strandbakke, Ragnar; Tarach, Mateusz Nature Materials, Vol. 18, Issue 7 https://doi.org/10.1038/s41563-019-0388-2	journal	June 2019
Triple ionic–electronic conducting oxides for next-generation electrochemical devices Papac, Meagan; Stevanović, Vladan; Zakutayev, Andriy Nature Materials, Vol. 20, Issue 3 https://doi.org/10.1038/s41563-020-00854-8	journal	December 2020
Silicon nanowires terminated with methyl functionalities exhibit stronger Si–C bonds than equivalent 2D surfaces Bashouti, Muhammad Y.; Paska, Yair; Puniredd, Sreenivasa Reddy Physical Chemistry Chemical Physics, Vol. 11, Issue 20 https://doi.org/10.1039/B820559K	journal	January 2009
Structural transitions and conductivity of BaPrO3 and BaPr0.9Y0.1O3−δ Knee, Christopher S.; Magrasó, Anna; Norby, Truls Journal of Materials Chemistry, Vol. 19, Issue 20 https://doi.org/10.1039/B820976F	journal	January 2009
Understanding chemical expansion in perovskite-structured oxides Marrocchelli, Dario; Perry, Nicola H.; Bishop, Sean R. Physical Chemistry Chemical Physics, Vol. 17, Issue 15 https://doi.org/10.1039/C4CP05885B	journal	January 2015
Steam electrolysis by solid oxide electrolysis cells (SOECs) with proton-conducting oxides Bi, Lei; Boulfrad, Samir; Traversa, Enrico Chem. Soc. Rev., Vol. 43, Issue 24 https://doi.org/10.1039/C4CS00194J	journal	January 2014
Transport properties and oxidation and hydration kinetics of the proton conductor Mo doped Nd_5.5WO_11.25−δ Ruf, Mischa; Solís, Cecilia; Escolástico, Sonia J. Mater. Chem. A, Vol. 2, Issue 43 https://doi.org/10.1039/C4TA03248A	journal	September 2014
Zr and Y co-doped perovskite as a stable, high performance cathode for solid oxide fuel cells operating below 500 °C Duan, Chuancheng; Hook, David; Chen, Yachao Energy & Environmental Science, Vol. 10, Issue 1 https://doi.org/10.1039/C6EE01915C	journal	January 2017
Protonic ceramic electrochemical cells for hydrogen production and electricity generation: exceptional reversibility, stability, and demonstrated faradaic efficiency Choi, Sihyuk; Davenport, Timothy C.; Haile, Sossina M. Energy & Environmental Science, Vol. 12, Issue 1 https://doi.org/10.1039/C8EE02865F	journal	January 2019
Silica: ubiquitous poison of metal oxide interfaces Staerz, Anna; Seo, Han Gil; Defferriere, Thomas Journal of Materials Chemistry A, Vol. 10, Issue 6 https://doi.org/10.1039/D1TA08469K	journal	January 2022
Tuning the Co/Fe ratio in BaCo_xFe_0.8−xZr_0.1Y_0.1O_3−δ, a promising triple ionic and electronic conducting oxide, to boost electrolysis and fuel cell performance Shin, Yewon; Kim, You-dong; Sanders, Michael Journal of Materials Chemistry A, Vol. 10, Issue 46 https://doi.org/10.1039/D2TA03150G	journal	January 2022
Evidence of Ba-rich surface segregation in Ba_1-xSr_xTiO₃ and Ba-rich surfactant in SrTiO₃/ Ba_1-xSr_xTiO₃ stacks grown by combinatorial pulsed laser deposition Agudelo-Estrada, Santiago; Barrett, Nick; Lubin, Christophe EPJ Web of Conferences, Vol. 273 https://doi.org/10.1051/epjconf/202227301008	journal	January 2022
Thermal expansion of AlN, sapphire, and silicon Yim, W. M.; Paff, R. J. Journal of Applied Physics, Vol. 45, Issue 3 https://doi.org/10.1063/1.1663432	journal	March 1974
Hydrogen content in doped and undoped BaPrO3 and BaCeO3 by cold neutron prompt-gamma activation analysis Jones, Camille Y.; Wu, Jian; Li, LiPing Journal of Applied Physics, Vol. 97, Issue 11 https://doi.org/10.1063/1.1922590	journal	June 2005
Proton-conducting oxides for energy conversion and storage Duan, Chuancheng; Huang, Jake; Sullivan, Neal Applied Physics Reviews, Vol. 7, Issue 1 https://doi.org/10.1063/1.5135319	journal	March 2020
A step-by-step guide to perform x-ray photoelectron spectroscopy Greczynski, Grzegorz; Hultman, Lars Journal of Applied Physics, Vol. 132, Issue 1 https://doi.org/10.1063/5.0086359	journal	July 2022
Pulsed laser deposition—invention or discovery? Venkatesan, T. Journal of Physics D: Applied Physics, Vol. 47, Issue 3 https://doi.org/10.1088/0022-3727/47/3/034001	journal	December 2013
Readily processed protonic ceramic fuel cells with high performance at low temperatures Duan, C.; Tong, J.; Shang, M. Science, Vol. 349, Issue 6254 https://doi.org/10.1126/science.aab3987	journal	July 2015
Oxides with Mixed Protonic and Electronic Conductivity Merkle, Rotraut; Hoedl, Maximilian F.; Raimondi, Giulia Annual Review of Materials Research, Vol. 51, Issue 1 https://doi.org/10.1146/annurev-matsci-091819-010219	journal	July 2021
Proton-Conducting Oxides Kreuer, K. D. Annual Review of Materials Research, Vol. 33, Issue 1, p. 333-359 https://doi.org/10.1146/annurev.matsci.33.022802.091825	journal	August 2003
Factors that Influence Cation Segregation at the Surfaces of Perovskite Oxides Lee, W.; Yildiz, B. ECS Transactions, Vol. 57, Issue 1 https://doi.org/10.1149/05701.2115ecst	journal	October 2013
Ion Conduction of BaPrO_3-δThin Film with Mixed Valence State for SOFC Anode Electrode Furuichi, Shoto; Tsuchiya, Takashi; Minohara, Makoto ECS Transactions, Vol. 75, Issue 42 https://doi.org/10.1149/07542.0099ecst	journal	January 2017
Structural and Electrical Properties of BaPrO_3-δ Thin Film with Oxygen Vacancies Furuichi, Shoto; Tsuchiya, Takashi; Horiba, Koji Transactions of the Materials Research Society of Japan, Vol. 42, Issue 2 https://doi.org/10.14723/tmrsj.42.15	journal	January 2017
Crystal Structure, Hydration, and Two-Fold/Single-Fold Diffusion Kinetics in Proton-Conducting Ba0.9La0.1Zr0.25Sn0.25In0.5O3−a Oxide Skubida, Wojciech; Niemczyk, Anna; Zheng, Kun Crystals, Vol. 8, Issue 3 https://doi.org/10.3390/cryst8030136	journal	March 2018
Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes Perry, Nicola; Ishihara, Tatsumi Materials, Vol. 9, Issue 10 https://doi.org/10.3390/ma9100858	journal	October 2016
Hole-ion Mixed Conduction of Orientation-Controlled BaPrO_3−δ Thin Film with Mixed Valence States Higuchi, Tohru; Oda, Asuka; Tsuchiya, Takashi Journal of the Physical Society of Japan, Vol. 84, Issue 11 https://doi.org/10.7566/JPSJ.84.114708	journal	November 2015

Similar Records

Layer-structured triple-conducting electrocatalyst for water-splitting in protonic ceramic electrolysis cells: Conductivities vs. activity

Journal Article · Mon Mar 29 20:00:00 EDT 2021 · Journal of Power Sources · OSTI ID:2479427

Synergistic Coupling of Proton Conductors BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3–δ and La₂Ce₂O₇ to Create Chemical Stable, Interface Active Electrolyte for Steam Electrolysis Cells

Journal Article · Thu May 02 20:00:00 EDT 2019 · ACS Applied Materials and Interfaces · OSTI ID:2479408

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
STEM-EDS
XPS
electron microscopy
optical transmission relaxation
pulsed laser deposition
surface chemistry
surface exchange kinetics
thin films
triple conductors

Proton surface exchange kinetics of perovskite triple conducting thin films for protonic ceramic electrolysis cells: BaPr0.9Y0.1O3–δ (BPY) vs. Ba1–xCo0.4Fe0.4Zr0.1Y0.1O3–δ (BCFZY)

Citation Formats

References (53)

Similar Records

Related Subjects

Proton surface exchange kinetics of perovskite triple conducting thin films for protonic ceramic electrolysis cells: BaPr_0.9Y_0.1O_3–δ (BPY) vs. Ba_1–xCo_0.4Fe_0.4Zr_0.1Y_0.1O_3–δ(BCFZY)