Tuning proton kinetics in BaCo 0.4 Fe 0.4 Zr 0.2– X Y X O 3– δ triple ionic-electronic conductors via aliovalent substitution

Duffy, Jack H.; Abernathy, Harry W.; Brinkman, Kyle S.

doi:10.1039/D3TA00654A

Title: Tuning proton kinetics in BaCo _0.4 Fe _0.4 Zr _{0.2– X} Y _X O _{3– δ} triple ionic-electronic conductors via aliovalent substitution

Journal Article · Tue Apr 25 00:00:00 EDT 2023 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/D3TA00654A· OSTI ID:1968522

^[1]; Abernathy, Harry W. ^[2];

^[1]

Department of Materials Science and Engineering, Clemson University, 515 Calhoun Drive, Clemson, SC 29634, USA, National Energy Technology Laboratory, United States Department of Energy, 3610 Collins Ferry Road, Morgantown, WV 26507, USA
National Energy Technology Laboratory, United States Department of Energy, 3610 Collins Ferry Road, Morgantown, WV 26507, USA

The BaCo_0.4Fe_0.4Zr_0.1Y_0.1O_3–δ (BCFZY0.1) triple ionic-electronic conductor (TIEC) has received thorough investigation as a potential cathode in protonic ceramic fuel cells (PCFCs) due to its excellent oxygen reduction reaction and concurrent conduction of electrons, oxygen ions, and protons. Proton conductivity and surface reactivity are paramount in PCFC cathodes to improve the active reaction area. However, few instances of direct proton kinetic measurements have been reported. In this work, a suite of BaCo_0.4Fe_0.4Zr_0.2–XY_XO_3–δ (X = 0, 0.1, 0.2) materials is synthesized and evaluated through hydrogen permeation and electrical conductivity relaxation measurements to investigate the effect of aliovalent substitution of Y³⁺ for Zr⁴⁺ on bulk proton conductivity and surface kinetics. The permeation results suggest that aliovalent substitution significantly improves the proton conductivity upon a 10% B-site doping of Y, while further incorporation of Y slightly decreases conductivity from the 10% optimum. Through three separate conductivity relaxation measurements, oxidation, hydration, and isotopic switching, an improvement in the proton kinetics with Y-doping is observed in humidified oxidizing conditions, emulating conditions in intermediate-temperature electrochemical devices. These observations suggest that aliovalient doping plays an important role in the incorporation and mobility of protons in TIEC materials.

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Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: USDOE; USDOE Office of Fossil Energy (FE)

OSTI ID:: 1968522

Alternate ID(s):: OSTI ID: 2006868

Report Number(s):: DOE/NETL-2023/3858; JMCAET

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Vol. 11 Journal Issue: 16; ISSN 2050-7488

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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Title: Tuning proton kinetics in BaCo _0.4 Fe _0.4 Zr _{0.2– X} Y _X O _{3– δ} triple ionic-electronic conductors via aliovalent substitution