Use of Interplay between A-Site Non-Stoichiometry and Hydroxide Doping to Deliver Novel Proton-Conducting Perovskite Oxides

Jin Goo Lee; Aaron B. Naden; Cristian D. Savaniu; Paul A. Connor; Julia L. Payne; Jonathan M. Skelton; Alexandra S. Gibbs; Jianing Hui; Stephen C. Parker; John T.S. Irvine

doi:10.1002/aenm.202101337

Use of Interplay between A-Site Non-Stoichiometry and Hydroxide Doping to Deliver Novel Proton-Conducting Perovskite Oxides

Jin Goo Lee, Aaron B. Naden, Cristian D. Savaniu, Paul A. Connor, Julia L. Payne, Jonathan M. Skelton, Alexandra S. Gibbs, Jianing Hui, Stephen C. Parker, John T.S. Irvine

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Abstract

The magnitude of ionic conductivity is known to depend upon both mobility and number of available carriers. For proton conductors, hydration is a key factor in determining the charge–carrier concentration in ABO₃ perovskite oxides. Despite the high reported proton mobility of calcium titanate (CaTiO₃), this titanate perovskite has thus far been regarded as a poor proton conductor due to the low hydration capability. Here, the enhanced proton conductivity of the defective calcium titanate Ca_0.92TiO_2.84(OH)_0.16 prepared by replacing lattice oxygens with hydroxyl groups via a solvothermal route is shown. Conductivity measurements in a humidified Ar atmosphere reveal that, remarkably, this material exhibits one order of magnitude higher bulk conductivity (10⁻⁴ Scm⁻¹ at 200 °C) than hydrated stoichiometric CaTiO₃ prepared by traditional solid-state synthesis due to the higher concentration of protonic defects and variation in the crystal structure. The replacement of Ca²⁺ by Ni²⁺ in the Ca₁₋_xTi₁O₃₋₂_x(OH)₂_x, which mostly exsolve metallic Ni nanoparticles along orthorhombic (100) planes upon reduction, is also demonstrated. These results suggest a new strategy by tailoring the defect chemistry via hydration or cation doping followed by exsolution for targeted energy applications.

Original language	English
Article number	2101337
Journal	Advanced Energy Materials
Volume	11
Issue number	37
Early online date	26 Aug 2021
DOIs	https://doi.org/10.1002/aenm.202101337
Publication status	Published - 7 Oct 2021

Bibliographical note

Funding Information:
This research was supported by the UK Engineering and Physical Sciences Research Council (grant nos.: EP/R023522/1, EP/R023751/1, EP/L017008/1 and EP/P007821/1). The authors would like to thank Prof. Martin Owen Jones for useful discussions. Experiments at the ISIS Neutron and Muon Source were supported by beamtime allocation RB1920629 from the Science and Technology Facilities Council. The authors would also like to thank Diamond Light Source for beamtime (proposal SP17198‐8), and the staff at beamline B18, in particular Alan Chadwick and Giannantonio Cibin, for assistance with XAS testing and data collection. Calculations were performed on the UK Archer high‐performance computing (HPC) facility, via the UK Materials Chemistry Consortium, which was funded by the EPSRC (EP/L000202, EP/R029431).

Funding Information:
This research was supported by the UK Engineering and Physical Sciences Research Council (grant nos.: EP/R023522/1, EP/R023751/1, EP/L017008/1 and EP/P007821/1). The authors would like to thank Prof. Martin Owen Jones for useful discussions. Experiments at the ISIS Neutron and Muon Source were supported by beamtime allocation RB1920629 from the Science and Technology Facilities Council. The authors would also like to thank Diamond Light Source for beamtime (proposal SP17198-8), and the staff at beamline B18, in particular Alan Chadwick and Giannantonio Cibin, for assistance with XAS testing and data collection. Calculations were performed on the UK Archer high-performance computing (HPC) facility, via the UK Materials Chemistry Consortium, which was funded by the EPSRC (EP/L000202, EP/R029431).

Publisher Copyright:
© 2021 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH

Keywords

defect chemistry
exsolution
hydration
perovskite
proton conductivity

ASJC Scopus subject areas

Renewable Energy, Sustainability and the Environment
General Materials Science

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/aenm.202101337Licence: CC BY

Cite this

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abstract = "The magnitude of ionic conductivity is known to depend upon both mobility and number of available carriers. For proton conductors, hydration is a key factor in determining the charge–carrier concentration in ABO3 perovskite oxides. Despite the high reported proton mobility of calcium titanate (CaTiO3), this titanate perovskite has thus far been regarded as a poor proton conductor due to the low hydration capability. Here, the enhanced proton conductivity of the defective calcium titanate Ca0.92TiO2.84(OH)0.16 prepared by replacing lattice oxygens with hydroxyl groups via a solvothermal route is shown. Conductivity measurements in a humidified Ar atmosphere reveal that, remarkably, this material exhibits one order of magnitude higher bulk conductivity (10−4 Scm−1 at 200 °C) than hydrated stoichiometric CaTiO3 prepared by traditional solid-state synthesis due to the higher concentration of protonic defects and variation in the crystal structure. The replacement of Ca2+ by Ni2+ in the Ca1−xTi1O3−2x(OH)2x, which mostly exsolve metallic Ni nanoparticles along orthorhombic (100) planes upon reduction, is also demonstrated. These results suggest a new strategy by tailoring the defect chemistry via hydration or cation doping followed by exsolution for targeted energy applications.",

keywords = "defect chemistry, exsolution, hydration, perovskite, proton conductivity",

author = "Lee, {Jin Goo} and Naden, {Aaron B.} and Savaniu, {Cristian D.} and Connor, {Paul A.} and Payne, {Julia L.} and {M. Skelton}, Jonathan and Gibbs, {Alexandra S.} and Jianing Hui and {C. Parker}, Stephen and Irvine, {John T.S.}",

note = "Funding Information: This research was supported by the UK Engineering and Physical Sciences Research Council (grant nos.: EP/R023522/1, EP/R023751/1, EP/L017008/1 and EP/P007821/1). The authors would like to thank Prof. Martin Owen Jones for useful discussions. Experiments at the ISIS Neutron and Muon Source were supported by beamtime allocation RB1920629 from the Science and Technology Facilities Council. The authors would also like to thank Diamond Light Source for beamtime (proposal SP17198‐8), and the staff at beamline B18, in particular Alan Chadwick and Giannantonio Cibin, for assistance with XAS testing and data collection. Calculations were performed on the UK Archer high‐performance computing (HPC) facility, via the UK Materials Chemistry Consortium, which was funded by the EPSRC (EP/L000202, EP/R029431). Funding Information: This research was supported by the UK Engineering and Physical Sciences Research Council (grant nos.: EP/R023522/1, EP/R023751/1, EP/L017008/1 and EP/P007821/1). The authors would like to thank Prof. Martin Owen Jones for useful discussions. Experiments at the ISIS Neutron and Muon Source were supported by beamtime allocation RB1920629 from the Science and Technology Facilities Council. The authors would also like to thank Diamond Light Source for beamtime (proposal SP17198-8), and the staff at beamline B18, in particular Alan Chadwick and Giannantonio Cibin, for assistance with XAS testing and data collection. Calculations were performed on the UK Archer high-performance computing (HPC) facility, via the UK Materials Chemistry Consortium, which was funded by the EPSRC (EP/L000202, EP/R029431). Publisher Copyright: {\textcopyright} 2021 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH",

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AU - Lee, Jin Goo

AU - Naden, Aaron B.

AU - Savaniu, Cristian D.

AU - Connor, Paul A.

AU - Payne, Julia L.

AU - M. Skelton, Jonathan

AU - Gibbs, Alexandra S.

AU - Hui, Jianing

AU - C. Parker, Stephen

AU - Irvine, John T.S.

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N2 - The magnitude of ionic conductivity is known to depend upon both mobility and number of available carriers. For proton conductors, hydration is a key factor in determining the charge–carrier concentration in ABO3 perovskite oxides. Despite the high reported proton mobility of calcium titanate (CaTiO3), this titanate perovskite has thus far been regarded as a poor proton conductor due to the low hydration capability. Here, the enhanced proton conductivity of the defective calcium titanate Ca0.92TiO2.84(OH)0.16 prepared by replacing lattice oxygens with hydroxyl groups via a solvothermal route is shown. Conductivity measurements in a humidified Ar atmosphere reveal that, remarkably, this material exhibits one order of magnitude higher bulk conductivity (10−4 Scm−1 at 200 °C) than hydrated stoichiometric CaTiO3 prepared by traditional solid-state synthesis due to the higher concentration of protonic defects and variation in the crystal structure. The replacement of Ca2+ by Ni2+ in the Ca1−xTi1O3−2x(OH)2x, which mostly exsolve metallic Ni nanoparticles along orthorhombic (100) planes upon reduction, is also demonstrated. These results suggest a new strategy by tailoring the defect chemistry via hydration or cation doping followed by exsolution for targeted energy applications.

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KW - exsolution

KW - hydration

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KW - proton conductivity

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Use of Interplay between A-Site Non-Stoichiometry and Hydroxide Doping to Deliver Novel Proton-Conducting Perovskite Oxides

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

UN SDGs

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