Oxygen surface exchange properties and electrochemical activity of lanthanum nickelates

Artur Majewski; Anna  Khodimchuk; Dmitry Zakharov; Maxim Ananyev; ian johnson; jawwad darr; Peter Slater; Robert Steinberger-Wilckens

doi:10.1016/j.jssc.2022.123228

Oxygen surface exchange properties and electrochemical activity of lanthanum nickelates

Artur Majewski, Anna Khodimchuk, Dmitry Zakharov, Maxim Ananyev, ian johnson, jawwad darr, Peter Slater, Robert Steinberger-Wilckens

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Abstract

Oxygen surface exchange properties of lanthanum nickelates La₂NiO_4+δ, La₃Ni₂O_7-δ and La₄Ni₃O_10-δ (LNOs) have been investigated using the Pulsed Isotope ¹⁸O/¹⁶O Exchange (PIE) technique in the temperature range 300–700 °C. The evaluation of the oxygen exchange rate from these lanthanum nickelates was conducted by measurement of isotope fractions ¹⁸O₂, ¹⁶O¹⁸O, and ¹⁶O₂ in the effluent pulse at the exhaust from the reactor with a packed bed. The rates of oxygen heterogenous surface exchange (r_H), dissociative adsorption (r_a) and incorporation (r_i) were calculated. The oxygen surface exchange was found to vary between the three nickelates, with r_H decreasing between samples La₃Ni₂O_7-δ > La₄Ni₃O_10-δ > La₂NiO_4+δ, which was attributed to a decreasing presence of Ni cations on the particle surfaces. Despite possessing the lowest oxygen surface exchange, La₂NiO_4+δ had the best electrode electrochemical performance, which was attributed to highly mobile interstitial oxygen atoms leading to the largest r_i (surface oxygen incorporation rate into the bulk) of the nickelates. This study reveals the key limiting factors determining lanthanum nickelate cathode performance in SOFCs, and we suggest avenues to improve these materials towards functional cathodes in devices.

Original language	English
Article number	123228
Number of pages	12
Journal	Journal of Solid State Chemistry
Volume	312
Early online date	15 May 2022
DOIs	https://doi.org/10.1016/j.jssc.2022.123228
Publication status	Published - Aug 2022

Bibliographical note

Funding Information:
The authors would like to express their appreciation to EPSRC, UK for support through the JUICED Hub (contract EP/R023662/1 ) funding. LEIS data collection was performed at the EPSRC National Facility for XPS (HarwellXPS).

Keywords

Solid oxide cell
Oxygen electrode
La2NiO4+δ
La3Ni2O7-δ
La4Ni3O10-δ
Oxygen surface exchange
Isotope exchange

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MajewskiA2022OxygenFinal published version, 2.68 MBLicence: Creative Commons: Attribution (CC BY)

https://www.sciencedirect.com/science/article/pii/S002245962200353X?via%3DihubLicence: Creative Commons: Attribution (CC BY)

ISCF Wave 1: (THe JUICED Hub [Joing University Industry Consortium for Energy (Materials)]) : UCL Lead
Ding, Y. (Co-Investigator), Slater, P. (Principal Investigator) & Steinberger-Wilckens, R. (Co-Investigator)
Engineering & Physical Science Research Council
8/11/17 → 6/11/21
Project: Research Councils

Supplemental Materials for the paper "Oxygen surface exchange properties and electrochemical activity of lanthanum nickelates"
Majewski, A. (Creator), Khodimchuk, A. V. (Creator), Zakharov, D. (Creator), Porotnikova, N. (Creator), Ananyev, M. (Creator), Johnson, I. D. (Creator), Darr, J. A. (Creator), Slater, P. (Creator) & Steinberger-Wilckens, R. (Creator), University of Birmingham, 28 Jun 2021
DOI: 10.25500/edata.bham.00000690
Dataset

Cite this

@article{b793d9f8cb854719aa82145adfacc611,

title = "Oxygen surface exchange properties and electrochemical activity of lanthanum nickelates",

abstract = "Oxygen surface exchange properties of lanthanum nickelates La2NiO4+δ, La3Ni2O7-δ and La4Ni3O10-δ (LNOs) have been investigated using the Pulsed Isotope 18O/16O Exchange (PIE) technique in the temperature range 300–700 °C. The evaluation of the oxygen exchange rate from these lanthanum nickelates was conducted by measurement of isotope fractions 18O2, 16O18O, and 16O2 in the effluent pulse at the exhaust from the reactor with a packed bed. The rates of oxygen heterogenous surface exchange (rH), dissociative adsorption (ra) and incorporation (ri) were calculated. The oxygen surface exchange was found to vary between the three nickelates, with rH decreasing between samples La3Ni2O7-δ > La4Ni3O10-δ > La2NiO4+δ, which was attributed to a decreasing presence of Ni cations on the particle surfaces. Despite possessing the lowest oxygen surface exchange, La2NiO4+δ had the best electrode electrochemical performance, which was attributed to highly mobile interstitial oxygen atoms leading to the largest ri (surface oxygen incorporation rate into the bulk) of the nickelates. This study reveals the key limiting factors determining lanthanum nickelate cathode performance in SOFCs, and we suggest avenues to improve these materials towards functional cathodes in devices.",

keywords = "Solid oxide cell, Oxygen electrode, La2NiO4+δ, La3Ni2O7-δ, La4Ni3O10-δ, Oxygen surface exchange, Isotope exchange",

author = "Artur Majewski and Anna Khodimchuk and Dmitry Zakharov and Maxim Ananyev and ian johnson and jawwad darr and Peter Slater and Robert Steinberger-Wilckens",

note = "Funding Information: The authors would like to express their appreciation to EPSRC, UK for support through the JUICED Hub (contract EP/R023662/1 ) funding. LEIS data collection was performed at the EPSRC National Facility for XPS (HarwellXPS).",

year = "2022",

month = aug,

doi = "10.1016/j.jssc.2022.123228",

language = "English",

volume = "312",

journal = "Journal of Solid State Chemistry",

issn = "0022-4596",

publisher = "Elsevier",

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T1 - Oxygen surface exchange properties and electrochemical activity of lanthanum nickelates

AU - Majewski, Artur

AU - Khodimchuk, Anna

AU - Zakharov, Dmitry

AU - Ananyev, Maxim

AU - johnson, ian

AU - darr, jawwad

AU - Slater, Peter

AU - Steinberger-Wilckens, Robert

N1 - Funding Information: The authors would like to express their appreciation to EPSRC, UK for support through the JUICED Hub (contract EP/R023662/1 ) funding. LEIS data collection was performed at the EPSRC National Facility for XPS (HarwellXPS).

PY - 2022/8

Y1 - 2022/8

N2 - Oxygen surface exchange properties of lanthanum nickelates La2NiO4+δ, La3Ni2O7-δ and La4Ni3O10-δ (LNOs) have been investigated using the Pulsed Isotope 18O/16O Exchange (PIE) technique in the temperature range 300–700 °C. The evaluation of the oxygen exchange rate from these lanthanum nickelates was conducted by measurement of isotope fractions 18O2, 16O18O, and 16O2 in the effluent pulse at the exhaust from the reactor with a packed bed. The rates of oxygen heterogenous surface exchange (rH), dissociative adsorption (ra) and incorporation (ri) were calculated. The oxygen surface exchange was found to vary between the three nickelates, with rH decreasing between samples La3Ni2O7-δ > La4Ni3O10-δ > La2NiO4+δ, which was attributed to a decreasing presence of Ni cations on the particle surfaces. Despite possessing the lowest oxygen surface exchange, La2NiO4+δ had the best electrode electrochemical performance, which was attributed to highly mobile interstitial oxygen atoms leading to the largest ri (surface oxygen incorporation rate into the bulk) of the nickelates. This study reveals the key limiting factors determining lanthanum nickelate cathode performance in SOFCs, and we suggest avenues to improve these materials towards functional cathodes in devices.

AB - Oxygen surface exchange properties of lanthanum nickelates La2NiO4+δ, La3Ni2O7-δ and La4Ni3O10-δ (LNOs) have been investigated using the Pulsed Isotope 18O/16O Exchange (PIE) technique in the temperature range 300–700 °C. The evaluation of the oxygen exchange rate from these lanthanum nickelates was conducted by measurement of isotope fractions 18O2, 16O18O, and 16O2 in the effluent pulse at the exhaust from the reactor with a packed bed. The rates of oxygen heterogenous surface exchange (rH), dissociative adsorption (ra) and incorporation (ri) were calculated. The oxygen surface exchange was found to vary between the three nickelates, with rH decreasing between samples La3Ni2O7-δ > La4Ni3O10-δ > La2NiO4+δ, which was attributed to a decreasing presence of Ni cations on the particle surfaces. Despite possessing the lowest oxygen surface exchange, La2NiO4+δ had the best electrode electrochemical performance, which was attributed to highly mobile interstitial oxygen atoms leading to the largest ri (surface oxygen incorporation rate into the bulk) of the nickelates. This study reveals the key limiting factors determining lanthanum nickelate cathode performance in SOFCs, and we suggest avenues to improve these materials towards functional cathodes in devices.

KW - Solid oxide cell

KW - Oxygen electrode

KW - La2NiO4+δ

KW - La3Ni2O7-δ

KW - La4Ni3O10-δ

KW - Oxygen surface exchange

KW - Isotope exchange

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U2 - 10.1016/j.jssc.2022.123228

DO - 10.1016/j.jssc.2022.123228

M3 - Article

SN - 0022-4596

VL - 312

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

M1 - 123228

ER -

Oxygen surface exchange properties and electrochemical activity of lanthanum nickelates

Abstract

Bibliographical note

Keywords

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Projects

ISCF Wave 1: (THe JUICED Hub [Joing University Industry Consortium for Energy (Materials)]) : UCL Lead

Datasets

Supplemental Materials for the paper "Oxygen surface exchange properties and electrochemical activity of lanthanum nickelates"

Cite this