Non-equilibrium thermodynamics of mixed ionic-electronic conductive electrodes and their interfaces: a Ni/CGO study

Nicholas J. Williams; Ieuan D. Seymour; Robert T. Leah; Aayan Banerjee; Subhasish Mukerjee; Stephen J. Skinner

doi:10.1039/d1ta07351f

Non-equilibrium thermodynamics of mixed ionic-electronic conductive electrodes and their interfaces: a Ni/CGO study

Nicholas J. Williams, Ieuan D. Seymour, Robert T. Leah, Aayan Banerjee, Subhasish Mukerjee, Stephen J. Skinner^*

^*Corresponding author for this work

Chemistry

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Abstract

Non-equilibrium thermodynamics describe the current-voltage characteristics of electrochemical devices. For conventional electrode-electrolyte interfaces, the local activation overpotential is used to describe the electrostatic potential step between the two materials as a current is generated. However, the activation overpotential for the metal/mixed ionic-electronic conducting (MIEC) composite electrodes studied in this work originates at the MIEC-gas interface. Moreover, we have studied the effects of non-equilibrium on the electrostatic surface potential and evaluated its influence over electrode kinetics. By investigating two phase (2PB) and three phase boundary (3PB) reactions at the Ni/Ce_1−xGd_xO_2−δ (Ni/CGO) electrode, we have demonstrated that the driving force for coupled ion-electron transfer is held at the CGO-gas interface for both reaction pathways. We also determined that the rate of coupled ion-electron transfer via the 3PB scales with the availability of free sites on the metallic surface, revealing a Sabatier-like relationship with regards to the selection of metallic phases. Finally, we demonstrated how the theory of the electrostatic surface potential can be applied to other systems outside of the well-studied H₂/H₂O electrode environment. These findings therefore provide an insight into the design of future electrode structures for a range of electrochemical devices.

Original language	English
Pages (from-to)	11121-11130
Number of pages	10
Journal	Journal of Materials Chemistry A
Volume	10
Issue number	20
Early online date	19 Apr 2022
DOIs	https://doi.org/10.1039/d1ta07351f
Publication status	Published - 28 May 2022

Bibliographical note

Funding Information:
This work was supported by Ceres Power Ltd. IDS and SJS acknowledge the EPSRC for funding through the award of grant EP/R002010/1.

Data Availability Statement

Electronic supplementary information (ESI) available. See https://www.rsc.org/suppdata/d1/ta/d1ta07351f/d1ta07351f1.pdf

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Cite this

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title = "Non-equilibrium thermodynamics of mixed ionic-electronic conductive electrodes and their interfaces: a Ni/CGO study",

abstract = "Non-equilibrium thermodynamics describe the current-voltage characteristics of electrochemical devices. For conventional electrode-electrolyte interfaces, the local activation overpotential is used to describe the electrostatic potential step between the two materials as a current is generated. However, the activation overpotential for the metal/mixed ionic-electronic conducting (MIEC) composite electrodes studied in this work originates at the MIEC-gas interface. Moreover, we have studied the effects of non-equilibrium on the electrostatic surface potential and evaluated its influence over electrode kinetics. By investigating two phase (2PB) and three phase boundary (3PB) reactions at the Ni/Ce1−xGdxO2−δ (Ni/CGO) electrode, we have demonstrated that the driving force for coupled ion-electron transfer is held at the CGO-gas interface for both reaction pathways. We also determined that the rate of coupled ion-electron transfer via the 3PB scales with the availability of free sites on the metallic surface, revealing a Sabatier-like relationship with regards to the selection of metallic phases. Finally, we demonstrated how the theory of the electrostatic surface potential can be applied to other systems outside of the well-studied H2/H2O electrode environment. These findings therefore provide an insight into the design of future electrode structures for a range of electrochemical devices.",

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note = "Funding Information: This work was supported by Ceres Power Ltd. IDS and SJS acknowledge the EPSRC for funding through the award of grant EP/R002010/1. ",

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T2 - a Ni/CGO study

AU - Williams, Nicholas J.

AU - Seymour, Ieuan D.

AU - Leah, Robert T.

AU - Banerjee, Aayan

AU - Mukerjee, Subhasish

AU - Skinner, Stephen J.

N1 - Funding Information: This work was supported by Ceres Power Ltd. IDS and SJS acknowledge the EPSRC for funding through the award of grant EP/R002010/1.

PY - 2022/5/28

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N2 - Non-equilibrium thermodynamics describe the current-voltage characteristics of electrochemical devices. For conventional electrode-electrolyte interfaces, the local activation overpotential is used to describe the electrostatic potential step between the two materials as a current is generated. However, the activation overpotential for the metal/mixed ionic-electronic conducting (MIEC) composite electrodes studied in this work originates at the MIEC-gas interface. Moreover, we have studied the effects of non-equilibrium on the electrostatic surface potential and evaluated its influence over electrode kinetics. By investigating two phase (2PB) and three phase boundary (3PB) reactions at the Ni/Ce1−xGdxO2−δ (Ni/CGO) electrode, we have demonstrated that the driving force for coupled ion-electron transfer is held at the CGO-gas interface for both reaction pathways. We also determined that the rate of coupled ion-electron transfer via the 3PB scales with the availability of free sites on the metallic surface, revealing a Sabatier-like relationship with regards to the selection of metallic phases. Finally, we demonstrated how the theory of the electrostatic surface potential can be applied to other systems outside of the well-studied H2/H2O electrode environment. These findings therefore provide an insight into the design of future electrode structures for a range of electrochemical devices.

AB - Non-equilibrium thermodynamics describe the current-voltage characteristics of electrochemical devices. For conventional electrode-electrolyte interfaces, the local activation overpotential is used to describe the electrostatic potential step between the two materials as a current is generated. However, the activation overpotential for the metal/mixed ionic-electronic conducting (MIEC) composite electrodes studied in this work originates at the MIEC-gas interface. Moreover, we have studied the effects of non-equilibrium on the electrostatic surface potential and evaluated its influence over electrode kinetics. By investigating two phase (2PB) and three phase boundary (3PB) reactions at the Ni/Ce1−xGdxO2−δ (Ni/CGO) electrode, we have demonstrated that the driving force for coupled ion-electron transfer is held at the CGO-gas interface for both reaction pathways. We also determined that the rate of coupled ion-electron transfer via the 3PB scales with the availability of free sites on the metallic surface, revealing a Sabatier-like relationship with regards to the selection of metallic phases. Finally, we demonstrated how the theory of the electrostatic surface potential can be applied to other systems outside of the well-studied H2/H2O electrode environment. These findings therefore provide an insight into the design of future electrode structures for a range of electrochemical devices.

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Non-equilibrium thermodynamics of mixed ionic-electronic conductive electrodes and their interfaces: a Ni/CGO study

Abstract

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