Theory of the electrostatic surface potential and intrinsic dipole moments at the mixed ionic electronic conductor (MIEC)-gas interface

Nicholas J. Williams; Ieuan D. Seymour; Robert T. Leah; Subhasish Mukerjee; Mark Selby; Stephen J. Skinner

doi:10.1039/d1cp01639c

Theory of the electrostatic surface potential and intrinsic dipole moments at the mixed ionic electronic conductor (MIEC)-gas interface

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

5 Citations (Scopus)

Abstract

The local activation overpotential describes the electrostatic potential shift away from equilibrium at an electrode/electrolyte interface. This electrostatic potential is not entirely satisfactory for describing the reaction kinetics of a mixed ionic-electronic conducting (MIEC) solid-oxide cell (SOC) electrode where charge transfer occurs at the electrode-gas interface. Using the theory of the electrostatic potential at the MIEC-gas interface as an electrochemical driving force, charge transfer at the ceria-gas interface has been modelled based on the intrinsic dipole potential of the adsorbate. This model gives a physically meaningful reason for the enhancement in electrochemical activity of a MIEC electrode as the steam and hydrogen pressure is increased in both fuel cell and electrolysis modes. This model was validated againstoperandoXPS data from previous literature to accurately predict the outer work function shift of thin film Sm_0.2Ce_0.8O_1.9in a H₂/H₂O atmosphere as a function of overpotential.

Original language	English
Pages (from-to)	14569-14579
Number of pages	11
Journal	Physical Chemistry Chemical Physics
Volume	23
Issue number	27
Early online date	7 May 2021
DOIs	https://doi.org/10.1039/d1cp01639c
Publication status	Published - 21 Jul 2021

Bibliographical note

Funding Information:
This work was supported by Ceres Power Ltd. All first principle calculations were performed using the Imperial College Research Computing Service (DOI: 10.14469/hpc/2232). We are also grateful for the discussion with Dr Alex Shard from the National Physical Laboratory, Teddington, UK, on analysingoperandoXPS data. We also acknowledge the support of the EPSRC through the award of a platform grant (EP/R002010/1) and through support for the Centre for Doctoral Training in the Advanced Characterisation of Materials (EP/L015277/1).

Funding Information:
This work was supported by Ceres Power Ltd. All first principle calculations were performed using the Imperial College Research Computing Service (DOI: 10.14469/hpc/2232). We are also grateful for the discussion with Dr Alex Shard from the National Physical Laboratory, Teddington, UK, on analysing operando XPS data. We also acknowledge the support of the EPSRC through the award of a platform grant (EP/R002010/1)

Publisher Copyright:
© the Owner Societies 2021.

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abstract = "The local activation overpotential describes the electrostatic potential shift away from equilibrium at an electrode/electrolyte interface. This electrostatic potential is not entirely satisfactory for describing the reaction kinetics of a mixed ionic-electronic conducting (MIEC) solid-oxide cell (SOC) electrode where charge transfer occurs at the electrode-gas interface. Using the theory of the electrostatic potential at the MIEC-gas interface as an electrochemical driving force, charge transfer at the ceria-gas interface has been modelled based on the intrinsic dipole potential of the adsorbate. This model gives a physically meaningful reason for the enhancement in electrochemical activity of a MIEC electrode as the steam and hydrogen pressure is increased in both fuel cell and electrolysis modes. This model was validated againstoperandoXPS data from previous literature to accurately predict the outer work function shift of thin film Sm0.2Ce0.8O1.9in a H2/H2O atmosphere as a function of overpotential.",

author = "Williams, {Nicholas J.} and Seymour, {Ieuan D.} and Leah, {Robert T.} and Subhasish Mukerjee and Mark Selby and Skinner, {Stephen J.}",

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Theory of the electrostatic surface potential and intrinsic dipole moments at the mixed ionic electronic conductor (MIEC)-gas interface

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