ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems

Autores
Van Duin, Adri C. T.; Merinov, Boris V.; Han, Sang Soo; Dorso, Claudio Oscar; Goddard III, William A.
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Proton-conducting perovskites such as Y-doped BaZiO3 (BYZ) are promising candidates as electrolytes for a proton ceramic fuel cell (PCFC) that might permit much lower temperatures (from 400 to 600 °C). However, these materials lead to relatively poor total conductivity (∼10-4 S/cm) because of extremely high grain boundary resistance. In order to provide the basis for improving these materials, we developed the ReaxFF reactive force field to enable molecular dynamics (MD) simulations of proton diffusion in the bulk phase and across grain boundaries of BYZ. This allows us to elucidate the atomistic structural details underlying the origin of this poor grain boundary conductivity and how it is related to the orientation of the grains. The parameters in ReaxFF were based entirely on the results of quantum mechanics (QM) calculations for systems related to BYZ. We apply here the ReaxFF to describe the proton diffusion in crystalline BYZ and across grain boundaries in BYZ. The results are in excellent agreement with experiment, validating the use of ReaxFF for studying the transport properties of these membranes. Having atomistic structures for the grain boundaries from simulations that explain the overall effect of the grain boundaries on diffusion opens the door to in silico optimization of these materials. That is, we can now use theory and simulation to examine the effect of alloying on both the interfacial structures and on the overall diffusion. As an example, these calculations suggest that the reduced diffusion of protons across the grain boundary results from the increased average distances between oxygen atoms in the interface, which necessarily leads to larger barriers for proton hopping. Assuming that this is the critical issue in grain boundary diffusion, the performance of BYZ for multigranular systems might be improved using additives that would tend to precipitate to the grain boundary and which would tend to pull the oxygens atoms together. Possibilities might be to use a small amount of larger trivalent ions, such as La or Lu or of tetravalent ions such as Hf or Th. Since ReaxFF can also be used to describe the chemical processes on the anode and cathode and the migration of ions across the electrode-membrane interface, ReaxFF opens the door to the possibility of atomistic first principles predictions on models of a complete fuel cell. © 2008 American Chemical Society.
Fil: Van Duin, Adri C. T.. California Institute of Technology; Estados Unidos
Fil: Merinov, Boris V.. California Institute of Technology; Estados Unidos
Fil: Han, Sang Soo. California Institute of Technology; Estados Unidos
Fil: Dorso, Claudio Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. California Institute of Technology; Estados Unidos
Fil: Goddard III, William A.. California Institute of Technology; Estados Unidos
Materia
Perovskites
Path
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/61995

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network_name_str CONICET Digital (CONICET)
spelling ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular SystemsVan Duin, Adri C. T.Merinov, Boris V.Han, Sang SooDorso, Claudio OscarGoddard III, William A.PerovskitesPathhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Proton-conducting perovskites such as Y-doped BaZiO3 (BYZ) are promising candidates as electrolytes for a proton ceramic fuel cell (PCFC) that might permit much lower temperatures (from 400 to 600 °C). However, these materials lead to relatively poor total conductivity (∼10-4 S/cm) because of extremely high grain boundary resistance. In order to provide the basis for improving these materials, we developed the ReaxFF reactive force field to enable molecular dynamics (MD) simulations of proton diffusion in the bulk phase and across grain boundaries of BYZ. This allows us to elucidate the atomistic structural details underlying the origin of this poor grain boundary conductivity and how it is related to the orientation of the grains. The parameters in ReaxFF were based entirely on the results of quantum mechanics (QM) calculations for systems related to BYZ. We apply here the ReaxFF to describe the proton diffusion in crystalline BYZ and across grain boundaries in BYZ. The results are in excellent agreement with experiment, validating the use of ReaxFF for studying the transport properties of these membranes. Having atomistic structures for the grain boundaries from simulations that explain the overall effect of the grain boundaries on diffusion opens the door to in silico optimization of these materials. That is, we can now use theory and simulation to examine the effect of alloying on both the interfacial structures and on the overall diffusion. As an example, these calculations suggest that the reduced diffusion of protons across the grain boundary results from the increased average distances between oxygen atoms in the interface, which necessarily leads to larger barriers for proton hopping. Assuming that this is the critical issue in grain boundary diffusion, the performance of BYZ for multigranular systems might be improved using additives that would tend to precipitate to the grain boundary and which would tend to pull the oxygens atoms together. Possibilities might be to use a small amount of larger trivalent ions, such as La or Lu or of tetravalent ions such as Hf or Th. Since ReaxFF can also be used to describe the chemical processes on the anode and cathode and the migration of ions across the electrode-membrane interface, ReaxFF opens the door to the possibility of atomistic first principles predictions on models of a complete fuel cell. © 2008 American Chemical Society.Fil: Van Duin, Adri C. T.. California Institute of Technology; Estados UnidosFil: Merinov, Boris V.. California Institute of Technology; Estados UnidosFil: Han, Sang Soo. California Institute of Technology; Estados UnidosFil: Dorso, Claudio Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. California Institute of Technology; Estados UnidosFil: Goddard III, William A.. California Institute of Technology; Estados UnidosAmerican Chemical Society2008-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/61995Van Duin, Adri C. T.; Merinov, Boris V.; Han, Sang Soo; Dorso, Claudio Oscar; Goddard III, William A.; ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems; American Chemical Society; Journal of Physical Chemistry A; 112; 45; 11-2008; 11414-114221089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp801082qinfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/jp801082qinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:28:37Zoai:ri.conicet.gov.ar:11336/61995instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:28:37.746CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems
title ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems
spellingShingle ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems
Van Duin, Adri C. T.
Perovskites
Path
title_short ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems
title_full ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems
title_fullStr ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems
title_full_unstemmed ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems
title_sort ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems
dc.creator.none.fl_str_mv Van Duin, Adri C. T.
Merinov, Boris V.
Han, Sang Soo
Dorso, Claudio Oscar
Goddard III, William A.
author Van Duin, Adri C. T.
author_facet Van Duin, Adri C. T.
Merinov, Boris V.
Han, Sang Soo
Dorso, Claudio Oscar
Goddard III, William A.
author_role author
author2 Merinov, Boris V.
Han, Sang Soo
Dorso, Claudio Oscar
Goddard III, William A.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Perovskites
Path
topic Perovskites
Path
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Proton-conducting perovskites such as Y-doped BaZiO3 (BYZ) are promising candidates as electrolytes for a proton ceramic fuel cell (PCFC) that might permit much lower temperatures (from 400 to 600 °C). However, these materials lead to relatively poor total conductivity (∼10-4 S/cm) because of extremely high grain boundary resistance. In order to provide the basis for improving these materials, we developed the ReaxFF reactive force field to enable molecular dynamics (MD) simulations of proton diffusion in the bulk phase and across grain boundaries of BYZ. This allows us to elucidate the atomistic structural details underlying the origin of this poor grain boundary conductivity and how it is related to the orientation of the grains. The parameters in ReaxFF were based entirely on the results of quantum mechanics (QM) calculations for systems related to BYZ. We apply here the ReaxFF to describe the proton diffusion in crystalline BYZ and across grain boundaries in BYZ. The results are in excellent agreement with experiment, validating the use of ReaxFF for studying the transport properties of these membranes. Having atomistic structures for the grain boundaries from simulations that explain the overall effect of the grain boundaries on diffusion opens the door to in silico optimization of these materials. That is, we can now use theory and simulation to examine the effect of alloying on both the interfacial structures and on the overall diffusion. As an example, these calculations suggest that the reduced diffusion of protons across the grain boundary results from the increased average distances between oxygen atoms in the interface, which necessarily leads to larger barriers for proton hopping. Assuming that this is the critical issue in grain boundary diffusion, the performance of BYZ for multigranular systems might be improved using additives that would tend to precipitate to the grain boundary and which would tend to pull the oxygens atoms together. Possibilities might be to use a small amount of larger trivalent ions, such as La or Lu or of tetravalent ions such as Hf or Th. Since ReaxFF can also be used to describe the chemical processes on the anode and cathode and the migration of ions across the electrode-membrane interface, ReaxFF opens the door to the possibility of atomistic first principles predictions on models of a complete fuel cell. © 2008 American Chemical Society.
Fil: Van Duin, Adri C. T.. California Institute of Technology; Estados Unidos
Fil: Merinov, Boris V.. California Institute of Technology; Estados Unidos
Fil: Han, Sang Soo. California Institute of Technology; Estados Unidos
Fil: Dorso, Claudio Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. California Institute of Technology; Estados Unidos
Fil: Goddard III, William A.. California Institute of Technology; Estados Unidos
description Proton-conducting perovskites such as Y-doped BaZiO3 (BYZ) are promising candidates as electrolytes for a proton ceramic fuel cell (PCFC) that might permit much lower temperatures (from 400 to 600 °C). However, these materials lead to relatively poor total conductivity (∼10-4 S/cm) because of extremely high grain boundary resistance. In order to provide the basis for improving these materials, we developed the ReaxFF reactive force field to enable molecular dynamics (MD) simulations of proton diffusion in the bulk phase and across grain boundaries of BYZ. This allows us to elucidate the atomistic structural details underlying the origin of this poor grain boundary conductivity and how it is related to the orientation of the grains. The parameters in ReaxFF were based entirely on the results of quantum mechanics (QM) calculations for systems related to BYZ. We apply here the ReaxFF to describe the proton diffusion in crystalline BYZ and across grain boundaries in BYZ. The results are in excellent agreement with experiment, validating the use of ReaxFF for studying the transport properties of these membranes. Having atomistic structures for the grain boundaries from simulations that explain the overall effect of the grain boundaries on diffusion opens the door to in silico optimization of these materials. That is, we can now use theory and simulation to examine the effect of alloying on both the interfacial structures and on the overall diffusion. As an example, these calculations suggest that the reduced diffusion of protons across the grain boundary results from the increased average distances between oxygen atoms in the interface, which necessarily leads to larger barriers for proton hopping. Assuming that this is the critical issue in grain boundary diffusion, the performance of BYZ for multigranular systems might be improved using additives that would tend to precipitate to the grain boundary and which would tend to pull the oxygens atoms together. Possibilities might be to use a small amount of larger trivalent ions, such as La or Lu or of tetravalent ions such as Hf or Th. Since ReaxFF can also be used to describe the chemical processes on the anode and cathode and the migration of ions across the electrode-membrane interface, ReaxFF opens the door to the possibility of atomistic first principles predictions on models of a complete fuel cell. © 2008 American Chemical Society.
publishDate 2008
dc.date.none.fl_str_mv 2008-11
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/61995
Van Duin, Adri C. T.; Merinov, Boris V.; Han, Sang Soo; Dorso, Claudio Oscar; Goddard III, William A.; ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems; American Chemical Society; Journal of Physical Chemistry A; 112; 45; 11-2008; 11414-11422
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/61995
identifier_str_mv Van Duin, Adri C. T.; Merinov, Boris V.; Han, Sang Soo; Dorso, Claudio Oscar; Goddard III, William A.; ReaxFF Readctive Force Field for the Y-doped BaZrO3 Proton Conductor with applications to diffusion Rates for Multigranular Systems; American Chemical Society; Journal of Physical Chemistry A; 112; 45; 11-2008; 11414-11422
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jp801082q
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/jp801082q
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
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instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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