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Effect of lattice volume and imperfections on the proton-phonon coupling in proton conducting lanthanide transition metal oxides: High pressure and high temperature neutron and impedance studies

English title Effect of lattice volume and imperfections on the proton-phonon coupling in proton conducting lanthanide transition metal oxides: High pressure and high temperature neutron and impedance studies (akronym: PROTONIQUE)
Applicant Braun Artur
Number 124812
Funding scheme Project funding (Div. I-III)
Research institution Labor für Hochleistungskeramik EMPA
Institution of higher education Swiss Federal Laboratories for Materials Science and Technology - EMPA
Main discipline Condensed Matter Physics
Start/End 01.09.2009 - 31.08.2012
Approved amount 201'242.00
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All Disciplines (2)

Discipline
Condensed Matter Physics
Physical Chemistry

Keywords (22)

proton conductors; fuel cells; proton-phonon coupling; proton conductor; hydrogen; perovskite; metal oxide ceramics; solid electrolyte; proton polaron; proton phonon coupling; neutron scattering; high pressure; ambient pressure XPS; in-situ electrochemistry; operando electrochemistry; ceramic fuel cell; solid oxide fuel cel; ionic transport properties; impedance spectroscopy; QENS; inelastic neutron scatering; epitaxial films

Lay Summary (English)

Lead
We verified with pressure dependent experiments that application of compressive strain increases the activation energy for proton conductivity in perovskite-type metal oxides such as Y-substituted barium zirconate and barium cerate. The results suggest that tensile strain engineering in epitxial ultrathin films could significantly enhance the proton conductivity, thus opening novel opportunities for protonics devices.
Lay summary

Proton conduction occurs by the hopping of a proton from one oxygen position to the next. We propose to study protonated and deuterated samples with neutron scattering. By locating protons/deuterons, a conduction mechanism may be hypothesized.Recent impedance studies show a clear influence of the synthesis method (chemical pressure) on the conductivity. The total conductivity was dominated by the grain boundary contribution. The apparent grain boundary conductivity may be related to the microstructure, in particular to the density, the particle size and to the grain-to-grain connectivity. The latter effect would be pressure dependent, too, but have no direct link to the lattice constant.Open questions and aimsThe project aims at understanding the influence of the near neighborhood structure in proton conductors on the bulk proton conductivity by combining electrical measurements, and neutron scattering as a function of temperature and pressure.Is the enhanced proton conductivity effectively a consequence of the increased lattice constant (atomic scale), or is it a result of more intimate grain-to-grain contact, i.e. a so-called grain boundary effect?There exists unambiguity on the term "grain boundary" in ceramic proton conductor literature. Grains are usually identified by scanning electron microscopy, whereas the typically much smaller crystallites can only be identified with transmission electron microscopy. Both present imperfections and may act as scatter centers for proton transport.How do crystallites and grains impede the proton transport?Is it possible to simulate the "chemical" pressure - which is done by A-site substitution - by application of a external pressure?Significance and broader benefitOur results have the potential to fine-tune the synthesis and processing of BZY and tailor them to enable new applications in solid state electrochemical devices.A broader benefit to the society will be particularly for energy conversion devices such as solid oxide fuel cells and hydrogen generation electrolysers, since global demand for energy is increasing while resources are limited and the environment is impaired.Our activities on proton conductors are compatible with a hydrogen economy. The extra know-how that we gain by applying neutron scattering on proton conductors is an investment in collateral activities on hydrogen related research.

 

[1] Q. Chen, A. Braun, S. Yoon, N. Bagdassarov, T. Graule, Effect of lattice volume and compressive strain on the conductivity of BaCeY-oxide ceramic proton conductors, J. Eur. Ceram. Soc. (2011) 31 (14) 2657-2661. http://dx.doi.org/10.1016/j.jeurceramsoc.2011.02.014

[2] Q. Chen, A. Braun, A. Ovalle, C.-D. Savaniu, T. Graule, N. Bagdassarov, Hydrostatic pressure decreases the proton mobility in the hydrated BaZr0.9Y0.1O3 proton conductor, Appl. Phys. Lett. 97, 041902 (2010) http://link.aip.org/link/?APL/97/041902   http://arxiv.org/abs/1106.1091

[3] A. Braun, A. Ovalle, S. Erat, V. Pomjakushin, A. Cervellino, W. Stolte, and T. Graule, Yttrium and hydrogen superstructure and correlation of lattice expansion and proton conductivity in the BaZr0.9Y0.1O2.95 proton conductor, Appl. Phys. Lett., 95, 224103, 2009.  http://apl.aip.org/resource/1/applab/v95/i22/p224103_s1

[4] A. Braun, S. Duval, J.P. Embs, F. Juranyi, P. Ried,  P. Holtappels, R. Hempelmann, U. Stimming, Th. Graule. Proton diffusivity in the BaZr0.9Y0.1O3-delta proton conductor.  J. Appl.  Electrochem. 2009, 39(4), 471-475. http://arxiv.org/abs/1106.1924  http://www.springerlink.com/content/c884r27365325361/fulltext.pdf

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Direct link to Lay Summary Last update: 30.12.2012

Responsible applicant and co-applicants

Employees

Publications

Publication
Observation of oxygen vacancy filling under water vapor in ceramic proton conductors in-situ with ambient pressure XPS
Chen Qianli, El Gabaly Farid, Aksoy Akgul Funda, Liu Zhi, Mun Bongjin Simon, Yamaguchi Shu, Braun Artur (2013), Observation of oxygen vacancy filling under water vapor in ceramic proton conductors in-situ with ambient pressure XPS, in Chemistry of Materials, 25(23), 4690-4696.
Proton diffusivity in spark plasma sintered BaCe0.8Y 0.2O3 - δ: In-situ combination of quasi-elastic neutron scattering and impedance spectroscopy
Chen Qianli, Banyte Juste, Zhang Xin, Embs Jan Peter, Braun Artur (2013), Proton diffusivity in spark plasma sintered BaCe0.8Y 0.2O3 - δ: In-situ combination of quasi-elastic neutron scattering and impedance spectroscopy, in Solid State Ionics, 252, 2-6.
Barium Cerate with yttria as proton conducting electrolyte
Navickas E., Braun A., Chen Q., Abakeviien B., Kubel F., Tamulevicius S., Fleig J. (2012), Barium Cerate with yttria as proton conducting electrolyte, in Book Series: Radiation Interaction with Material and Its Use in Technologies , Book Editor: Grigonis, A(4th Intern), 107-110.
Effect of lattice volume and strain on the conductivity of BaCeY-oxide ceramic proton conductors
Qianli Chen Artur Braun Songhak Yoon Nikolai Bagdassarov Thomas Graule (2012), Effect of lattice volume and strain on the conductivity of BaCeY-oxide ceramic proton conductors, arxiv, Cornell.
Effect of lattice volume and compressive strain on the conductivity of BaCeY-oxide ceramic proton conductors
Chen Q, Braun A, Yoon S, Bagdassarov N, Graule T (2011), Effect of lattice volume and compressive strain on the conductivity of BaCeY-oxide ceramic proton conductors, in Journal of the European Ceramic Society, 31(14), 2657-2661.
The effect of compressive strain on the Raman modes of the dry and hydrated BaCe0.8Y0.2O3 proton conductor
Chen Qianli, Huang Tzu-Wen, Baldini Maria, Hushur Anwar, Pomjakushin Vladimir, Clark Simon, Mao Wendy, Manghnani Murli, Braun Artur, Graule Thomas (2011), The effect of compressive strain on the Raman modes of the dry and hydrated BaCe0.8Y0.2O3 proton conductor, in The Journal of Physical Chemistry C, 115(48), 24021-24027.
Hydrostatic pressure decreases the proton mobility in the hydrated BaZr0.9 Y0.1 O3 proton conductor
Chen Q, Braun A, Ovalle A, Savaniu C-D, Graule T, Bagdassarov N (2010), Hydrostatic pressure decreases the proton mobility in the hydrated BaZr0.9 Y0.1 O3 proton conductor, in Applied Physics Letters, 97(4), 041902-1-041902-3.
Fundamental understanding of conductivity in fuel cell components at high temperatures
Braun A, Erat S, Zhang X, Pignedoli CA, Passerone D (2009), Fundamental understanding of conductivity in fuel cell components at high temperatures, in EMPA Activities, (2009-2010 ), 4-5.
Yttrium and hydrogen superstructure and correlation of lattice expansion and proton conductivity in the BaZr0.9Y0.1O2.95 proton conductor
Braun Artur, A. Ovalle V. Pomjakushin A. Cervellino S. Erat W. C. Stolte T. Graule (2009), Yttrium and hydrogen superstructure and correlation of lattice expansion and proton conductivity in the BaZr0.9Y0.1O2.95 proton conductor, in Applied Physics Letters, 95(22), 224103-1-224103-3.
Experimental neutron scattering evidence for proton polaron in hydrated metal oxides proton conductors
Braun Artur , Chen Qianli, Experimental neutron scattering evidence for proton polaron in hydrated metal oxides proton conductors, in Nature Communications, 8.

Collaboration

Group / person Country
Types of collaboration
ILL France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Univ. St. Andrews Great Britain and Northern Ireland (Europe)
- Publication
Univ. Montpellier France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
State Key Laboratory of Metastable Material Science and Technology, Yanshan University China (Asia)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Hanyang University, Ansan Korean Republic (South Korea) (Asia)
- Exchange of personnel
Stanford University United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
University of Hawaii, Hawaii Institute of Geophysics and Planetology United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Advanced Light Source United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Sandia National Laboratories United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
Goethe Universität Frankfurt, Insitute of Geophysics Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
PSI Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Hanyang University Korean Republic (South Korea) (Asia)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
ALTECH 2017 Talk given at a conference X-rays And Neutrons: The Pick & Shovel For The Materials Scientist 24.05.2017 Strassbourg, France Braun Artur;
International Conference on Photonics and Solar Water Splitting(PSWS-2015) Talk given at a conference (p,T) parameterization of the proton-phonon coupling in proton conducting electrolytes 12.03.2015 Ernakulam, Kerala, India Braun Artur;
AOFC 2015 Talk given at a conference Proton-Phonon Coupling in Solid Electrolyte Membranes for Intermediate Temperature Ceramic Fuel CellsCrossover from hydrates to hydrides to proton conductors 11.03.2015 Kolkata, India Braun Artur;
2nd International Workshop on Nanotechnology, Renewable & Sustainability Talk given at a conference (p,T) paramterization of proton phonon coupling in ceramic proton conducting electrolytes 19.09.2014 Xi'an, China, China Braun Artur;
Solid State Proton Conductors 17 Talk given at a conference (p,T) paramterization of proton phonon coupling in ceramic proton conducting electrolytes 15.09.2014 Seoul, Korea, Korean Republic (South Korea) Braun Artur;
Swiss Physical Society Annual Meeting 2014 Talk given at a conference (p,T) parameterization of the proton-phonon coupling in proton conducting electrolytes 30.06.2014 Fribourg, Switzerland Strässle Thierry; Embs Jan Peter; Chen Qianli; Braun Artur;
Swiss Society for Crystallography Annual Meeting Poster Effect of Lattice Volume and Strain on the Conductivity of Ceramic Proton Conductors 16.09.2011 Bern, Switzerland Chen Qianli;
European Fuel Cell Forum Talk given at a conference Investigation of the Transport Properties on the Strained Ceramic Proton Conductors under Pressure 28.07.2011 Luzern, Schweiz, Switzerland Braun Artur; Chen Qianli;
481. Wilhelm and Else Heraeus Seminar Energy Materials Research by Neutrons and Synchrotron Radiation Talk given at a conference Structure and transport in fuel cell components 09.05.2011 Bad Godesberg, Germany, Germany Braun Artur;
MRS Spring Meeting 2011 Talk given at a conference Probing the Effects of Pressure-induced Strain and Imperfections on the Proton Transport Properties of Ceramic Proton Conductors 25.04.2011 San Francisco, California USA, United States of America Braun Artur; Chen Qianli;
8th Symposium on Fuel Cell Modeling and Experimental Validation Talk given at a conference Diagnostics and analysis of electro chemical energy storage and conversion devices, components, and materials with synchrotron x-ray and neutron scattering and spectroscopy 08.03.2011 Bonn, Germany, Germany Braun Artur;
Neutrons for Global Energy Solutions Talk given at a conference Ceramic proton conductors for intermediate temperature solid oxide fuel cells and other electrochemical applications 26.09.2010 Bonn, Germany, Germany Braun Artur;
Swiss Society for Crystallography Annual Meeting 2010 Talk given at a conference Some applications of synchrotron and neutron scattering and spectroscopy to energy materials research. 17.09.2010 Genf, Schweiz, Switzerland Chen Qianli; Braun Artur;
11th International Conference on Ceramic Processing Science, ICCPS‐11 Talk given at a conference Correlation of s tructure and proton conductivity in BaZrY-oxide 29.08.2010 Zürich, Schweiz, Switzerland Braun Artur; Chen Qianli;
Advanced Materials and Technologies (13th International Conference-School) Talk given at a conference X-rays and neutrons: small probes for big problems 27.08.2010 Palanga, Lithuania, Lithuania Braun Artur;
NIMS Conference 2010 Talk given at a conference Some Applications of Synchrotron andNeutron Scattering and Spectroscopy toEnergy Materials Research 12.07.2010 Tsukuba, Japan, Japan Braun Artur;


Self-organised

Title Date Place
MRS spring meeting 2011 Symposium J: Protons in Solids 25.04.2011 San Francisco California USA, United States of America
PhD Student's Symposium 2010 07.10.2010 Dübendorf, Schweiz, Switzerland

Communication with the public

Communication Title Media Place Year
New media (web, blogs, podcasts, news feeds etc.) The ins and outs of hydrogen International Innovation, EuroFocus Issue 18, January 2013, pp 85-87 (Research Media, UK) International 2012
New media (web, blogs, podcasts, news feeds etc.) 2nd Prize of the Swiss Society for Crystallography MaNEP Newsletter Nr. 23 Western Switzerland 2010
New media (web, blogs, podcasts, news feeds etc.) NMI3 SUPPORTING YOUNG PHD STUDENT TO ATTEND European Neutron Portal International 2010

Awards

Title Year
Dr. Qianli Chen: "Young Scientist Prize of the Swiss Neutron Scattering Society". The prize is awarded for the outstanding scientific achievements presented in the PhD thesis. Award Ceremony in Fribourg, 1st July 2014. 2014
Dr. Qianli Chen Humboldt-Forschungsstipendium Auswahldatum: November 2013 Dienstadresse zum Zeitpunkt der Auswahlsitzung: Eidgenössische Materialprüfungs- und Forschungsanstalt (EMPA), Dübendorf, Schweiz Herkunftsland: China, VR Fachgebiet: Elektrochemie Gastgeber/in: Dr. Katrin F. Domke (MPI für Polymerforschung, Mainz, Deutschland) 2013
2nd Poster Prize of the Swiss Crystallographic Society 2011
2nd Poster Prize of the Swiss Crystallographic Society 2010

Associated projects

Number Title Start Funding scheme
147413 International Exploratory Workshop on Soft X-rays, Electrochemistry, and Energy Materials 01.05.2013 International Exploratory Workshops

Abstract

Lanthanide transition metal oxides are known for their proton conducting properties and believed to be promising solid electrolyte materials for intermediate temperature electrochemical devices. The fundamental physical and chemical processes of the proton-phonon dynamics are not well known. The current opinion is that in these compounds, oxygen vacancies are created by doping with a lower valent cation or by off-stoichiometric composition. In wet atmosphere, the vacancies are filled by the oxygen of the H2O molecule and the protons enter the interstitial lattice positions. Then, the H+ would be available as a mobile positive charge carrier for electric transport, subject to thermal activation.As a matter of fact, many oxides dissolve small amounts of water and become proton conductors at elevated temperatures, where the water molecule dissociates into H+ and OH-. Some oxides have maximum proton conductivity at around 500°C, a temperature much lower than for oxygen vacancy conduction in conventional solid electrolytes. Guided by mechanistic intuition, Iwahara demonstrated some 25 years ago that the small hydrogen ion (proton) is more mobile and can diffuse more quickly than the larger oxygen ion. Because of that an oxidic electrolyte may conduct protons, rather than, or in addition to oxygen ions.In a recent PhD thesis, it was found that the activation energy for H+ transport in BaZrY-oxide decreased with increasing lattice spacing. In particular, the conductivity varies by three orders of magnitude with the lattice parameter, and the activation energy varies by a factor of two. This seems to suggest that “protons need space” in order to be mobile in solids.This seemingly trivial finding is actually novel and not established in the proton conductor community, although potential relations between the activation energy and structure parameters were pointed out as early as 1988. For the ultimate and exact proof of the aforementioned hypothesis, or to present potential alternative explanations for the observed effect on the conductivity, we propose to combine direct pressure dependent and temperature dependent analytical techniques in order to monitor the proton transport: on the macroscopic scale with electrochemical techniques, and on the molecular scale with synchrotron x-ray and neutron scattering techniques. A Braun, S. Duval, J.P. Embs, F. Juranyi, P. Ried, P. Holtappels, R. Hempelmann, U. Stimming, Th. Graule. Proton diffusivity in the BaZr0.9Y0.1O3-delta proton conductor. J. Appl. Electrochem. 2009, 39(4), 471-475.http://arxiv.org/abs/1106.1924http://www.springerlink.com/content/c884r27365325361/fulltext.pdf
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