Functional Oxide Materials exhibiting Ionic Conductivity for Future Energy Conversion Needs
Doktorsavhandling, 2013

Fuel cells are electrochemical devices that transform the chemical energy in hydrogen and oxygen into electrical energy at high efficiencies and produce only water vapour emissions. Materials with the perovskite or fluorite structure types are commonly employed as the ion conducting ceramic electrolyte membranes in intermediate and high temperature fuel cells. However, due to the desire for lower operating temperatures of ~ 600 °C, there exists several challenges, namely: i) insufficient ionic conductivity (minimum required ~ 10-2 Scm-1), ii) poor densification and iii) poor conductivity across grain boundaries. Another problem for proton conducting ceramic fuel cells is the lack of suitable cathode materials with appropriate mixed protonic-electronic conduction. In-situ cells to characterize these materials with concurrent techniques are also not available. The works herein try to address these challenges by exploring the structure property interplay of several candidate materials. The main techniques used were: Thermogravimetric Analysis, powder X-ray and neutron diffraction and electrochemical impedance spectroscopy. The proton conductivity of In3+-BaZrO3 was improved through co-doping with Yb3+ compared to individually doped In3+-BaZrO3 and Yb3+-BaZrO3 samples. Spark plasma sintering of In3+-BaZrO3 achieved high densities (92 %) samples, and the grain boundary conductivity was boosted in comparison to conventionally sintered samples. The oxygen deficient perovskite system, Ba3In2ZrO8, substituted with Ga3+ and Y3+ and Gd3+ and Y3+ combinations was shown to posses’ mixed ionic-electronic conduction with the Ga3+ containing sample having the greatest electron hole contribution. The crystal structure and conductivity of an alternative system to BaZrO3, Sc3+ substituted BaSnO3, was explored and BaSn0.6Sc0.4O3-δ found to have a proton conductivity as high as the current leading materials, i.e., 1.07×10-3 S cm-1 at 600 °C. Disorder in the anion sub-lattice of the pyrochlore-fluorite, Y2(Ti1–xZrx)2O7 system, studied using advanced analysis of neutron diffraction data, was found to significantly enhance O2- ion conductivity; in comparison disorder in the cation sub-lattice did not greatly influence the conductivity. This work also demonstrates two cells developed for in-situ conductivity and hydration studies coupled to neutron diffraction using In3+-BaZrO3 samples, and new insights into the hydration behaviour with respect to temperature and the thermal parameters of the oxygen anions were gained.

neutron diffraction

perovskites

oxygen deficient perovskites

BaSnO3

Rietveld refinements

BaZrO3

in-situ cells

proton conduction

deuteron position

Ba3In2ZrO8

10:an, Kemivägen 10
Opponent: Nikolaos Bonanos, Senior Scientist,Department of Energy Conversion and Storage, Technical University of Denmark, Denmark.

Författare

FRANCIS GACHAO KINYANJUI

Chalmers, Kemi- och bioteknik, Oorganisk miljökemi

In-situ conductivity and hydration studies of proton conductors using neutron powder diffraction

Solid State Ionics,; Vol. 225(2012)p. 312-316

Paper i proceeding

Improved Proton Conductivity in Spark-Plasma Sintered Dense Ceramic BaZr0.5In0.5O3-delta

Electrochemical and Solid-State Letters,; Vol. 13(2010)p. B130-B134

Artikel i vetenskaplig tidskrift

Proton Conductivity in Mixed B-Site Doped Perovskite Oxide BaZr[sub 0.5]In[sub 0.25]Yb[sub 0.25]O[sub 3 - delta]

Journal of the Electrochemical Society,; Vol. 157(2010)p. B1819-B1824

Artikel i vetenskaplig tidskrift

Pyrochlore to Fluorite Transition: The Y2(Ti1-xZrx)2O7 (0.0 ≤ x ≤ 1.0) System

Chemistry of Materials,; Vol. 24(2012)p. 4294-4300

Artikel i vetenskaplig tidskrift

Ämneskategorier

Oorganisk kemi

Keramteknik

Materialkemi

Annan materialteknik

Styrkeområden

Energi

Materialvetenskap

ISBN

978-91-7385-884-7

Doktorsavhandlingar vid Chalmers tekniska högskola. Ny serie: 0346-718X

10:an, Kemivägen 10

Opponent: Nikolaos Bonanos, Senior Scientist,Department of Energy Conversion and Storage, Technical University of Denmark, Denmark.

Mer information

Skapat

2017-10-07