• Journal of the Korean Ceramic Society
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• v.53 no.5
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• pp.521-528
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• 2016

Kinetic Monte Carlo (KMC) and graph searches show that proton conduction limiting barriers and trajectories in $BaZr_{0.875}Y_{0.125}O_3$ are affected by the presence of other protons. At 1000 K, KMC limiting conduction barriers increase from 0.39 eV to 0.45 eV as the proton number is increased. The proton-proton radial distribution begins to rise at $2{\AA}$ and peaks at $4{\AA}$, which is half the distance expected, based on the proton concentration. Density functional theory (DFT) calculations find proton/proton distances of 2.60 and $2.16{\AA}$ in the lowest energy two-proton configurations. A simple average of the limiting barriers for 7-10 step periodic long range paths found via graph theory at 1100 K shows an increase in activation barrier from 0.32 eV to 0.37 eV when a proton is added. Both KMC and graph theory show that protons can affect each other's pathways and raise the overall conduction barriers.

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.301-305
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• 2016

We investigate proton conduction in a nonstoichiometric ${\Sigma}3$ $BaZrO_3$ (210)[001] tilt grain boundary using density functional theory (DFT). We employ the space charge layer (SCL) and structural disorder (SD) models with the introduction of protons and oxygen vacancies into the system. The segregation energies of proton and oxygen vacancy are determined as -0.70 and -0.54 eV, respectively. Based on this data, we obtain a Schottky barrier height of 0.52 V and defect concentrations at 600K, in agreement with the reported experimental values. We calculate the energy barrier for proton migration across the grain boundary core as 0.61 eV, from which we derive proton mobility. We also obtain the proton conductivity from the knowledge of proton concentration and mobility. We find that the calculated conductivity of the nonstoichiometric grain boundary is similar to those of the stoichiometric ones in the literature.

• Journal of the Korean Ceramic Society
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• v.38 no.11
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• pp.993-999
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• 2001

Phase formation and proton conduction in BaO doped LaSc $O_3$with perovskite structure were studied. L $a_{0.6}$B $a_{0.4}$Sc $O_{2.8}$, viz. 40at% $Ba^{2+}$ ion doped composition, showed a single cubic phase, while the other compositions doped less than 30 at% $Ba^{2+}$ ion showed the cubic phase and the orthorhombic one. Above $650^{\circ}C$ oxygen ion conduction was dominant in $N_2$atmosphere and below this temperature proton conduction was observed in wet atmosphere. All compositions were found to be the pure proton conductors below 30$0^{\circ}C$. The proton conductivity (bulk) of L $a_{0.6}$B $a_{0.4}$Sc $O_{2.8}$ was higher than those of any other composition.osition.ion.

• Journal of the Korean Ceramic Society
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• v.41 no.8
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• pp.623-627
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• 2004

Phase formation and electrical conduction behavior of Ba-doped LaBaGa $O_4$ layered perovskite were studied. Orthorhombic single phase of $K_2$Ni $F_4$-type structure was observed for the composition range of 0$\leq$x$\leq$0.2 in the La$\_$1＋x/Ba$\_$1＋x/Ga $O_4$$\_$4-$\delta$/ system by X-ray analysis. In the dry atmosphere, La$\_$0.8/Ba$\_$1.2/Ga$\_$3.9/ exhibited mixed conduction of oxygen ion and hole (p-type) at high p( $O_2$). However, in water vapor containing atmosphere, it showed proton conduction due to the incorporation of water into oxygen vacancies. As the temperature decreased, the contribution of proton conductivity to the total conduction increased and proton conduction was dominant below 350$^{\circ}C$. The activation energy for proton conduction was calculated as 0.72 eV.

• Journal of the Korean Ceramic Society
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• v.47 no.5
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• pp.474-478
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• 2010

We studied the energy barrier for proton conduction with volume variation in $BaZrO_3$ using a first principles study to investigate an optimum volume for the proton conduction. The volume increase of $BaZrO_3$ was expected to decrease the energy barrier for proton rotation and to increase that for proton transfer, and these trends could be extrapolated when the volume was decreased. However, the energy barriers for the proton transfer with the volume decrease were increased, while all the other energy barriers varied as expected. We could explain this unexpected behavior by the bent Zr-O-Zr structure, when the volume was decreased.

• Journal of the Korean Electrochemical Society
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• v.6 no.2
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• pp.141-144
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• 2003

Proton conducting polymeric gels as the electrolytes of electrochemical capacitors have been prepared by two different methods: 1) swelling a polymethacrylate-based polymer matrix in aqueous solutions of inorganic and organic acids, and 2) polymerizing complexes of anhydrous acids and prepolymers with organic plasticizer. The FT-IR spectra strongly suggest that the carbonyl groups in the polymer matrix interact with protons from the doped acids. High ionic (proton) conductivity in the range of $6\times10^{-4}-4\times10^{-2}\;S\;cm^{-1}$ was obtained at room temperature for the aqueous gels. The non-aqueous polymer complexes showed rather low ionic conductivity, but it was about $10^{-3}\;S\;cm^{-1}\;at\;70^{\circ}C$ for the $H_3PO_4$ doped polymer electrolyte. The mechanisms of ion (proton) conduction in the polymeric systems are discussed.

• Journal of the Korean Ceramic Society
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• v.39 no.7
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• pp.635-641
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• 2002

Electrical conduction of $SrZrO_3$ doped with $Y_2O_3$ was measured as a function of gas atmosphere and temperature by impedance spectroscopy. Hydrogen dissolution, due to an enhanced driving force in the presence of oxygen, results in protonation by water incorporation. Proton conductivity increased with water vapor pressure, ${P_w}^{1/2}$. In the pure hydrogen atmosphere, the dissolution of hydrogen,$H_2(g)=2H_{i}$ +2e', is supposed to be driven by a reduced activity of electrons, ascribable to their trapping in oxygen vacancies. The activation energy of electrical conductivity was 50 kJ/mol, in wet argon atmosphere in the temperature range of $600~900^{\circ}C$, similar to those reported for proton conduction in the literature. Grain boundary effect in proton conduction was substantial in the 10% doped case at temperatures lower than $700^{\circ}C$.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.282-285
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• 2009

This study presents preparation and characterization of composite membranes based on ionic liquids. The ionic liquids act as water in sulfonated membranes. On the behalf of ionic conduction through ionic liquid inside the membranes, non-aqueous membranes showed Arrenhius dependence on temperature with no external humidification. It was implied that hopping mechanism of proton was dominant in the ionic liquid based membranes. In addition, small angle X-ray (SAXS) studies provided the information on morphology of ionic clusters formed by the interaction between sulfonic acid groups of the polymers and ionic liquids. The SAXS spectra showed matrix peaks, ionomer peaks and Prodo's law for Nafion based composite membranes and only matrix peaks for hydrocarbon based ones. However, ionic conductivity and atomic force microscopy (AFM) images showed the clear formation of ionic clusters of the hydrocarbon based composite membranes. It implies for ionic liquid based high temperature membranes that it is important to use sulfonated polymers as solid matrix of ionic liquid which can form clear ionic clusters in SAXS spectra.

• The Korean Journal of Ceramics
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• v.5 no.3
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• pp.288-295
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• 1999

Partial conductivities contributed by electron holes, oxygen ions, and protons were caluclated in $SrZr_{0.95}Y_{0.05}O_{2.975}$, using the reported formulae derived from the defect chemistry of HTPCs. Required parameters were obtained from the graphical analysis of total conductivity variation against partial pressure of water vapor and oxygen. Predicted overall conductivities showed a reasonable agreement with experimental measurements. The conductivity of the material showed a linear increase with square root of the water vapor pressure. This increase was due to proton conduction in an almost pure ionic conductivity. The calculation of partial conductivities at $800^{\circ}C$ resulted in an almost pure ionic conductivity at $P_{02}=10^{-10}$ atm and a predominant hole conductivity at $P_{02}=10^{-10}$ atm. Pure proton conduction was not expected at this temperature, contrary to the earlier reports. Discussions were made in relation with reported thermodynamic data and defect structure of the material. It was shown that from the total conductivity dependence on water vapor pressure, the pure ionic conductivity at low oxygen partial pressures could be separated into protonic and oxygen ionic conductivity in $ZrO_2$-based HTPCs.

• Proceedings of the Korean Ceranic Society Conference
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• 2003.04a
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• pp.201.2-201
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• 2003