• 한국세라믹학회지
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• 제53권5호
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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.

• 한국세라믹학회지
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• 제53권3호
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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.

• 한국세라믹학회지
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• 제38권11호
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• pp.993-999
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• 2001

Bao를 첨가한 perovskite 구조 LaSc $O_3$의 생성상과 proton 전도에 대해 연구하였다. La자리에 $Ba^{2+}$를 40 at% 첨가한 조성에서는 입방정 단일상이 생성된 반면, $Ba^{2+}$를 30 at% 이하로 첨가한 조성은 입방정과 사방정이 생성되었다. $N_2$분위기에서 $650^{\circ}C$ 이상의 온도에서는 주로 산소이온에 의한 전도를 나타내었고, 그 이하의 온도에서는 wet 분위기에서 proton 전도가 관찰되었다. 모든 조성의 물질은 30$0^{\circ}C$ 이하에서는 순수한 proton 전도체의 거동을 보였으며, proton에 의한 bulk(grain)의 전도도는 L $a_{0.6}$B $a_{0.4}$Sc $O_{2.8}$의 경우에 가장 높았다.높았다.다.

• 한국세라믹학회지
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• 제41권8호
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• pp.623-627
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• 2004

Ba가 첨가된 LaBaGa $O_4$ 층상 perovskite의 생성상과 전도거동에 대해 고찰하였다. LaBaGa $O_4$의 La-site에 20at% 이하의 $Ba^{2＋}$ 이온을 첨가한 조성은 $K_2$Ni $F_4$구조 사방정 단일상을 형성하였다. 건조분위기에서 L $a_{0.8}$B $a_{1.2}$G $a_{3.9}$는 높은 산소분압영역에서 산소이온전도와 hole(p-type)전도의 혼합전도를 나타내었다. 수증기분위기에서는 수증기가 산소빈자리로 유입되어 proton전도가 발생되었으며, 온도가 낮아질수록 총전도에 대한 proton 전도도의 기여가 증가하여 35$0^{\circ}C$ 이하의 온도에서는 proton 전도가 지배적인 전도를 나타내었다. Proton 전도에 대한 활성화 에너지는 0.72 eV였다.

• 한국세라믹학회지
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• 제47권5호
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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.

• 전기화학회지
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• 제6권2호
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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.

• 한국세라믹학회지
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• 제39권7호
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• pp.635-641
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• 2002

고온 프로톤전도체인 $Y_2O_3$가 도핑된 $SrZrO_3$에 대하여 전기전도도의 가스 분위기 및 온도 의존도를 impedance spectroscopy로 측정하였다. 수소의 용해는 산소가 공존할 때 더 큰 열역학적 추진력을 갖게 되어 결과적으로 수증기 형태로 결정 속으로 유입되며, 프로톤전도도는 ${P_w}^{1/2}$ (수증기분압)에 의존하여 증가하였다. 순수 수소 분위기에서의 수소의 용해반응 $H_2(g)=2H_{i}$ +2e'은 전자가 산소이온공공에 trapping됨에 따른 열역학적 활동도의 감소에 의해 반응의 추진력이 커지며 그 결과 저온에서는 아르곤 분위기에서 보다 높은 전기전도도를 나타내었다. 전기전도도의 활성화에너지는 $600~900^{\circ}C$ 온도범위의 아르곤분위기에서 50kJ/mo1로 문헌에 나타난 프로톤전도도의 그것과 비슷한 크기를 나타냈다. 프로톤전도도의 입계저항은 10% 도핑한 경우 $700^{\circ}C$ 이하의 저온에서 현저하게 나타났다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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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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• 제5권3호
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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.

• 한국세라믹학회:학술대회논문집
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• 한국세라믹학회 2003년도 춘계총회 및 연구발표회 초록집
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• pp.201.2-201
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• 2003