• Journal of the Korean Ceramic Society
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• v.51 no.4
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• pp.248-259
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• 2014

Acceptor-doped cerium pyrophosphates have shown significant proton conductivity of > $10^{-2}Scm^{-1}$ in the range of $100-300^{\circ}C$ and are considered promising candidates for use as electrolytes in proton-conducting, ceramic electrolyte fuel cells (PCFCs). But, cerium pyrophosphates themselves do not have structural protons, and protons incorporate into their material bulk only as impurities on exposure to a hydrogen-containing atmosphere. However, proton incorporation and proton conduction in these materials are expected to be affected by factors such as the nature (ionic size and charge) and concentration of the aliovalent dopant, processing history (synthesis route and microstructure), and the presence of residual phosphorous phosphate ($P_mO_n$) phases. An exact understanding of these aspects has not yet been achieved, leading to large differences in the magnitude of proton conductivity of cerium pyrophosphates reported in various studies. Herein, we systematically address some of these aspects, and present an overview of factors affecting proton conductivity inacceptor-doped $CeP_2O_7$.

• Journal of the Korean Ceramic Society
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• v.45 no.11
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• pp.694-700
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• 2008

Proton conducting oxides based on the $BaCe_{0.9}M_{0.1}O_{3-{\delta}}$ (M = La, AL) were tested for the alternative electrolyte materials of fuel cell. The power density for single cell of Air |Pt| $BaCe_{0.9}M_{0.1}O_{3-{\delta}}$ |Pt| $H_2(3%H_2O)$ system was maximum $0.04W/cm^2$ at $1000^{\circ}C$. In this system, proton transport number was proved to depend on the lattice parameters and the distortion of $CeO_6$ octahedral as a function of the ionic radii of acceptor ions. This proton conducting oxide system requires developing the new electrode materials for application.

• Journal of the Korean Ceramic Society
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• v.53 no.5
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• pp.506-510
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• 2016

The eutectic melt of BaO-CuO flux is known to be a potential sintering aid for $Ba(Zr,Y)O_3$ (BZY) electrolyte for proton-conducting ceramic fuel cells (PCFCs). A density of BZY higher than 97% of theoretical density can be achieved via sintering at $1300^{\circ}C$ for 2 h using a flux composed of 28 mol% BaO and 72 mol% CuO. In the present study, chemical and structural evolution of BaO-CuO flux throughout the sintering process was investigated. An intermediate holding step at $1100^{\circ}C$ leads to formation of various impurity compounds such as $BaCuO_{1.977}$, $Ba_{0.92}Cu_{1.06}O_{2.28}$ and $Cu_{16}O_{14.15}$, which exhibit significantly larger unit cell volumes than the matrix. The presence of such secondary compounds with large lattice mismatch can potentially lead to mechanical failure. On the other hand, direct heating to the final sintering temperature produced CuO and $Cu_2O$ as secondary phases, whose unit cell volumes are close to that of the matrix. Therefore, the final composition of the flux is strongly affected by the thermal history, and a proper sintering schedule should be used to obtain the desired properties of the final product.

• Journal of the Korean Ceramic Society
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• v.56 no.1
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• pp.91-97
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• 2019

The effect of different Ni-containing additives on the sintering behavior and electric conductivity of the proton conducting electrolyte $BaCe_{0.35}Zr_{0.5}Y_{0.15}O_{3-{\delta}}$ (BCZY5) was investigated. Ni-doped, NiO-added, and $BaY_2NiO_5$(BYN)-added (all 4 mol%) BCZY5 samples were prepared by the solid state synthesis method and sintered at $1400^{\circ}C$ for 6 h. Among the three samples, the onset of densification was observed at the lowest temperature for NiO-added BCZY5, which is attributed to the formation of an intermediate phase at a low melting temperature. The BYN-added sample, where no consumption of the constitutional elements of the electrolyte was expected during sintering, exhibited the highest electrical conductivity whereas the doped sample had the lowest conductivity. The electrical conductivities at $500^{\circ}C$ under humid argon atmosphere were measured to be 2.0, 4.8, and $6.2mS{\cdot}cm^{-1}$ for Ni-doped and NiO- and BYN-added samples, respectively.

• Journal of the Korean Ceramic Society
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• v.42 no.2 s.273
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• pp.77-80
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• 2005

A series of proton conductive composite membranes based on poly(vinyl alcohol) and phosphosilicate gels powders were successfully prepared. The proton conductivity of these composite was attributed to the phosphosilicate gel, which derived from tetraethoxysilane and phosphoric acid by sol-gel process at a molar ratio of P/Si = 1.5. The proton conductivity increased with increasing both the content of phosphosilicate gel and relative humidity. Temperature dependence of conductivity showed a Vogel-Tamman-Fulcher type behavior, indicating that proton was transferred through a liquidlike phase formed in micropores of phosphosilicate gel. The high conductivity of 0.065 S/cm with a membrane containing 60 wt$\%$ of the gel was obtained at $60^{\circ}C$ at $90\%$ relative humidity.

• Journal of the Korean Ceramic Society
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• v.42 no.1
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• pp.50-55
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• 2005

New fast proton-conducting organic-inorganic nanocomposite membranes were successfully fabricated using polymer matrix obtained through proper oxidation of thiol ligands in (3-Mercaptopropyl) trimethoxysilane (MPTS) and hydrolysis/condensation reaction of (3-glycidoxypropyl) trimethoxysilane (GPTS). The obtained nanocomposite membranes showed relatively hirh proton-conductivity over $10^{-2}S/cm$ at $ 25^{circ}C$. The proton conductivities of the fabricated composite membranes increased up to $3.6{\times}10^{-1}$ S/cm cm by increasing temperature and relative humidity to $70^{circ}C$ and 100 $100RH\%$. The high proton conductivity of the composites Is due to the proton conducting path through the GPTS-derived 'pseudo-polyethylene oxide 'network in which sulfonic acid ligands work as a proton donor.

• Applied Chemistry for Engineering
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• v.24 no.4
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• pp.337-343
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• 2013

Membrane reactors have been showing a promising future and attracted increasing attention in the scientific community as they possess advantages in terms of enhanced catalytic activity and selectivity, combination of processes (reaction and separation), simplicity in process design, and safety in operation. In particular, solid electrolyte membrane reactor principles are realized in fuel cells, electrolyzers and reactors for hydrogenation of carbon dioxide and other economically viable reactions. In this review, as a young generation of ion conducting materials, high temperature proton conductors are discussed in terms of the current status of material development and their various applications.

• Journal of the Korean Ceramic Society
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• v.55 no.4
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• pp.358-363
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• 2018

To improve the polarization property of cathodes, which is the main factor limiting the performance of protonic ceramic fuel cells (PCFCs), $K_2NiF_4-type$ $Pr_2NiO_{4+{\delta}}$, which is expected to exhibit a triple conducting property (proton, oxygen ion, and hole conductions) was applied to PCFCs and its properties were investigated. Low-temperature microwave heat-treatment was used to achieve both sufficient interface adhesion between the electrolyte and the cathode layers and suppression of the secondary phase formation due to migration of elements such as barium and cerium. Through this fabrication method, a high performance of $0.82W{\cdot}cm^{-2}$ and low ohmic resistance of $0.06{\Omega}{\cdot}cm^2$ were obtained in an $Ni-BaCe_{0.55}Zr_{0.3}Y_{0.15}O_{3-{\delta}}$ | $BaCe_{0.55}Zr_{0.3}Y_{0.15}O_{3-{\delta}}$ | $Pr_2NiO_{4+{\delta}}$ single cell at $650^{\circ}C$. This result verifies that the $K_2NiF_{4+{\delta}}-type$ cathode shows good chemical compatibility which, in turn, will make it a potent candidate as a PCFC cathode.

• Journal of the Korean Ceramic Society
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• v.51 no.4
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• pp.271-277
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• 2014

To overcome the limitations of the solid oxide fuel cells (SOFCs) due to the high temperature operation, there has been increasing interest in proton conducting fuel cells (PCFCs) for reduction of the operating temperature to the intermediate temperature range. In present work, the perovskite $BaCe_{0.85-x}Zr_xY_{0.15}O_{3-\delta}$ (BCZY, x = 0.1, 0.3, 0.5, and 0.7) were synthesized via solid state reaction (SSR) and adopted as an electrolyte materials for PCFCs. Powder characteristics were examined using X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Brunauer, Emmett and Teller (BET) surface area analysis. Single phase BCZY were obtained in all compositions, and chemical stability was improved with increasing Zr content. Anode-supported cell with $Ni-BaCe_{0.55}Z_{0.3}Y_{0.15}O_{3-\delta}$ (BCZY3) anode, BCZY3 electrolyte and BCZY3-$Ba_{0.5}Sr_{0.5}Co_{0.8}Fe_{0.2}O_{3-\delta}$ (BSCF) composite cathode was fabricated and electrochemically characterized. Open-circuit voltage (OCV) was 1.05 V, and peak power density of 370 ($mW/cm^2$) was achieved at $650^{\circ}C$.

• Journal of Electrochemical Science and Technology
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• v.9 no.3
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• pp.212-219
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• 2018

Perovskite type ceramic membranes which exhibit dual ion conduction (proton and oxygen ion conduction) can permeate water and can aid solving operational problems such as temperature gradient and carbon deposition associated with a working solid oxide fuel cell. From this point of view, it is crucial to reveal water transport mechanism and especially the nature of the surface sites that is necessary for water incorporation and evolution. $BaCe_{0.8}Y_{0.2}O_{3-{\alpha}}$ (BCY20) was used as a model proton and oxygen ion conducting membrane in this work. Four different catalytically modified membrane configurations were used for the investigations and water flux was measured as a function of temperature. In addition, CO was introduced to the permeate side in order to test the stability of membrane against water and $CO/CO_2$ and post operation analysis of used membranes were carried out. The results revealed that water incorporation occurs on any exposed electrolyte surface. However, the magnitude of water permeation changes depending on which membrane surface is catalytically modified. The platinum increases the water flux on the feed side whilst it decreases the flux on the permeate side. Water flux measurements suggest that platinum can block water permeation on the permeate side by reducing the access to the lattice oxygen in the surface layer.