• 한국세라믹학회지
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• 제51권4호
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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 $CeP_2O_7$.

• 한국세라믹학회지
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• 제45권11호
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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.

• 한국세라믹학회지
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• 제53권5호
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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.

• 한국세라믹학회지
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• 제56권1호
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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.

• 한국세라믹학회지
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• 제42권2호
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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.

• 한국세라믹학회지
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• 제42권1호
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• pp.50-55
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• 2005

(3-Mercaptopropyl) trimethoxysilane(MPTS)의 thoil기(-SH)의 적절한 산화 및 (3-glycidoxypropyl) trimethooxysilane(GHS)와의 수화/중축합 반응을 통하여 얻어진 고분자 기질을 사용하여 새로운 고 프로톤 전도성 유기-무기 나노복합막을 성공적으로 합성하였다. 합성된 나노복합막으로부터 얻어진 프로톤 전도도는 $25^{circ}C$에서 $10^{-2} S/cm$ 이상의 높은 값을 나타내었으며, 온도와 상대습도를 $70^{circ}C$와 $100RH\%$로 증가시킴에 따라 전도도는 $3.6{\times}10^{-1}$ S/cm까지 증가하였다. 복합체의 높은 프로톤 전도도는 MPTS 말단의 thiol의 산화에 의해 얻어지는 아황산기$(-SO_{3}^{-})$가 프로톤 donor로서 작용하고, GHS로부터 유도된 'pseudo polyethylene oxide' 네트워크가 프로톤의 전도 path로 작용하고 있음을 나타낸다.

• 공업화학
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• 제24권4호
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• pp.337-343
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• 2013

멤브레인 반응기는 멤브레인과 반응기를 결합하여 반응과 분리의 단위공정을 하나로 결합함으로써 전체공정을 단순화하고 반응효율을 높이고자 하는 혁신 기술로써, 멤브레인을 이용한 생성물의 선택적 제거를 통해 열역학적 평형을 뛰어넘는 전환율, 부반응물 생성 억제에 의한 반응 효율 및 선택성을 향상시킬 수 있다. 특히 이온전도성 세라믹을 이용한 멤브레인 반응기는 연료전지의 개발, 고순도 산소/수소의 분리/정제, 이산화탄소의 전환 및 다양한 화학제품제조에 까지 응용될 수 있기 때문에 시장의 확대와 더불어 크게 발전할 수 있을 것으로 기대된다. 본 총설에서는 수소이온 전도성 세라믹 멤브레인 반응기에 대한 연구동향과 다양한 응용분야 및 향후 전망 등에 고찰해 보고자 한다.

• 한국세라믹학회지
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• 제55권4호
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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.

• 한국세라믹학회지
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• 제51권4호
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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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• 제9권3호
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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.