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Title: Characterization and electrochemical properties of P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses as proton conducting electrolyte

Abstract

The H{sub 2}/O{sub 2} fuel cell based on the proton conducting P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses was prepared by sol-gel technique. Structural characterization were carried out using X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance ({sup 31}P MAS NMR), N{sub 2} adsorption-desorption analysis, differential thermal analysis (DTA) and thermal gravimetric analysis (TGA) and impedance measurements. The absorption bonds of Si-O-Si, Si-O-P and Si-O-Zr were observed in the P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses which were heat treated at 600 deg. C. A sample (5P{sub 2}O{sub 5}-4ZrO{sub 2}-91SiO{sub 2}, mol%) was selected as the electrolyte for the H{sub 2}/O{sub 2} fuel cell test and yielded the maximum power density value of 8.5 mW/cm{sup 2} using electrochemical measurements at 30 deg. C under relative humidity atmosphere.

Authors:
 [1];  [2];  [2]
  1. Department of Material Science and Engineering, Nagoya Institute of Technology, Showa, Nagoya 466-8555 (Japan). E-mail: ptuma2002@yahoo.co.in
  2. Department of Material Science and Engineering, Nagoya Institute of Technology, Showa, Nagoya 466-8555 (Japan)
Publication Date:
OSTI Identifier:
20891665
Resource Type:
Journal Article
Resource Relation:
Journal Name: Materials Research Bulletin; Journal Volume: 41; Journal Issue: 4; Other Information: DOI: 10.1016/j.materresbull.2005.10.002; PII: S0025-5408(05)00377-6; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTION SPECTROSCOPY; DIFFERENTIAL THERMAL ANALYSIS; ELECTROCHEMISTRY; ELECTROLYTES; FOURIER TRANSFORM SPECTROMETERS; FUEL CELLS; GLASS; HEAT TREATMENTS; INFRARED SPECTRA; NANOSTRUCTURES; PHOSPHATES; PHOSPHORUS 31; PHOSPHORUS OXIDES; POWER DENSITY; SILICON OXIDES; SOL-GEL PROCESS; THERMAL GRAVIMETRIC ANALYSIS; X-RAY DIFFRACTION; ZIRCONIUM OXIDES

Citation Formats

Uma, T., Nakao, A., and Nogami, M. Characterization and electrochemical properties of P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses as proton conducting electrolyte. United States: N. p., 2006. Web. doi:10.1016/j.materresbull.2005.10.002.
Uma, T., Nakao, A., & Nogami, M. Characterization and electrochemical properties of P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses as proton conducting electrolyte. United States. doi:10.1016/j.materresbull.2005.10.002.
Uma, T., Nakao, A., and Nogami, M. Thu . "Characterization and electrochemical properties of P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses as proton conducting electrolyte". United States. doi:10.1016/j.materresbull.2005.10.002.
@article{osti_20891665,
title = {Characterization and electrochemical properties of P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses as proton conducting electrolyte},
author = {Uma, T. and Nakao, A. and Nogami, M.},
abstractNote = {The H{sub 2}/O{sub 2} fuel cell based on the proton conducting P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses was prepared by sol-gel technique. Structural characterization were carried out using X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance ({sup 31}P MAS NMR), N{sub 2} adsorption-desorption analysis, differential thermal analysis (DTA) and thermal gravimetric analysis (TGA) and impedance measurements. The absorption bonds of Si-O-Si, Si-O-P and Si-O-Zr were observed in the P{sub 2}O{sub 5}-ZrO{sub 2}-SiO{sub 2} glasses which were heat treated at 600 deg. C. A sample (5P{sub 2}O{sub 5}-4ZrO{sub 2}-91SiO{sub 2}, mol%) was selected as the electrolyte for the H{sub 2}/O{sub 2} fuel cell test and yielded the maximum power density value of 8.5 mW/cm{sup 2} using electrochemical measurements at 30 deg. C under relative humidity atmosphere.},
doi = {10.1016/j.materresbull.2005.10.002},
journal = {Materials Research Bulletin},
number = 4,
volume = 41,
place = {United States},
year = {Thu Apr 13 00:00:00 EDT 2006},
month = {Thu Apr 13 00:00:00 EDT 2006}
}
  • Fast proton-conducting P{sub 2}O{sub 5}{endash}ZrO{sub 2}{endash}2SiO{sub 2} glasses were successfully prepared by the hydrolysis of metal alkoxides. The glasses obtained by heating at 150 to 400{degree}C are chemically stable and exhibit high conductivities of {approximately}10{sup 4}S/cm at room temperature, conductivities that are higher by {approximately}4 order than that of glasses containing no P{sub 2}O{sub 5}. These high conductivities were regarded as the fast proton transfer accelerated by molecular water bonded with POH groups. These glasses have a high potential for practical applications. {copyright} {ital 1997 American Institute of Physics.}
  • BaZr 0.1Ce 0.7Y 0.1Yb 0.1O 3-δ (BZCYYb) exhibits adequate protonic conductivity as well as sufficient chemical and thermal stability over a wide range of SOFC operating conditions, while layered perovskite PrBaCo 2O 5+δ (PBCO) has advanced electrochemical properties. This research fully takes advantage of these advanced properties and develops a novel protonic ceramic membrane fuel cell (PCMFC) of Ni–BZCYYb|BZCYYb|PBCO. The performance of the button cell was tested under intermediate-temperature range from 600 to 700 °C with humified H 2 (~3% H 2O) as fuel and ambient air as oxidant. The results show that the open circuit potential ofmore » 0.983 V and the maximal power density of 490 mW cm -2 were achieved at 700 °C. By co-doping barium zirconate–cerate with Y and Yb, the conductivity of electrolyte was significantly improved. The polarization processes of the button cell were characterized using the complicated electrochemical impedance spectroscopy technique. The results indicate that the polarization resistances contributed from both charge migration processes and mass transfer processes increase with decreasing cell voltage loads. However the polarization resistance induced by mass transfer processes is negligible in the studied button cell.« less
  • Fast protonic conductors were prepared in the P{sub 2}O{sub 5}-containing silicate glasses using the sol-gel method. The 5P{sub 2}O{sub 5}{center_dot}5ZrO{sub 2} {center_dot} 90SiO{sub 2} glasses, obtained by heating at 200 to 800 C, were crack-free and chemically stable and exhibited room temperature conductivities of 10{sup {minus}3} S/cm, which were higher by {approximately}5 orders of magnitude than that of the dried gel or porous silica glass. These high conductivities were regarded as the fast proton mobility accelerated by molecular water which was chemically bonded with POH groups. Fast proton-conducting solids have attracted much attention, because they have a large potential formore » use in clean energy fields, such as hydrogen gas sensors and hydrogen fuel cells.« less
  • A series of glasses based on the system 48SiO{sub 2}-(36-X) ZnO-6CaO-8SrO-2P{sub 2}O{sub 5}-XTa{sub 2}O{sub 5} with X varying from 0 mol% (Ta0) to 8 mol% (Ta4) were fabricated. The structural features as a function of Ta{sub 2}O{sub 5} content were investigated by network connectivity (NC) calculations, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The thermal properties of the glasses were obtained by performing simultaneous thermal analysis (STA). XRD showed that all compositions were predominantly amorphous, however the incorporation of tantalum pentoxide (Ta{sub 2}O{sub 5}) resulted in a small degree of crystallinity within the sample.more » Replacing ZnO with Ta{sub 2}O{sub 5} increases the glass transition, crystallization and melting temperatures. Further, Ta{sub 2}O{sub 5} incorporation results in higher thermal stability suggesting a greater glass forming tendency and the insertion of Ta in the glass network. XPS and FTIR spectroscopy revealed that Ta behaves as a glass former and that Zn has an intermediary role in the vitreous network. - Highlights: • ZnO substitution for Ta{sub 2}O{sub 5} in the glass system SiO{sub 2}-ZnO-CaO-SrO-P{sub 2}O{sub 5} is presented. • ZnO substitution results in greater glass forming tendency. • Ta{sub 2}O{sub 5} addition results in the formation of Si−O−Ta and Ta−O−Ta linkages. • Ta{sub 2}O{sub 5} addition increases the glass thermal stability. • ZnO behaves as an intermediate in this glass system.« less
  • Luminescence of phosphate glasses such as CaO⋅P{sub 2}O{sub 5} and SrO⋅P{sub 2}O{sub 5} is compared with that of phosphorus doped crystalline α-quartz and phosphosilicate glass with content 3P{sub 2}O{sub 5}⋅7SiO{sub 2}. Water and OH groups are found by IR spectra in these materials. The spectrum of luminescence contains many bands in the range 1.5 - 5.5 eV. The luminescence bands in UV range at 4.5-5 eV are similar in those materials. Decay duration in exponential approximation manifests a time constant about 37 ns. Also a component in μs range was detected. PL band of μs component is shifted to lowmore » energy with respect to that of ∼37 ns component. This shift is about 0.6 eV. It is explained as singlet-triplet splitting of excited state. Below 14 K increase of luminescence kinetics duration in μs range was observed and it was ascribed to zero magnetic field splitting of triplet excited state of the center. Yellow-red luminescence was induced by irradiation in phosphorus doped crystalline α-quartz, phosphosilicate glasses. The yellowl uminescence contains two bands at 600 and 740 nm. Their decay is similar under 193 nm laser and may be fitted with the first order fractal kinetics or stretched exponent. Thermally stimulated luminescence contains only band at 600 nm. The 248 nm laser excites luminescence at 740 nm according to intra center process with decay time constant about 4 ms at 9 K. Both type of luminescence UV and yellow were ascribed to different defects containing phosphorus. P-doped α-quartz sample heated to 550 co become opalescent. Ir spectra related to water and OH groups are changed. Photoluminescence intensity of all three bands, UV (250 nm), yellow (600 nm) and red (740 nm) strongly diminished and disappeared after heating to 660 C°. Radiation induced red luminescence of non-bridging oxygen luminescence center (NBO) appeared in crystal after heat treatment. We had observed a crystalline version of this center (l. Skuja et al, Nuclear Instruments and Methods in Physics Research B 286,159-168 (2012)). Effect of heat treatment explained as sedimentation of phosphorus in some state. Keeping of treated sample at 450-500 C° leads to partial revival of ability to create yellow luminescence center under irradiation.« less