NDLI: Proton conduction in non-doped and acceptor-doped metal pyrophosphate (MP<sub>2</sub>O<sub>7</sub>) composite ceramics at intermediate temperatures

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Journal of Materials Chemistry Vol - 22 Issue - 8

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Proton conduction in non-doped and acceptor-doped metal pyrophosphate (MP₂O₇) composite ceramics at intermediate temperatures

Content Provider	Royal Society of Chemistry (RSC)
Author	Shen, Yanbai Sato, Yousuke Nishida, Masakazu Kanematsu, Wataru Hibino, Takashi
Copyright Year	2012
Abstract	Proton conductors capable of operating in the temperature range of 100–600 °C have received great interest for many application areas such as fuel cells, sensors, and electrolyzers; however, very few materials that can satisfy these demands have been reported to date. Here, we report a promising candidate for a solid electrolyte in intermediate-temperature electrochemical devices. First, MP2O7–MO2 composite ceramics (M = Sn, Si, Ti, and Zr) were prepared by reacting a porous MO2 substrate with an 85% H3PO4 solution at 600 °C. Although all the tested MO2 could react with H3PO4 to form the corresponding metal pyrophosphate layers on the surfaces of the exterior and interior substrate, the extent of MP2O7 growth in the obtained samples and their relative density were strongly dependent on the M species. These factors were the best for the SnP2O7–SnO2 composite ceramic, yielding the highest electrical conductivity in the temperature range of interest. Next, different low valence cations (cation = Mg2+, Sc3+, Ga3+, Y3+, In3+, La3+, Sm3+, Eu3+, and Gd3+) were doped into the SnP2O7–SnO2 composite ceramic. The most positive effect on the electrical conductivity was observed when Sm3+ was used as the dopant; the electrical conductivity of this sample was approximately one order of magnitude higher than that of the non-doped sample, especially at low temperatures below 250 °C. Fourier transform infrared (FTIR) and proton magic angle spinning (MAS) nuclear magnetic resonance (NMR) analyses revealed that the quantity of protons incorporated in the SnP2O7 layer and their mobility were increased by the doping of Sm into the composite ceramic. As a consequence, the electrical conductivity of the Sm-doped SnP2O7–SnO2 composite ceramic reached ∼10−2 S cm−1 in the temperature range of 100–600 °C. Proton conduction in this sample was also investigated by various electrochemical techniques. The protons function as the predominant charge carrier in the sample, and the proton transport number was almost unity in both static and dynamic conditions.
Starting Page	3973
Ending Page	3981
Page Count	9
File Format	HTM / HTML PDF
ISSN	09599428
Volume Number	22
Issue Number	9
Journal	Journal of Materials Chemistry
DOI	10.1039/c2jm15335a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Proton Fourier Electrolyte Electrochemistry Zirconium Pyrophosphate Electrical resistivity and conductivity Ion Dopant Fourier transform Infrared spectroscopy Hydrogen Magic angle spinning Nuclear magnetic resonance Charge carrier
Content Type	Text
Resource Type	Article
Subject	Chemistry Materials Chemistry

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