, Volume 43, Issue 4, pp 398-409

Anionic high-temperature conduction in single crystals of nonstoichiometric phases R1 − y M y F3 − y (R = La-Lu, M = Ca, Sr, Ba) with the tysonite (LaF3) structure

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Abstract

Electrophysical properties of single crystals of nonstoichiometric phases R1 − y M y F3 − y , where R = La-Lu, M = Ca, Sr, or Ba, with the tysonite (LaF3) structure, which are present in a metastable state after being grown and cooled, are measured in the temperature interval extending from 300 to 1073 K. It is discovered that, during a sufficiently long high-temperature investigation, solid solutions R1 − y Ca y F3 − y , where R = Tb, Dy, or Ho, undergo irreversible variations in the phase composition in the temperature region 723 to 823 K. This level of temperatures, which correspond to partial decomposition of phases R1 − y Ca y F3 − y with the rare-earth elements of the end of the period, lies above the temperatures to which the fluoride solid electrolytes are usually heated when used in solid-state electrochemical devices. The temperature and concentration dependences of the phases’ electroconduction are explained in the framework of the vacancy mechanism of anionic transport.

Original Russian Text © N.I. Sorokin, B.P. Sobolev, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 4, pp. 420–431.
The paper is dedicated to the memory of Prof. M.W. Breiter, formerly of the Vienna Technical University, Austria.