Experimental demonstration of the path- and time-dependence of open-circuit voltage of galvanic cells involving a multinary compound under multiple chemical potential gradients

摘要

It was mathematically predicted and numerically demonstrated [Yoo and Martin, Phys. Chem. Chem. Phys. 12 (1210) 14699] that the open-circuit voltage U of a galvanic cell, involving a multinary compound with multiple ionic carriers subjected to multiple chemical potential differences, be path- and time-dependent, unlike a cell involving a pure binary or a multinary compound with a single type ionic carrier. The path- and time-dependence of U is now experimentally demonstrated with a galvanic cell,μ~(O2)′, μ~(H2)O′|SrC~(e0.95)Y~(b0.05)O3 _(-δ)|μ~(O2)″,μ~(H2)O″involving a proton-conducting, mixed ionic electronic conductor, e.g., SrCe _(0.95)Yb_(0.05)O_(3-δ) with H~+ and O~(2-) as ionic carriers subjected to the chemical potential differences of oxygen and water. The results are compared with a cell involving a multinary Zr0.84Y0.16O1.92 but with a single type ionic carrier O~(2-),μ~(O2′),μ~(H2)O′|Z ~(r0.84Y0.16O1.92)|μ~(O2)″, μ~(H2)O″where U is path-independent in any case and time-independent as long as the electrode equilibria prevail. Implications of the path- and time-dependence of U are discussed.