Solid State Ionics, Vol.181, No.11-12, 545-550, 2010
Solid-hydroxide-proton conductors in new electrochemical cells "hydrogenated metal-protonics"
Recent studies have revealed that electrochemical activity of solid-state cells is formed by a hydrogenated metal (Pd or Ti) and one of the hydroxide compounds KOH center dot H2O, KOH + NaOH, and KOH + KOH center dot H2O (Baikov et al., 2007-2008). Two equimolar eutectics, KOH + NaOH and KOH + KOH center dot H2O, and chemical compound KOH center dot H2O are solid superprotonics within the temperature intervals of 360-458, 360-370 and 320-420 K, respectively: their conductivities are above 1 mS/cm, and the activation energies are below 0.4 eV. The anomalies observed in the behavior of the conductivity with temperature correlate with those in the heat capacity in the region of 360 +/- 1 K. The isotopic effect (H double left right arrow D) of the protonic conductivity for KOH center dot H2O and the high-temperature form of KOH + NaOH is, on the average, 1.4 +/- 0.15. The solid monohydrate NaOH center dot H2O is a protonic (0.4 mS/cm) in the 300-335 K region with an activation energy of approximate to 0.3 eV. The significance of self-organized microheterogeneity of the solid eutectic KOH + NaOH for high conductivity is discussed. The electrochemical cells Pd vertical bar KOH center dot H2O vertical bar C, PdHx vertical bar KOH + NaOH vertical bar PdOy and Ti vertical bar KOH center dot H2O vertical bar C can operate as low-power rechargeable batteries producing an emf of -1.3 V within the temperature region of 360-420 K. (c) 2010 Elsevier B.V. All rights reserved.
Keywords:Solid hydroxides;Superprotonic conductivity;Phase transitions;Isotopic effects;Self-organized microheterogeneity;Electrochemical cells "solid hydroxide-protonic conductor-hydrogenated metal"