Thermoelectricity in Confined Liquid Electrolytes.

The electric field in an extended phase of a liquid electrolyte exposed to a temperature gradient is attributed to different thermophoretic mobilities of the ion species. As shown herein, such Soret-type ion thermodiffusion is not required to induce thermoelectricity even in the simplest electrolyte if it is confined between charged walls. The space charge of the electric double layer leads to selective ion diffusion driven by a temperature-dependent electrophoretic ion mobility, which-for narrow channels-may cause thermovoltages larger in magnitude than for the classical Soret equilibrium.