Thermoelectric Power by the Diffusion of Protons in a Nanoporous Structure
Michael A. Reznikov
Physical Optics Corporation, 20600 Gramercy Place, Torrance, CA 90501, U.S.A.
The work presents the model for the ionic thermoelectric phenomenons, which is basedon the consideration of Grotthuss, hopping mechanism for the proton conductivity. The Seebeck coefficient and figure of merit are estimated in good agreement with experimental data.
Most solid-state thermoelectric (TE) generators, based on the Seebeck effect, suffer from power loss due to the parasitic flow of heat. While low-dimensional structures, such as quantumwells, superlattices, quantum wires, and quantum dots, offer new ways to decrease the thermal(phonon) conductivity while improving the electric conductivity [1,2], their energy conversionefficiency is relatively low and fabrication is very expensive. Therefore, there is a need for newTE materials for waste heat recovery and electricity generation that have a high figure of merit(ZT) and the potential for large-scale production at costs competitive with conventionaltechnologies, considering the entire system over its lifetime.It is known that the receptors of marine sharks and skates (rays), which contain theextracellular hydrogel, are the most exquisite sensors of thermal fluctuations [3-5]. Wedemonstrated that these ionic structures can be mimicked by natural and synthetic gels , andexhibit very high TE voltage, a few mV/K at low, room temperatures. These materials currentlyare commercially available due to progress in fuel cell technology, where they are used as protonconductive membranes.
Theoretical models for thermoelectricity [7, 8] based on electronic structure are presumably inappropriate for proton-conductive substances. First of all, the density of mobileions depends much less on the temperature than the density of free electrons. Second, themobility of ions is very sensitive to temperature, due to the thermodiffusion mechanism of charge transfer .Dynamic capturing and release of protons is the base mechanism of protonic transfer innature. A mechanism for proton mobility was suggested to be comprised of the cyclicisomerization between the two forms of protonated water, H
, which is coupled tohydrogen-bond dynamics in the second solvation shell of the H
. The formation of a highfraction of pore bulk water in proton exchange membranes (PEMs) is desirable for highconductivity because of the dominance of the Grotthuss diffusion mechanism in conductivity,which occurs in bulk water rather than at the surface. The Grotthuss mechanism is the proton-hopping-mechanism where each oxygen atom simultaneously passes and receives a singlehydrogen atom. . Due to interaction with the wall of a pore, localized water molecules createdeeper traps for protons than those in the bulk water. This is illustrated in figure 1 (courtesy of ).