Thermodynamics of thermoelectric phenomena and applications (Q400912)

This review reconsiders the interrelation between optimal performance and local entropy production by using the compatibility approach together with fundamental thermodynamic considerations relevant for thermoelectricity (TE). First, a historical overview of the above problem is presented. Then, the thermodynamics of thermoelectricity is derived from the classical thermodynamics of cyclic systems. Non-equilibrium thermodynamics of coupled transport processes are described using the Onsager-de Groot-Callen model. It is assumed that all non-equilibrium processes are steady-state processes, which means that a mapping of spatial variation of intensive parameters \((T, p,\dots)\) is constant over the time, or may vary very slowly compared to the microscopic relaxation time. As a result, the authors derive complete expressions for the heat flux and electrical current density in a thermoelectric material. The Onsager force-flux derivation is obtained from the laws of conservation of energy and matter, and thermoelectric coefficients are obtained from two expressions of particle and heat flux density. By using the entropy per carrier, a complete correspondence between kinetic factors and transport parameters is got. Then the consequences of the Onsager theory are obtained, leading to the expressions of heat and entropy production. The volumetric heat production is estimated from the total energy flux, and the total entropy production is given by the summation of the force-flux products. The review summarizes thermoelectric applications (thermoelectric generator, cooler and heater). It is shown that the traditional Peltier and Thomson contributions can be expressed in a unique and compact form, only differing in the boundary conditions, ensuring a simple derivation of practical design expressions for the TE applications. The basic derivation of a general conductivity matrix is performed by considering the Peltier-Thomson coefficient and the local energy balance expression. By using relative current density and thermoelectric potential, the authors reconsider the question of the optimal efficiency of a thermogenerator. It is shown that the best thermodynamic working conditions are obtained when the relative current density is equal to a specific value directly depending on the material properties. This strongly influences the design of the TE devices since the TE materials should work under specific thermodynamic conditions in terms of temperature and electromechanical potential differences. Finally, the authors discuss an optimum device design and functionally graded materials.