Structural modifications and non-monotonic carrier concentration in Bi2Se0.3Te2.7 by reversible electrochemical lithium reactions

Reversible electrochemical lithium intercalation/deintercalation reactions have been applied to integrally modify the thermoelectric performance of Bi2Se0.3Te2.7 compounds. The carrier concentration of Bi2Se0.3Te2.7 has been precisely controlled experimentally through the adjustment of the residual lithium content. The variations of electronic transport properties of LixBi2Se0.3Te2.7, including electrical conductivity, Seebeck coefficient and carrier concentration, as a function of the intercalated lithium amount (x), show a special non-monotonic P-type to N-type doping trend. This variation is caused by the competition of two mechanisms controlling the carrier concentration: (i) decreasing of the Se/Te ratio through a Li-Se reaction that reduces the amount of the Te-Bi or Se-Bi antisite defects and therefore the electron concentration; (ii) n-type doping by lithium that provides the electron. Moreover, the nanoparticle exfoliation during lithium intercalation and deintercalation reactions leads to the formation of an internal nanocrystalline composite structure which effectively reduces the lattice thermal conductivity. Through an integral modification of both electrical and thermal transport properties, the maximum ZT value of LixBi2Se0.3Te2.7 was improved by nearly 25%. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.