ABSTRACT
CoSb3 thermoelectric skutterudite has been filled with rare-earth metals (M = La, Ce, Yb) and partially doped with Sn in specimens of M x Co4Sb12-y Sn y stoichiometry. This has been achieved under high-pressure conditions at 3.5 GPa in a piston-cylinder hydrostatic press. A structural investigation using synchrotron X-ray diffraction data reveals a phase segregation in twin skutterudite phases with filling fraction fluctuation and different unit-cell sizes. As a result of three effects acting as phonon scatterers, namely the rattling effect of M at the wide 8a cages of the cubic Im3Ì structure, the phase segregation, and the intrinsic disorder introduced by Sn substitution at the Sb sublattice, the total thermal conductivity (κ) dramatically falls to reach minimum values under 2 W m-1 K-1, well below those typically exhibited by other thermoelectric materials based upon single-filled skutterudites. The power factor is substantially enhanced to 1.11 mW m-1 K-2 in Yb0.5Co4Sb11.6Sn0.4 with respect to the unfilled composition, as a result of the charge transfer promoted by the filler.
ABSTRACT
The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together with a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. Besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.
