Thermoelectric enhancement in perovskite type textured Me0.85TiO3 ceramics by synergistic high-entropy and microstructure manipulations

Enhancing the figure-of-merit (ZT) for thermoelectric ceramics essentially needs strategies that aim to concurrently optimize electron and phonon transport properties to decouple their coupling relationship. This work developed < 001 >-textured Me0.85TiO3(Me = La, Sr, Ba, Ca) ceramics (LSBC-T) with a texture fraction of 92 % fabricated by a tape casting process combined with template grain-growth method, in which 10 wt% (001) oriented plate-like SrTiO3 serves as template seed and A-site deficient high-entropy (La0.25Sr0.25Ba0.25Ca0.25)(0.85)TiO3 composite was used as matrix material. A peak ZT of 0.27 was attained at 1073 K in the sample parallel to the tape casting direction which was twice the ZT = 0.13 of the non-textured sample. Quantitative analysis of atomic displacement disorder of A-site elements would provide an atomistic-scale understanding of grain orientation evolution with high texture degree and the low thermal conductivity of 1.79 W/(m center dot K) at 1073 K. The complex multi-scale defects consist of cation and oxygen vacancies, edge dislocations, parallel grain boundaries, phase interfaces, nanoscale metal/inorganic coexisting clusters, and metal Bi sandwich layer, which act as additional phonon scattering centers while affecting carrier transport, covering all frequency phonons (100 GHz-15 THz). In addition, multi-scale parallel interfaces, including atomic-scale crystal (00l) plane of SrTiO3 seed, nano-scale "core-shell" interface parallel to the (00l) plane, metal Bi particle forming a sandwich layer in SrTiO3 seed, and "brick-wall" textured grain boundaries, make the electrical and thermal conductivity exhibiting obvious anisotropy in this LSBC-T high-entropy textured ceramics. By utilizing texture engineering in high-entropy systems, this work provides a theoretical foundation and technical support for the advancement of microstructure manipulations to reduce the inherent lattice thermal conductivity, achieve electrical and thermal conductivity anisotropy to decouple the electron-phonon coupling relationship, and thereby enhance thermoelectric properties.