RESUMO
The increasing energy demand and the ever more pressing need for clean technologies of energy conversion pose one of the most urgent and complicated issues of our age. Thermoelectricity, namely the direct conversion of waste heat into electricity, is a promising technique based on a long-standing physical phenomenon, which still has not fully developed its potential, mainly due to the low efficiency of the process. In order to improve the thermoelectric performance, a huge effort is being made by physicists, materials scientists and engineers, with the primary aims of better understanding the fundamental issues ruling the improvement of the thermoelectric figure of merit, and finally building the most efficient thermoelectric devices. In this Roadmap an overview is given about the most recent experimental and computational results obtained within the Italian research community on the optimization of composition and morphology of some thermoelectric materials, as well as on the design of thermoelectric and hybrid thermoelectric/photovoltaic devices.
RESUMO
Copper-based chalcogenides have emerged as promising thermoelectric materials due to their high thermoelectric performance, tunable transport properties, earth abundance and low toxicity. We have presented an overview of experimental results and first-principal calculations investigating the thermoelectric properties of various polymorphs of Cu2SnS3 (CTS), Cu2ZnSnS4 (CZTS), and Cu2ZnSnSe4 (CZTSe) synthesized by high-energy reactive mechanical alloying (ball milling). Of particular interest are the disordered polymorphs of these materials, which exhibit phonon-glass-electron-crystal behavior-a decoupling of electron and phonon transport properties. The interplay of cationic disorder and nanostructuring leads to ultra-low thermal conductivities while enhancing electronic transport. These beneficial transport properties are the consequence of a plethora of features, including trap states, anharmonicity, rattling, and conductive surface states, both topologically trivial and non-trivial. Based on experimental results and computational methods, this report aims to elucidate the details of the electronic and lattice transport properties, thereby confirming that the higher thermoelectric (TE) performance of disordered polymorphs is essentially due to their complex crystallographic structures. In addition, we have presented synchrotron X-ray diffraction (SR-XRD) measurements and ab initio molecular dynamics (AIMD) simulations of the root-mean-square displacement (RMSD) in these materials, confirming anharmonicity and bond inhomogeneity for disordered polymorphs.
RESUMO
The thermoelectric behavior and stability of Cu2SnS3 (CTS) has been investigated in relation to different preparations and sintering conditions, leading to different microstructures and porosities. The studied system is CTS in its cubic polymorph, produced in powder form via a bottom-up approach based on high-energy reactive milling. The as-milled powder was sintered in two batches with different synthesis conditions to produce bulk CTS samples: manual cold pressing followed by traditional sintering (TS), or open die pressing (ODP). Despite the significant differences in densities, ~75% and ~90% of the theoretical density for TS and ODP, respectively, we observed no significant difference in electrical transport. The stable, best performing TS samples reached zT ~0.45, above 700 K, whereas zT reached ~0.34 for the best performing ODP in the same conditions. The higher zT of the TS sintered sample is due to the ultra-low thermal conductivity (κ ~0.3-0.2 W/mK), three-fold lower than ODP in the entire measured temperature range. The effect of porosity and production conditions on the transport properties is highlighted, which could pave the way to produce high-performing TE materials.
