Yingcai Zhu

Enhancing thermoelectric performance in hierarchically structured BiCuSeO by increasing bond covalency and weakening carrier–phonon coupling

BiCuSeO oxyselenides are promising thermoelectric materials at intermediate temperatures, primarily due to their ultralow lattice thermal conductivity (κL) and high Seebeck coefficient. The intrinsically low carrier mobility in these materials, normally below ∼20 cm2 V−1 s−1 at 300 K, however, largely limits further improvements of their thermoelectric properties. In this study, by introducing less electronegative Te into the conductive Cu–Se layers, we demonstrate that the enhanced chemical bond covalency results in smaller effective mass and thus improved carrier mobility, through the weakening of carrier-phonon coupling. The improved carrier mobility by Te-doping largely retains the electrical conductivity values and thus high power factors even with decreased carrier concentrations. Meanwhile, the hierarchical structural features including dual point defects, nanoinclusions, grain boundaries, etc., originating from the nonequilibrium self-propagating high-temperature synthesis (SHS) processes, further reduce κL close to the amorphous limit. Ultimately, a maximum ZT value of ∼1.2 at 873 K is achieved in Bi0.96Pb0.04CuSe0.95Te0.05O, ∼35% improvement as compared with that of Te-free Bi0.96Pb0.04CuSeO and ∼2.4 times higher than that of the pristine sample. Furthermore, our study elucidates that weakening of carrier–phonon coupling through regulating chemical bonding within the conductive functionalities can be an effective avenue for further improving the thermoelectric performance of BiCuSeO.

Cd-doping a facile approach for better thermoelectric transport properties of BiCuSeO oxyselenides

BiCuSeO-based thermoelectric materials have spurred tremendous interest among the thermoelectric community due to their ultra-low thermal conductivity and relatively large Seebeck coefficient (S). In this work, we have reported the effect of Cd-doping at the Bi site, instead of the previously studied Cu site, on the thermoelectric performance of BiCuSeO by modifying the insulating layer. While maintaining good phase purity, Cd was successfully doped at the Bi site as confirmed by X-ray absorption fine structure spectroscopy. The Cd-doping substantially improves the electrical conductivity by a factor of 20 through bond anharmonicity at room temperature while increasing the Cd concentration over 5%. Further, the incorporation of the lighter atom at the Bi site creates phonon scattering centers and results in weak bonding between the layers, resulting in a remarkable perturbation of the local geometric and electronic structure. BiCuSeO with 5% Cd-doping maintains a large S and a high electrical conductivity up to 923 K and exhibits the highest power factor values (600 μW m−1 K−2 at 323 K and 447 μW m−1 K−2 at 923 K) and the largest ZT (0.98 at 923 K). Cd-doping at the Bi site in p-type thermoelectric BiCuSeO was shown to be a very good technique for improving the thermoelectric performance and could be extended to other thermoelectric materials to enhance the efficiency of thermoelectric devices for energy-harvesting.

Enhanced Thermoelectricity in High-Temperature β-Phase Copper(I) Selenides Embedded with Cu2Te Nanoclusters

We report remarkably enhanced thermoelectric performance of Te doped Cu2Se in midtemperature range. Through ball-milling process followed by spark plasma sintering (SPS), nanoscale Cu2Te clusters were embeded in the matrix of Cu2Se, inducing a drastic enhancement of thermoelectric performance by reducing the thermal conductivity without degrading the power factor. A large ZT value of 1.9 was achieved at 873 K for Cu2Se1.9Te0.1, which is about 2 times larger than that of the pure Cu2Se. The nanoscale heat management by Cu2Te nanoclusters in superionic conductors opens up an avenue for thermoelectric materials research.

Chemical speciation of lead in secondary fly ash using X-ray absorption spectroscopy

In this study, fly ash samples were collected from bag houses in a Chinese municipal solid waste incinerator (MSWI) and secondary fly ash (SFA) samples were collected from a high-temperature tubular electric furnace by thermal treatment of MSWI fly ash at 1050, 1100, 1150, 1200, and 1250 °C.We determined the speciation and atomic coordinates of lead in SFA using X-ray absorption spectroscopy (XAS) techniques. The results obtained by X-ray absorption near edge structure (XANES) spectra revealed that the mass fraction of PbO in MSWI fly ash was 57.9% (wt %) while PbCl2 and PbS were the dominant species in SFA. Extended X-ray absorption fine structure (EXAFS) data analysis indicated the atomic coordinates of Pb were proportional to the weights of PbCl2 and PbS, in good agreement with the XANES spectra. These findings highlight lead evaporation processes in the MSWI fly ash during heat treatment and provide a method for consistent speciation analysis of environmental samples using XAS.

Lattice Dynamics and Thermal Conductivity in Cu2Zn1–xCoxSnSe4

The quaternary compound Cu2ZnSnSe4 (CZTSe), as a typical candidate for both solar cells and thermoelectrics, is of great interest for energy harvesting applications. Materials with a high thermoelectric efficiency have a relatively low thermal conductivity, which is closely related to their chemical bonding and lattice dynamics. Therefore, it is essential to investigate the lattice dynamics of materials to further improve their thermoelectric efficiency. Here we report a lattice dynamic study in a cobalt-substituted CZTSe system using temperature-dependent X-ray absorption fine structure spectroscopy (TXAFS). The lattice contribution to the thermal conductivity is dominant, and its reduction is mainly ascribed to the increment of point defects after cobalt substitution. Furthermore, a lattice dynamic study shows that the Einstein temperature of atomic pairs is reduced after cobalt substitution, revealing that increasing local structure disorder and weakened bonding for each of the atomic pairs are achieved, which gives us a new perspective for understanding the behavior of lattice thermal conductivity.

Enhanced thermoelectric performance through grain boundary engineering in quaternary chalcogenide Cu2ZnSnSe4

Quaternary chalcogenide Cu2ZnSnSe4 (CZTSe) is a promising wide band-gap p-type thermoelectric material. The structure and thermoelectric properties of lead substituted Cu2ZnSn1-xPbxSe4 are investigated. Lead primarily exists in the framework of PbSe as demonstrated by x-ray diffraction and calculation of x-ray absorption near-edge structure spectroscopy. The second phase distributes at the boundaries of CZTSe with thickness in several hundreds of nanometer. With appropriate grain boundary engineering, the enhancement of power factor and a decrease of thermal conductivity can be achieved simultaneously. As a result, a maximum figure of merit zT of 0.45 is obtained for the sample with x=0.02 at 723K.Quaternary chalcogenide Cu2ZnSnSe4 (CZTSe) is a promising wide band-gap p-type thermoelectric material. The structure and thermoelectric properties of lead substituted Cu2ZnSn1-xPbxSe4 are investigated. Lead primarily exists in the framework of PbSe as demonstrated by x-ray diffraction and calculation of x-ray absorption near-edge structure spectroscopy. The second phase distributes at the boundaries of CZTSe with thickness in several hundreds of nanometer. With appropriate grain boundary engineering, the enhancement of power factor and a decrease of thermal conductivity can be achieved simultaneously. As a result, a maximum figure of merit zT of 0.45 is obtained for the sample with x=0.02 at 723K.

Structural phase transitions in ionic conductor Bi2O3 by temperature dependent XPD and XAS

The superionic behavior of cubic δ-phase Bi2O3, a metastable phase at high temperature, is of great interests from both scientific and technological perspectives. With the highest ionic conductivity among all known compounds, the δ-phase Bi2O3 possesses promising applications in solid-oxide fuel cells. Previous investigations pointed out the α to δ- phase transition occurs during the heating process, as supported by the X-ray and Neutron diffraction experiments. Through in situ measurements of the long-range order structure and the local structure by X-ray powder diffraction and X-ray absorption spectroscopy, we investigated the evolution of the structures under different temperatures. Both techniques provided ample evidence that the existence of meta-stable β-phase are crucial for forming the defective fluorite cubic δ phase. Our finding suggested that the phase transition from tetragonal β-phase to δ-phase is an influencing factor for the generation of the oxygen-ion pathways.