Lungang Chen

Low thermal conductivity and high thermoelectric figure of merit in n-type BaxYbyCo4Sb12 double-filled skutterudites

Filled skutterudites are one of the most promising thermoelectric materials for power generation applications. The choice and concentration of filler atoms are key aspects for achieving high thermoelectric figure of merit values. We report on the high temperature thermoelectric properties in the double-filled skutterudites BaxYbyCo4Sb12. The combination of Ba and Yb fillers inside the voids of the skutterudite structure provides a broad range of resonant phonon scattering and consequently a strong suppression in the lattice thermal conductivity is observed. A dimensionless thermoelectric figure of merit of 1.36 at 800K is achievable for n-type BaxYbyCo4Sb12.

Effects of partial substitution of Ni by Pd on the thermoelectric properties of ZrNiSn-based half-Heusler compounds

We report on the effects of partial substitution of nickel by palladium on the thermoelectric properties of ZrNiSn-based half-Heusler compounds. It is shown that the substitution of palladium for nickel results in a significant, beneficial reduction of the thermal conductivity. The Seebeck coefficient also decreases, but only by a small amount. In the Hf0.5Zr0.5Ni0.8Pd0.2Sn0.99Sb0.01 compound, a power factor of 22.1 μW K−2 cm−1 and a thermal conductivity as low as 4.5 W/m K are measured at room temperature. The dimensionless figure of merit ZT increases with increasing temperature and reaches a maximum value of 0.7 at about 800 K.

Thermoelectric properties of tetrahedrally bonded wide-gap stannite compounds Cu2ZnSn1-xInxSe4

It is usually accepted that good thermoelectric (TE) materials should be narrow-gap semiconductors. Here we show an example that the tetrahedrally bonded stannite compound Cu2ZnSnSe4 with a band gap of 1.44 eV can also exhibit a high figure of merit at intermediate temperature. The highly distorted structure strives for the relatively low thermal conductivity, and the tunability of the electrical properties were demonstrated through doping. The maximum ZT of Cu2ZnSn0.90In0.10Se4 reaches 0.95 at 850 K. This work may open a way for exploring high-performance TE materials with the family of widely existing tetrahedrally bonded semiconductors.

Synthesis of YbyCo4Sb12∕Yb2O3 composites and their thermoelectric properties

Composites containing Yb-filled CoSb3 and well-distributed Yb2O3 particles are synthesized by in situ reaction method. The structural, chemical, and transport properties of the composites are studied. Some Yb2O3 particles with microsize locate at the grain boundaries of matrix and others distribute within YbyCo4Sb12 grains as nanoscale inclusions. The combination of the “rattling” of Yb ions inside the voids of CoSb3 and the phonon scattering of the oxide defects results in a remarkable reduction in the lattice thermal conductivity. The thermoelectric performance of the composites is significantly improved, and the maximum figures of merit reach 1.3 for the Yb0.25Co4Sb12∕Yb2O3 and 1.2 for the Yb0.21Co4Sb12∕Yb2O3 composites at 850K.

Synthesis and thermoelectric properties of KyCo4Sb12

Polycrystalline K-filled CoSb3 are synthesized successfully. The uplimit for K filling is at least 0.45, being higher than those of either alkaline-earth (AE) or rare-earth (RE) metals but being in consistent with our earlier theoretical prediction. The measured transport properties (300–800K) show that K filling does not lower thermal conductivity much in comparison with AE or RE filling due to the relatively low mass of K atom. However, it improves electrical conductivity, retains large Seebeck coefficient, and leads to a reasonably good thermoelectric performance for the filled skutterudites. The maximum figure of merit ZT reaches 1 at 800K for K0.38Co4Sb12.

Synthesis and thermoelectric properties of Sr-filled skutterudite SryCo4Sb12

Strontium-filled skutterudites SryCo4Sb12 have been synthesized by a melting method. The filling fraction of Sr in CoSb3 skutterudite is up to y=0.40, closely consistent with the calculated value by density functional theory methods. The lattice parameters increase linearly with the increase of Sr content, and the relative change in lattice parameters is in agreement with theoretical prediction. Hall effect measurements have been performed by Van de Pauw method at room temperature. All samples filled with Sr atom exhibit n-type conduction. The thermal and electrical transport properties have been measured in the temperature range of 300–850K. The lattice thermal conductivity of SryCo4Sb12 is significantly depressed as compared to that of the unfilled CoSb3. The dimensionless thermoelectric figure of merit, ZT, increases with increasing temperature and reaches a maximum value of 0.9 for Sr0.28Co4Sb12 at 850K.

High-temperature electrical and thermal transport properties of fully filled skutterudites RFe4Sb12 (R = Ca, Sr, Ba, La, Ce, Pr, Nd, Eu, and Yb)

Fully filled skutterudites RFe_(4)Sb_(12) (R = Ca, Sr, Ba, La, Ce, Pr, Nd, Eu, and Yb) have been prepared and the high-temperature electrical and thermal transport properties are investigated systematically. Lattice constants of RFe_(4)Sb_(12) increase almost linearly with increasing the ionic radii of the fillers, while the lattice expansion in filled structure is weakly influenced by the filler valence charge states. Using simple charge counting, the hole concentration in RFe_(4)Sb_(12) with divalent fillers (R = Ca, Sr, Ba, Eu, and Yb) is much higher than that in RFe4Sb12 with trivalent fillers (R = La, Ce, Pr, and Nd), resulting in relatively high electrical conductivity and low Seebeck coefficient. It is also found that RFe_(4)Sb_(12) filled skutterudites having similar filler valence charge states exhibit comparable electrical conductivity and Seebeck coefficient, and the behavior of the temperature dependence, thereby leading to comparable power factor values in the temperature range from 300 to 800 K. All RFe_(4)Sb_(12) samples possess low lattice thermal conductivity. The correlation between the lattice thermal resistivity WL and ionic radii of the fillers is discussed and a good relationship of W_L ~ (r_(cage)−r_(ion))^3 is observed in lanthanide metal filled skutterudites. CeFe_(4)Sb_(12), PrFe_(4)Sb_(12), and NdFe_(4)Sb_(12) show the highest thermoelectric figure of merit around 0.87 at 750 K among all the filled skutterudites studied in this work.

Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2–ZrO2 catalysts

Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel.

Recent advances in high-performance bulk thermoelectric materials

Thermoelectric (TE) materials facilitate direct heat-to-electricity conversion. The performance of a TE material is characterised by its figure of merit zT (=S2 σT/κ) that depends on both electronic transport properties, i.e. the Seebeck coefficient S and the electrical conductivity σ, and on thermal transport properties, i.e. the thermal conductivity κ of a material. The intrinsically counter-correlated behaviour between electronic and thermal transport properties makes the enhancement of zT a very challenging task. In the past 10 years, the zTs in bulk TE materials have been significantly enhanced due to intensive exploratory efforts, the discovery of new physical phenomena and effects, and applications of advanced synthesis methods. In this review, we summarise the recent progress in bulk TE materials. After the introduction of fundamental principles of thermoelectricity, the recently achieved enhancements in the TE performance encompassing the use of electronic band structure engineering, lattice phonon engineering and nanostructure tailoring will be emphasised. Next, the highlights of typical TE materials will be presented, focusing especially on the great progress achieved during the past decade. Finally, new techniques and approaches developed to fabricate TE materials will be outlined and their impact on the performance and economic viability of large-scale TE applications will be considered. The progress made during the past dozen or so years provides great opportunities for the use of bulk TE materials in a much broader range of applications and bodes well for a more efficient utilisation of energy.

The high temperature thermoelectric performances of Zr0.5Hf0.5Ni0.8Pd0.2Sn0.99Sb0.01 alloy with nanophase inclusions

The Zr0.5Hf0.5Ni0.8Pd0.2Sn0.99Sb0.01∕ZrO2 nanocomposites have been prepared by spark plasma sintering technique. The thermoelectric properties were measured in the temperature range of 300–900K. Thermal conductivity for the nanocomposites is considerably reduced, because the nanophase scatters the thermal phonons which transport most of the heat in the ZrNiSn-based alloy. Seebeck coefficient for the nanocomposites is enhanced due to the potential barrier scattering. The dimensionless figure of merit ZT is improved, with ZT≈0.75 at 800K for the samples containing 9vol% ZrO2 nanoinclusions. The results obtained suggest that considerable improvements in the thermoelectric figure of merit may be obtainable by inducing appropriate nanoinclusions into the matrix.