Phonon engineering through crystal chemistry

Mitigation of the global energy crisis requires tailoring the thermal conductivity of materials. Low thermal conductivity is critical in a broad range of energy conversion technologies, including thermoelectrics and thermal barrier coatings. Here, we review the chemical trends and explore the origins of low thermal conductivity in crystalline materials. A unifying feature in the latest materials is the incorporation of structural complexity to decrease the phonon velocity and increase scattering. With this understanding, strategies for combining these mechanisms can be formulated for designing new materials with exceptionally low thermal conductivity

Ca_3AlSb_3: an inexpensive, non-toxic thermoelectric material for waste heat recovery

Thermoelectric materials directly convert thermal energy into electrical energy, offering a promising solid-state solution for waste heat recovery. For thermoelectric devices to make a significant impact on energy and the environment the major impediments are the efficiency, availability and toxicity of current thermoelectric materials. Typically, efficient thermoelectric materials contain heavy elements such as lead and tellurium that are toxic and not earth abundant. Many materials with unusual structures containing abundant and benign elements are known, but remain unexplored for thermoelectric applications. In this paper we demonstrate, with the discovery of high thermoelectric efficiency in Ca_3AlSb_3, the use of elementary solid-state chemistry and physics to guide the search and optimization of such materials

Thermoelectric properties of Zn-doped Ca_5In_2Sb_6

The Zintl compound Ca_5Al_2Sb_6 is a promising thermoelectric material with exceptionally low lattice thermal conductivity resulting from its complex crystal structure. In common with the Al analogue, Ca_5In_2Sb_6 is naturally an intrinsic semiconductor with a low p-type carrier concentration. Here, we improve the thermoelectric properties of Ca_5In_2Sb_6 by substituting Zn^(2+) on the In^(3+) site. With increasing Zn substitution, the Ca_5In_(2−x)Zn_xSb_6 system exhibits increased p-type carrier concentration and a resulting transition from non-degenerate to degenerate semiconducting behavior. A single parabolic band model was used to estimate an effective mass in Ca_5In_2Sb_6 of m^* = 2m_e, which is comparable to the Al analogue, in good agreement with density functional calculations. Doping with Zn enables rational optimization of the electronic transport properties and increased zT in accordance with a single parabolic band model. The maximum figure of merit obtained in optimally Zn-doped Ca_5In_2Sb_6 is 0.7 at 1000 K. While undoped Ca_5In_2Sb_6 has both improved electronic mobility and reduced lattice thermal conductivity relative to Ca_5Al_2Sb_6, these benefits did not dramatically improve the Zn-doped samples, leading to only a modest increase in zT relative to optimally doped Ca_5Al_2Sb_6

Chain-Forming Zintl Antimonidcs as Novel Thermoelectric Materials

Zintl phases, a subset of intermetallic compounds characterized by covalently-bonded "sub-structures," surrounded by highly electropositive cations, exhibit precisely the characteristics desired for thermoelectric applications. The requirement that Zintl compounds satisfy the valence of anions through the formation of covalent substructures leads to many unique, complex crystal structures. Such complexity often leads to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical modes in the phonon dispersion. To date, excellent thermoelectric properties have been demonstrated in several Zintl compounds. However, compared with the large number of known Zintl phases, very few have been investigated as thermoelectric materials. From this pool of uninvestigated compounds, we selected a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked MSb4 tetrahedra, where $M$ is a triel element. The compounds discussed in this thesis (A5M2Sb6 and A3MSb3, where A = Ca or Sr and M = Al, Ga and In) crystallize as four distinct, but closely related "chain-forming" structure types. This thesis describes the thermoelectric characterization and optimization of these phases, and explores the influence of their chemistry and structure on the thermal and electronic transport properties. Due to their large unit cells, each compound exhibits exceptionally low lattice thermal conductivity (0.4 - 0.6 W/mK at 1000 K), approaching the predicted glassy minimum at high temperatures. A combination of Density Functional calculations and classical transport models were used to explain the experimentally observed electronic transport properties of each compound. Consistent with the Zintl electron counting formalism, A5M2Sb6 and A3MSb3 phases were found to have filled valence bands and exhibit intrinsic electronic properties. Doping with divalent transition metals (Zn2+ and Mn2+) on the M3+ site, or Na1+ on the A3+ site allowed for rational control of the carrier concentration and a transition towards degenerate semiconducting behavior. In optimally-doped samples, promising peak zT values between 0.4 and 0.9 were obtained, highlighting the value of continued investigations of complex Zintl phases.</p

Zintl Phases for Thermoelectric Applications

The inventors demonstrate herein that various Zintl compounds can be useful as thermoelectric materials for a variety of applications. Specifically, the utility of Ca3AlSb3, Ca5Al2Sb6, Ca5In2Sb6, Ca5Ga2Sb6, is described herein. Carrier concentration control via doping has also been demonstrated, resulting in considerably improved thermoelectric performance in the various systems described herein

Behaviour of sandy soil subjected to dynamic loading

This thesis presents the kinematics occurring during lab-based dynamic compaction tests using high speed photography and image correlation techniques. High speed photography and X-ray microtomography have been used to analyse the behaviour of sandy soil subjected to dynamic impact. In particular, the densification mechanism of granular soils due to dynamic compaction is the main theme of the thesis. High speed photography and digital image correlation (DIC) techniques have enabled the deformation patterns, soil strains and strain localisations to be observed. Image correlation and X-ray scans revealed the formation, rate and growth of narrow tabular bands of intense deformation and significant volumetric change and provided answers towards a better understanding of the densification mechanism in dry granular soils due to dynamic compaction. As a quantitative tool, high speed photography has allowed the propagation of localised deformation and strain fields to be identified and has suggested that compaction shock bands control the kinematics of dynamic compaction. The displacement and strain results from high speed photography showed that soil deformation in the dynamic tests was dominated by a general bearing capacity mechanism similar to that widely stated in classic soil mechanics texts. Comparative static loading tests have been conducted to enable the dynamic effects to be clearly distinguished. This has enabled the densification process taking place below the soil surface to be investigated and identified. Simulations of the physical models were carried out using LS-DYNA finite element formulations for comparison and verification purposes. The FE simulations verified the general characteristics from the photography findings. However, simulation results were unable to predict the exact details of the strain localisation due to surface impacts during physical model tests

Thermoelectric properties of the Yb_9Mn_(4.2-x)Zn_xSb_9 solid solutions

Yb_9Mn_(4.2)Sb_9 has been shown to have extremely low thermal conductivity and a high thermoelectric figure of merit attributed to its complex crystal structure and disordered interstitial sites. Motivated by previous work which shows that isoelectronic substitution of Mn by Zn leads to higher mobility by reducing spin disorder scattering, this study investigates the thermoelectric properties of the solid solution, Yb_9Mn_(4.2−x)Zn_xSb_9 (x = 0, 1, 2, 3 and 4.2). Measurements of the Hall mobility at high temperatures (up to 1000 K) show that the mobility can be increased by more than a factor of 3 by substituting Zn into Mn sites. This increase is explained by the reduction of the valence band effective mass with increasing Zn, leading to a slightly improved thermoelectric quality factor relative to Yb_9Mn_(4.2)Sb_9. However, increasing the Zn-content also increases the p-type carrier concentration, leading to metallic behavior with low Seebeck coefficients and high electrical conductivity. Varying the filling of the interstitial site in Yb_9Zn_(4+y)Sb_9 (y = 0.2, 0.3, 0.4 and 0.5) was attempted, but the carrier concentration (~10^(21) cm^(−3) at 300 K) and Seebeck coefficients remained constant, suggesting that the phase width of Yb_9Zn_(4+y)Sb_9 is quite narrow

Thermoelectric properties and electronic structure of the Zintl phase Sr_5Al_2Sb_6

The Zintl phase Sr_5Al_2Sb_6 has a large, complex unit cell and is composed of relatively earth-abundant and non-toxic elements, making it an attractive candidate for thermoelectric applications. The structure of Sr_5Al_2Sb_6 is characterized by infinite oscillating chains of AlSb_4 tetrahedra. It is distinct from the structure type of the previously studied Ca_5M_2Sb_6 compounds (M = Al, Ga or In), all of which have been shown to have promising thermoelectric performance. The lattice thermal conductivity of Sr_5Al_2Sb_6 (∼0.55 W mK^(-1) at 1000 K) was found to be lower than that of the related Ca_5M_2Sb_6 compounds due to its larger unit cell (54 atoms per primitive cell). Density functional theory predicts a relatively large band gap in Sr_5Al_2Sb_6, in agreement with the experimentally determined band gap of E_g ∼ 0.5 eV. High temperature electronic transport measurements reveal high resistivity and high Seebeck coefficients in Sr_5Al_2Sb_6, consistent with the large band gap and valence-precise structure. Doping with Zn^(2+) on the Al^(3+) site was attempted, but did not lead to the expected increase in carrier concentration. The low lattice thermal conductivity and large band gap in Sr_5Al_2Sb_6 suggest that, if the carrier concentration can be increased, thermoelectric performance comparable to that of Ca_5Al_2Sb_6 could be achieved in this system

Enhanced thermoelectric properties of the Zintl phase BaGa_2Sb_2 via doping with Na or K

Na- or K-doped samples of Ba_(1−x)(Na, K)xGa_2Sb_2 were prepared by ball-milling followed by hot-pressing. The topological analysis of the electron density of BaGa_2Sb_2 implies a polar covalent nature of the Sb–Ga bonds in which the Sb atoms receive the electrons transferred from Ba rather than the Ga atoms. Successful doping of BaGa_2Sb_2 with Na or K was confirmed with combined microprobe and X-ray diffraction analysis. Alkali metal doping of BaGa_2Sb_2 increased the p-type charge carrier concentration to almost the predicted optimum values (∼10^(20) h^+ cm^(−3)) needed to achieve high thermoelectric performance. With increasing alkali metal concentration, electronic transport was shifted from non-degenerate semiconducting behaviour observed for BaGa_2Sb_2 to degenerate one for Na- or K-doped compounds. Overall, the thermoelectric figure of merit, zT, values reached up to ∼0.65 at 750 K, considerably higher than the undoped sample (zT ∼ 0.1 at 600 K), and a slight improvement relative to previously reported Zn-doped samples (∼0.6 at 800 K)

An unlikely route to low lattice thermal conductivity: small atoms in a simple layered structure

In the design of materials with low lattice thermal conductivity, compounds with high density, low speed of sound, and complexity at either the atomic, nano- or microstructural level are preferred. The layered compound Mg$_3$Sb$_2$ defies these prevailing paradigms, exhibiting lattice thermal conductivity comparable to PbTe and Bi$_2$Te$_3$, despite its low density and simple structure. The excellent thermoelectric performance ($zT$ $\sim$ 1.5) in $n$-type Mg$_3$Sb$_2$ has thus far been attributed to its multi-valley conduction band, while its anomalous thermal properties have been largely overlooked. To explain the origin of the low lattice thermal conductivity of Mg$_3$Sb$_2$, we have used both experimental methods and ab initio phonon calculations to investigate trends in the elasticity, thermal expansion and anharmonicity of $A$Mg$_2Pn_2$ Zintl compounds with $A$ = Mg, Ca, Yb, and $Pn$ = Sb and Bi. Phonon calculations within the quasi-harmonic approximation reveal large mode Gr\"uneisen parameters in Mg$_3$Sb$_2$ compared with isostructural compounds, in particular in transverse acoustic modes involving shearing of adjacent anionic layers. Measurements of the elastic moduli and sound velocity as a function of temperature using resonant ultrasound spectroscopy provide a window into the softening of the acoustic branches at high temperature, confirming their exceptionally high anharmonicity. We attribute the anomalous thermal behavior of Mg$_3$Sb$_2$ to the diminutive size of Mg, which may be too small for the octahedrally-coordinated site, leading to weak, unstable interlayer Mg-Sb bonding. This suggests more broadly that soft shear modes resulting from undersized cations provide a potential route to achieving low lattice thermal conductivity low-density, earth-abundant materials.Comment: 11 pages, 9 figure