Spontaneously formed porous and composite materials

In recent years, a number of routes to porous materials have been developed which do not involve the use of pre-formed templates or structure-directing agents. These routes are usually spontaneous, meaning they are thermodynamically downhill. Kinetic control, deriving from slow diffusion of certain species in the solid state, allows metastable porous morphologies rather than dense materials to be obtained. While the porous structures so formed are random, the average architectural features can be well-defined, and the porosity is usually highly interconnected. The routes are applicable to a broad range of functional inorganic materials. Consequently, the porous architectures have uses in energy transduction and storage, chemical sensing, catalysis, and photoelectrochemistry. This is in addition to more straightforward uses deriving from the pore structure, such as in filtration, as a structural material, or as a cell-growth scaffold. In this feature article, some of the methods for the creation of porous materials are described, including shape-conserving routes that lead to hierarchical macro/mesoporous architectures. In some of the preparations, the resulting mesopores are aligned locally with certain crystallographic directions. The coupling between morphology and crystallography provides a macroscopic handle on nanoscale structure. Extension of these routes to create biphasic composite materials are also described

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

Transport properties of the layered Zintl compound SrZnSb_2

Transport properties of the layered Zintl compound SrZnSb_2 have been characterized from room temperature to 725 K on polycrystalline samples. SrZnSb_2 samples were found to be p-type with a Hall carrier concentration of 5×10^(20) cm^(−3) at room temperature, and a small Seebeck coefficient and electrical resistivity are observed. A single band model predicts that, even with optimal doping, significant thermoelectric performance will not be achieved in SrZnSb_2. A relatively low lattice thermal conductivity is observed, κ_L~1.2 W m^(−1) K^(−1), at room temperature. The thermal transport of SrZnSb_2 is compared to that of the layered Zintl compounds AZn2Sb_2 (A=Ca,Yb,Sr,Eu), which have smaller unit cells and larger lattice thermal conductivity, κ_L~2 W m^(−1) K^(−1), at 300K. Ultrasonic measurements, in combination with kinetic theory and the estimated κ_L values, suggest that the lower κ_L of SrZnSb_2 is primarily the result of a reduction in the volumetric specific heat of the acoustic phonons due to the increased number of atoms per unit cell. Therefore, this work recommends that unit cell size should be considered when selecting Zintl compounds for potential thermoelectric application

Zintl Chemistry for Designing High Efficiency Thermoelectric Materials

Zintl phases and related compounds are promising thermoelectric materials; for instance, high zT has been found in Yb_(14)MnSb_(11), clathrates, and the filled skutterudites. The rich solid-state chemistry of Zintl phases enables numerous possibilities for chemical substitutions and structural modifications that allow the fundamental transport parameters (carrier concentration, mobility, effective mass, and lattice thermal conductivity) to be modified for improved thermoelectric performance. For example, free carrier concentration is determined by the valence imbalance using Zintl chemistry, thereby enabling the rational optimization of zT. The low thermal conductivity values obtained in Zintl thermoelectrics arise from a diverse range of sources, including point defect scattering and the low velocity of optical phonon modes. Despite their complex structures and chemistry, the transport properties of many modern thermoelectrics can be understood using traditional models for heavily doped semiconductors

High temperature thermoelectric efficiency in Ba8Ga16Ge30

The high thermoelectric figure of merit (zT) of Ba8Ga16Ge30 makes it one of the best n-type materials for thermoelectric power generation. Here, we describe the synthesis and characterization of a Czochralski pulled single crystal of Ba8Ga16Ge30 and polycrystalline disks. Measurements of the electrical conductivity, Hall effect, specific heat, coefficient of thermal expansion, thermal conductivity, and Seebeck coefficient were performed up to 1173 K and compared with literature results. Dilatometry measurements give a coefficient of thermal expansion of 16×10^−6 K^−1 up to 1175 K. The trend in electronic properties with composition is typical of a heavily doped semiconductor. The maximum in the thermoelectric figure of merit is found at 1050 K with a value of 0.8. The correction of zT due to thermal expansion is not significant compared to the measurement uncertainties involved. Comparing the thermoelectric efficiency of segmented materials, the effect of compatibility makes Ba8Ga16Ge30 more efficient than the higher zT n-type materials SiGe or skutterudite CoSb3

A high temperature apparatus for measurement of the Seebeck coefficient

A high temperature Seebeck coefficient measurement apparatus with various features to minimize typical sources of error is designed and built. Common sources of temperature and voltage measurement error are described and principles to overcome these are proposed. With these guiding principles, a high temperature Seebeck measurement apparatus with a uniaxial 4-point contact geometry is designed to operate from room temperature to over 1200 K. This instrument design is simple to operate, and suitable for bulk samples with a broad range of physical types and shapes

Thermoelectric properties of p-type LiZnSb: Assessment of ab initio calculations

In response to theoretical calculations on the thermoelectric performance of LiZnSb, we report the pertinent transport properties between room temperature and 523 K. Nominal LiZnSb samples are found to be p-type, with a carrier concentration in the range (4–7)×10^(20) cm^(−3). The thermoelectric figure of merit (zT) is found to be 0.02–0.08 at 523 K. Analysis of material transport parameters and previously reported ab initio calculations demonstrates that even with optimal doping, p-type LiZnSb is unlikely to achieve zT>0.2 at 523 K. The accuracy of the high zT estimate (zT>2) for n-type compositions from ab initio calculations is discussed within the current synthetic limits

Valence band study of thermoelectric Zintl-phase SrZn_2Sb_2 and YbZn_2Sb_2: X-ray photoelectron spectroscopy and density functional theory

The electronic structure of SrZn_2Sb_2 and YbZn_2Sb_2 is investigated using density functional theory and high-resolution x-ray photoemission spectroscopy. Both traditional Perdew-Burke-Ernzerhof and state-of-the-art hybrid Heyd-Scuseria-Ernzerhof functionals have been employed to highlight the importance of proper treatment of exchange-dependent Zn  3d states, Yb 4f states, and band gaps. The role of spin-orbit corrections in light of first-principles transport calculations are discussed and previous claims of Yb^(3+) valence are investigated with the assistance of photoelectron as well as scanning and transmission electron microscopy