Engineering Transport Properties in Interconnected Enargite-Stannite Type Cu2+x Mn1-x GeS4 Nanocomposites.

Understanding the mechanisms that connect heat and electron transport with crystal structures and defect chemistry is fundamental to develop materials with thermoelectric properties. In this work, we synthesized a series of self-doped compounds Cu2+x Mn1-x GeS4 through Cu for Mn substitution. Using a combination of powder X-ray diffraction, high resolution transmission electron microscopy and precession-assisted electron diffraction tomography, we evidence that the materials are composed of interconnected enargite- and stannite-type structures, via the formation of nanodomains with a high density of coherent interfaces. By combining experiments with ab initio electron and phonon calculations, we discuss the structure-thermoelectric properties relationships and clarify the interesting crystal chemistry in this system. We demonstrate that excess Cu+ substituted for Mn2+ dopes holes into the top of the valence band, leading to a remarkable enhancement of the power factor and figure of merit ZT.

The crucial role of selenium for sulphur substitution in the structural transitions and thermoelectric properties of Cu5FeS4 bornite.

Bornite Cu5FeS4-xSex (0 ≤ x ≤ 0.6) compounds have been synthesized, using mechanical alloying, combined with spark plasma sintering (SPS). High temperature in situ neutron powder diffraction data collected on pristine Cu5FeS4 from room temperature up to 673 K show that SPS enables the stabilization of the intermediate cubic (IC) semi-ordered form (Fm3[combining macron]m, aIC ∼ 10.98 Å) at the expense of the ordered orthorhombic form (Pbca, aO ∼ 10.95 Å, bO ∼ 21.86 Å, cO ∼ 10.95 Å) in the 300-475 K temperature range, whereas above 475 K the IC form coexists with the high temperature cubic (C) form (Fm3[combining macron]m, aC ∼ 5.50 Å). The ability of Se for S substitution to induce disorder and consequently to enhance the IC phase formation is also emphasized. This disordering effect is explained by the high quenching efficiency of the SPS method compared to conventional heating. The existence of topotactic phase transformations, as well as Se for S substitution is shown to have a significant effect on the transport properties. As expected, electrical transport properties indicate a change towards a more metallic behaviour with increasing Se content. The electrical resistivity reduces from ∼21.4 mΩ cm for the pristine Cu5FeS4 to ∼3.95 mΩ cm for Cu5FeS3.4Se0.6 at room temperature. A maximum power factor of 4.9 × 10-4 W m-1 K-2 is attained at 540 K for x = 0.4 composition. The influence of selenium substitution on the carrier effective mass and mobility is discussed based on single parabolic band approximation. Furthermore, a detailed investigation of the thermal conductivity by this isovalent anion substitution reveals a significant reduction of the lattice thermal conductivity due to the alloying effect. Finally, the important role of structural transitions in the thermoelectric properties is addressed. A maximum ZT of 0.5 is attained at 540 K for Cu5FeS3.8Se0.2 composition.

Searching for new thermoelectric materials: some examples among oxides, sulfides and selenides.

Different families of thermoelectric materials have been investigated since the discovery of thermoelectric effects in the mid-19th century, materials mostly belonging to the family of degenerate semi-conductors. In the last 20 years, new thermoelectric materials have been investigated following different theoretical proposals, showing that nanostructuration, electronic correlations and complex crystallographic structures (low dimensional structures, large number of atoms per lattice, presence of 'rattlers'…) could enhance the thermoelectric properties by enhancing the Seebeck coefficient and/or reducing the thermal conductivity. In this review, the different strategies used to optimize the thermoelectric properties of oxides and chalcogenides will be presented, starting with a review on thermoelectric oxides. The thermoelectric properties of sulfides and selenides will then be discussed, focusing on layered materials and low dimensional structures (TiS2 and pseudo-hollandites). Some sulfides with promising ZT values will also be presented (tetrahedrites and chalcopyrites).

On the effects of substitution, intercalation, non-stoichiometry and block layer concept in TiS2 based thermoelectrics.

TiS2 based layered sulfides have recently received increasing interest from the thermoelectric community. Due to its layered structure, the TiS2 compound with its enormous capacity for chemical substitution and intercalation offers different means to optimize the thermoelectric response through concomitant tuning of carrier concentration and decrease of the lattice thermal conductivity. In this review, we first discuss and summarize the crystal structures and physical/chemical properties of TiS2 based layered sulfides. Then, the approaches that successfully enhanced the thermoelectric performances in the TiS2 ceramic samples densified by Spark Plasma sintering are outlined, which include intercalation, non-stoichiometry, cationic substitution, and the block layer concept.

Invited article: A round robin test of the uncertainty on the measurement of the thermoelectric dimensionless figure of merit of Co0.97Ni0.03Sb3.

A round robin test aiming at measuring the high-temperature thermoelectric properties was carried out by a group of European (mainly French) laboratories (labs). Polycrystalline skutterudite Co0.97Ni0.03Sb3 was characterized by Seebeck coefficient (8 labs), electrical resistivity (9 labs), thermal diffusivity (6 labs), mass volume density (6 labs), and specific heat (6 labs) measurements. These data were statistically processed to determine the uncertainty on all these measured quantities as a function of temperature and combined to obtain an overall uncertainty on the thermal conductivity (product of thermal diffusivity by density and by specific heat) and on the thermoelectric figure of merit ZT. An increase with temperature of all these uncertainties is observed, in agreement with growing difficulties to measure these quantities when temperature increases. The uncertainties on the electrical resistivity and thermal diffusivity are most likely dominated by the uncertainty on the sample dimensions. The temperature-averaged (300-700 K) relative standard uncertainties at the confidence level of 68% amount to 6%, 8%, 11%, and 19% for the Seebeck coefficient, electrical resistivity, thermal conductivity, and figure of merit ZT, respectively. Thermal conductivity measurements appear as the least accurate. The moderate value of the temperature-averaged relative expanded (confidence level of 95%) uncertainty of 17% on the mean of ZT is essential in establishing Co0.97Ni0.03Sb3 as a high temperature standard n-type thermoelectric material.

High temperature thermoelectric properties of Mo3Sb(7-x)Te(x) (0.0≤x≤1.8).

Polycrystalline Mo(3)Sb(7-x)Te(x) samples with nominal Te concentrations of x=0.0, 0.3, 1.0, 1.6 and 2.2 have been synthesized by a powder metallurgical route. High temperature thermoelectric properties measurements including thermopower (300-900 K), electrical resistivity (300-800 K) and thermal conductivity (300-1000 K) were carried out. The temperature and compositional variations of the thermopower can be satisfactorily explained by assuming a single parabolic band model with dominant acoustic phonon scattering. However, such a simple model fails to describe the electronic thermal conductivity for low Te concentration. The dimensionless figure of merit, ZT, increases on increasing both the temperature and the Te content to reach a maximum value of 0.3 at 800 K that can be extrapolated to ∼0.6 at 1000 K for Mo(3)Sb(5.4)Te(1.6).

Microstructure and crystallographic texture of Charonia lampas lampas shell.

Charonia lampas lampas shell is studied using scanning electron microscopy and X-ray diffraction combined analysis of the preferred orientations and cell parameters. The Charonia shell is composed of three crossed lamellar layers of biogenic aragonite. The outer layer exhibits a 001 fibre texture, the intermediate crossed lamellar layer is radial with a split of its c-axis and single twin pattern of its a-axis, and the inner layer is comarginal with split c-axis and double twinning. A lost of texture strength is quantified from the inner layer outward. Unit-cell refinements evidence the intercrystalline organic influence on the aragonite unit-cell parameters anisotropic distortion and volume changes in the three layers. The simulation of the macroscopic elastic tensors of the mineral part of the three layers, from texture data, reveals an optimisation of the elastic coefficient to compression and shear in all directions of the shell as an overall.

Superspace crystal symmetry of thermoelectric misfit cobalt oxides and predicted structural models.

Single crystals of thermoelectric misfit lamellar cobalt oxide phases in the Bi-Ca-Co-O and I-Bi-Ca-Co-O systems were synthesized. They are characterized by aperiodic structures involving two partially independent sublattices: a CdI(2)-type pseudohexagonal CoO(2) layer and a rocksalt-type BiCaO(2) slab allowing the intercalation of iodine. The crystal symmetry of these structures is discussed using the four-dimensional superspace formalism. The superspace Laue classes of the iodine-free and the intercalated compounds are P2/m(0delta(1/2)) (a(1) = 4.901, b(1) = 4.730, b(2) = 2.80, c(1) = 14.66 A, beta = 93.49 degrees ) and A2/m(0delta1) (a'1 = 4.903, b'1 = 4.742, c'1 = 36.51 A, beta = 87.30 degrees ), respectively. A comparison is given with the related Bi-Sr-Co-O misfit compounds. The present structures are compatible with the presence of an intrinsic modulation with a wavelength matching the misfit aperiodicity in the b direction. Preliminary partial structure refinements confirm the layer stacking of the structure and the intercalation of I between the Bi-O layers for the second phase. A comparison with other cobalt oxide phases, as well as symmetry and metric considerations allow us to predict average structures for these new phases and to describe the common structural features assumed for all these lamellar misfit cobalt oxides.

Nanoblock coupling effect in iodine intercalated [Bi(0.82)CaO(2)](2)[CoO(2)](1.69) layered cobaltite.

We report on the structural, microstructural, and electronic properties of iodine intercalated [Bi0.82CaO2]2[CoO2]1.69 misfit cobaltite. We first prove through a detailed and careful structural study that the block layer structure can be modified in the desired way. Iodine enters the material between the [BiO] double layers, and the c-cell parameter of the pristine compound is elongated by 3.6 Angstrom. On the basis of this result, we point out the coupling between the block-layer structure and the transport properties. Additionally, we provide in-depth commentary and discussion of some extra results, clarifying some doping effects in the quasi-2D studied phase. Finally, we also propose some expressions that might be useful to material scientists for the tuning of the properties of such compounds.