Melanie J. Kirkham

Lattice thermal conductivity of the Cu3SbSe4-Cu3SbS4 solid solution

The compositional dependence of the crystal structure and lattice thermal conductivity in the Cu3SbSe4-Cu3SbS4 system has been studied. The lattice parameters of the Cu3SbSe4-xSx compounds decrease linearly with x, and the tetragonal structure (space group 14−2m no. 121) of the end compounds is maintained at all compositions. The lattice thermal conductivity is much lower than that predicted by a simple rule of mixtures, which is typical for a solid solution. The Debye model produces a very reasonable fit to the experimental lattice thermal conductivity data when phonon scattering due to atomic mass and size differences between Se and S is taken into account. Compounds in this series are likely to improve upon the thermoelectric performance of Cu3SbSe4, which has shown ZT = 0.72 when optimized.

Novel cell design for combined in situ acoustic emission and x-ray diffraction study during electrochemical cycling of batteries

An in situ acoustic emission (AE) and x-ray diffraction cell for use in the study of battery electrode materials has been designed and tested. This cell uses commercially available coin cell hardware retrofitted with a metalized polyethylene terephthalate (PET) disk, which acts as both an x-ray window and a current collector. In this manner, the use of beryllium and its associated cost and hazards is avoided. An AE sensor may be affixed to the cell face opposite the PET window in order to monitor degradation effects, such as particle fracture, during cell cycling. Silicon particles, which were previously studied by the AE technique, were tested in this cell as a model material. The performance of these cells compared well with unmodified coin cells, while providing information about structural changes in the active material as the cell is repeatedly charged and discharged.

The temperature dependence of thermal expansion for p-type Ce0.9Fe3.5Co0.5Sb12and n-type Co0.95Pd0.05Te0.05Sb3skutterudite thermoelectric materials

During waste heat recovery applications, thermoelectric (TE) materials experience thermal gradients and thermal transients, which produce stresses that scale with the TE materials coefficient of thermal expansion (CTE). Thus, the temperature-dependent CTE is an important parameter for the design of mechanically robust TE generators. For three skutterudite thermoelectric compositions, n-type Co0.95Pd0.05Te0.05Sb3 (with and without 0.1 at. % cerium doping) and p-type Ce0.9Fe3.5Co0.5Sb12, the CTE was measured using two methods, i.e. X-ray diffraction on powder and bulk specimens and dilatometry on bulk specimens. Each bulk specimen was hot pressed using powders milled from cast ingots. Between 300 K and 600 K, the mean CTE values were 9.8–10.3 × 10−6 K−1 for the non-cerium-doped n-type, 11.6 × 10−6 K−1 for the 0.1 at. % cerium-doped n-type and from 12.7 to 13.3 × 10−6 K−1 for the p-type. In the literature, similar CTE values are reported for other Sb-based skutterudites. For temperatures >600 K, an unrecovered dilatational strain (perhaps due to bloating) was observed, which may impact applications. Also, the submicron particle sizes generated by wet milling were pyrophoric; thus, during both processing and characterization, exposure of the powders to oxygen should be limited.

The role of boron segregation in enhanced thermoelectric power factor of CoSi1−xBx alloys

We report on the influence of boron segregation on the thermoelectric properties of CoSi. Contrary to previous suggestions, and in stark contrast to aluminum substitution, boron does not enter the lattice on the Si site, but rather segregates to the grain boundaries in these alloys. Through a combination of x-ray diffraction, scanning electron microscope, and scanning Auger techniques, we present clear evidence of the formation of a CoB phase at the grain boundaries. Consistent with the failure of B to substitute for Si, we observe no changes in the electron concentration or the Seebeck coefficient under boron substitution. The electrical resistivity, on the other hand, displays a non-monotonic behavior with increasing boron concentration, first decreasing for small amounts of boron, before increasing at higher levels of substitution. We attribute this behavior to a combination of an initial healing effect of boron on microcracks, followed by the eventual increase in electron scattering by the secondary CoB phase at higher concentrations.

Non-vacuum deposition of aqueous-based CuIn x Ga 1−x Se 2 (CIGS) nanoparticles for solar applications

CuInxGa1−xSe2 (CIGS) as an absorber material in solar cells is already known to present a less toxic alternative to current solar cells based on toxic elements such as CdTe. CIGS developed as nanoparticles in solution are ideal for non-vacuum deposition methods which help achieve lower-cost solar cells, compared to high vacuum deposition methods. This study investigates deposition, processing, and characterization of aqueous-based CIGS nanoparticles. The films are deposited via sono-deposition, spin coating method, and drop cast method. The as-deposited thin films are characterized via X-Ray Diffraction (XRD), Optical Microscope, and Scanning Electron Microscopy (SEM, and STEM). The films are then annealed via Pulsed Thermal Processing (PTP) technique, and post-PTP characterization shows change in the morphology of CIGS nanoparticles.

AGES: Automated Gas Environment System for in situ neutron powder diffraction

High fluxes available at modern neutron and synchrotron sources have opened up a wide variety of in situ and operando studies of real processes using scattering techniques. This has allowed the user community to follow chemistry in the beam, which often requires high temperatures, gas flow, etc. In this paper, we describe an integrated gas handling system for the general-purpose powder diffraction beamline Powgen at the Spallation Neutron Source. The Automated Gas Environment System (AGES) allows control of both gas flow and temperature (room temperature to 850 °C), while measuring the partial pressure of oxygen and following the effluent gas by mass spectrometry, concurrent with neutron powder diffraction, in order to follow the structural evolution of materials under these conditions. The versatility of AGES is illustrated by two examples of experiments conducted with the system. In solid oxide fuel cell electrode materials, oxygen transport pathways in double perovskites PrBaCo2O5+δ and NdBaCo2O5+δ were elucidated by neutron diffraction measurements under atmosphere with oxygen partial pressures (pO2) of 10-1 to 10-4 (achieved using mixtures of nitrogen and oxygen) and temperatures from 575 to 850 °C. In another example, the potential oxygen storage material La1-xSrxFeO3 was measured under alternating flows of 15% CH4 in N2 and air (20% O2 in N2) at temperatures from 135 to 835 °C. From the oxygen stoichiometry, the optimal composition for oxygen storage was determined.

Synthesis of a Ferrolite: A Zeolitic All-Iron Framework

Crystals of the first sodalite-type zeolite containing an all-iron framework, a ferrolite, Ba8 (Fe12 O24 )Nay (OH)6 ⋅x H2 O, were synthesized using the hydroflux method in nearly quantitative yield. Ba8 (Fe12 O24 )Nay (OH)6 ⋅x H2 O crystallizes in the cubic space group Pm3‾m with a=10.0476(1) Å. Slightly distorted FeO4 tetrahedra are linked to form Fe4 O4 and Fe6 O6 rings, which in turn yield channels and internal cavities that are characteristic of the sodalite structure. Barium, sodium, and hydroxide ions and water molecules are found in the channels and provide charge balance. Magnetic measurements indicate that the ferrolite exhibits magnetic order up to at least 700 K, with the field-cooled and zero-field-cooled curves diverging. Analysis of the 57 Fe Mössbauer spectra revealed two spectral components that have equal spectral areas, indicating the presence of two subsets of iron centers in the structure. Dehydrated versions of the ferrolite were also prepared by heating the sample.