Anisotropic Small-Polaron Hopping In W:Bivo4 Single Crystals

DC electrical conductivity, Seebeck and Hall coefficients are measured between 300 and 450 K on single crystals of monoclinic bismuth vanadate that are doped n-type with 0.3% tungsten donors (W:BiVO4). Strongly activated small-polaron hopping is implied by the activation energies of the Arrhenius conductivities (about 300 meV) greatly exceeding the energies characterizing the falls of the Seebeck coefficients' magnitudes with increasing temperature (about 50 meV). Small-polaron hopping is further evidenced by the measured Hall mobility in the ab-plane (10(-1) cm(2) V-1 s(-1) at 300 K) being larger and much less strongly activated than the deduced drift mobility (about 5 x 10(-5) cm(2) V-1 s(-1) at 300 K). The conductivity and n-type Seebeck coefficient is found to be anisotropic with the conductivity larger and the Seebeck coefficient's magnitude smaller and less temperature dependent for motion within the ab-plane than that in the c-direction. These anisotropies are addressed by considering highly anisotropic next-nearest-neighbor (approximate to 5 angstrom) transfers in addition to the somewhat shorter (approximate to 4 angstrom), nearly isotropic nearest-neighbor transfers. (C) 2015 AIP Publishing LLC.U.S. Department of Energy (DOE), DE-FG02-09ER16119Welch Foundation Grant F-1436Hemphill-Gilmore Endowed FellowshipNSF MIRT DMR 1122603Chemical EngineeringTexas Materials InstituteChemistr

A soft X-ray spectroscopic perspective of electron localization and transport in tungsten doped bismuth vanadate single crystals

Polarization dependent V L-edge XAS spectra showing anisotropy in the electronic band structure of a W:BiVO4 single crystal.</p

Blade-Type Reaction Front in Micrometer-Sized Germanium Particles during Lithiation

To investigate the lithium transport mechanism in micrometer-sized germanium (Ge) particles, in situ focused ion beam–scanning electron microscopy was used to monitor the structural evolution of individual Ge particles during lithiation. Our results show that there are two types of reaction fronts during lithiation, representing the differences of reactions on the surface and in bulk. The cross-sectional SEM images and transmission electron microscopy characterizations show that the interface between amorphous LixGe and Ge has a wedge shape because of the higher Li transport rate on the surface of the particle. The blade-type reaction front is formed at the interface of the amorphous LixGe and crystalline Ge and is attributed to the large strain at the interface

Transition metal-doped Ni-rich layered cathode materials for durable Li-ion batteries

Doping is a well-known strategy to enhance the electrochemical energy storage performance of layered cathode materials. Many studies on various dopants have been reported; however, a general relationship between the dopants and their effect on the stability of the positive electrode upon prolonged cell cycling has yet to be established. Here, we explore the impact of the oxidation states of various dopants (i.e., Mg2+, Al3+, Ti4+, Ta5+, and Mo6+) on the electrochemical, morphological, and structural properties of a Ni-rich cathode material (i.e., Li[Ni0.91Co0.09]O2). Galvanostatic cycling measurements in pouch-type Li-ion full cells show that cathodes featuring dopants with high oxidation states significantly outperform their undoped counterparts and the dopants with low oxidation states. In particular, Li-ion pouch cells with Ta5+- and Mo6+-doped Li[Ni0.91Co0.09]O2 cathodes retain about 81.5% of their initial specific capacity after 3000 cycles at 200???mA???g???1. Furthermore, physicochemical measurements and analyses suggest substantial differences in the grain geometries and crystal lattice structures of the various cathode materials, which contribute to their widely different battery performances and correlate with the oxidation states of their dopants

In Situ and Operando Investigation of the Dynamic Morphological and Phase Changes of Selenium-doped Germanium Electrode during (De)Lithiation Processes

To understand the effect of selenium doping on the good cycling performance and rate capability of a Ge0.9Se0.1 electrode, the dynamic morphological and phase changes of the Ge0.9Se0.1 electrode were investigated by synchrotron-based operando transmission X-ray microscopy (TXM) imaging, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The TXM results show that the Ge0.9Se0.1 particle retains its original shape after a large volume change induced by (de)lithiation and undergoes a more sudden morphological and optical density change than pure Ge. The difference between Ge0.9Se0.1 and Ge is attributed to a super-ionically conductive Li–Se–Ge network formed inside Ge0.9Se0.1 particles, which contributes to fast Li-ion pathways into the particle and nano-structuring of Ge as well as buffering the volume change of Ge. The XRD and XAS results confirm the formation of a Li–Se–Ge network and reveal that the Li–Se–Ge phase forms during the early stages of lithiation and is an inactive phase. The Li–Se–Ge network also can suppress the formation of the crystalline Li15Ge4 phase. These in situ and operando results reveal the effect of the in situ formed, super-ionically conductive, and inactive network on the cycling performance of Li-ion batteries and shed light on the design of high capacity electrode materials

Surface Alloy Composition Controlled O₂ Activation on Pd–Au Bimetallic Model Catalysts

Oxygen is an important reactant in several catalytic conversions and partial oxidation reactions on Pd–Au alloy surfaces; however, adsorption and dissociation are not fully understood, especially as a function of the surface alloy composition. In this study, we probe the influence of the atomic makeup of the surface of Pd–Au catalysts regarding control of the catalytic activity toward O₂ dissociation and the reactivity of the resulting oxygen adatoms. To experimentally investigate this, we prepared various bimetallic surfaces under ultrahigh vacuum via evaporation of Pd onto a Au(111) surface. Hydrogen molecules were used to characterize the composition of the Pd–Au surfaces, which we simplistically group into two categories: (i) Pd–Au interface sites and (ii) Pd(111)-like island sites. When the Pd coverage is 1.0 ML, which predominantly indicates Pd–Au interface sites, no dissociative adsorption of O₂ at 300 K is observed, but dissociation begins to be measurable on the surfaces with larger Pd loadings (greater than 1.5 ML), which we believe leads to Pd(111)-like islands on the surface. We also find that adsorbed oxygen atoms are very reactive at the Pd–Au interface sites via measurements of the CO oxidation reaction at relatively low temperatures (<200 K); however, CO oxidation can also take place at higher temperatures (∼400 K) and in this case is very dependent on Pd coverage, being strongly related to the number of Pd­(111)-like islands, which bind O_a relatively strongly. From our experimental results, we estimate the barrier to dissociation of O₂ and also the CO oxidation reaction barrier, which is an indirect measure of the reactivity of the adsorbed atomic oxygen. From our analysis, we find that, upon increasing Pd coverage, the dissociation barrier for O₂ steadily decreases and, further, the reaction barrier for CO oxidation continuously increases. Finally, oxygen molecularly adsorbs on the Pd–Au bimetallic surface and is a precursor to dissociative O₂ chemisorption, just as with pure Pd surfaces, and additionally, the enhanced reactivity of adsorbed atomic oxygen originates at the interfaces between Pd and Au domains

Sub-stoichiometric, chalcogen-containing-germanium, tin, or lead anodes for lithium or sodium ion batteries

The disclosure relates to an anode or an electrolytic capacitor electrode including an active anode material containing a chalcogen-containing-germanium composition in which the germanium:chalcogen atom ratio is between 80:20 and 98:2. The disclosure also relates to an anode including an active anode material containing a lithium and germanium-containing alloy wherein the lithium:germanium atom ratio is 22:5 or less. The anode also includes a non-cycling lithium chalcogenide. The disclosure further relates to lithium ion batteries including such anodes. The disclosure additionally relates to capacitor electrodes containing similar materials and capacitors containing such electrodes.Board of Regents, University of Texas Syste

Hydrogen Adsorption and Absorption with Pd–Au Bimetallic Surfaces

Pd–Au bimetallic catalysts have shown promising performance in numerous reactions that involve hydrogen. Fundamental studies of hydrogen interactions with Pd–Au surfaces could provide useful insights into the reaction mechanisms over Pd–Au catalysts, which may, in turn, guide future catalyst design. In this study, the interactions of hydrogen (i.e., adsorption, absorption, diffusion, and desorption) with Pd/Au(111) model surfaces were studied using temperature-programmed desorption (TPD) under ultrahigh-vacuum conditions. Our experimental results reveal Pd–Au bimetallic surfaces readily dissociate H₂ and yet also weakly bind H adatoms, properties that could be beneficial for catalytic reactions involving hydrogen. The presence of contiguous Pd sites, characterized by reflection–absorption infrared spectroscopy using CO as a probe molecule (CO-RAIRS), was found to be vital for the dissociative adsorption of H₂ at 77 K. The H adatom binds to Pd–Au alloy sites more strongly than to Au(111) but more weakly than to Pd(111) as indicated by its desorption temperature (∼200 K). With hydrogen exposure at slightly higher temperatures (i.e., 100–150 K), extension of a low-temperature desorption feature was observed, suggesting the formation of subsurface H atoms (or H absorption). Experiments using deuterium indicate that H–D exchange over the Pd–Au bimetallic surface obeys Langmuir–Hinshelwood kinetics and that H/D adatoms are mobile on the surface at low temperatures