76 research outputs found
Real space investigation of structural changes at the metal-insulator transition in VO2
Synchrotron X-ray total scattering studies of structural changes in rutile
VO2 at the metal-insulator transition temperature of 340 K reveal that
monoclinic and tetragonal phases of VO2 coexist in equilibrium, as expected for
a first-order phase transition. No evidence for any distinct intermediate phase
is seen. Unbiased local structure studies of the changes in V--V distances
through the phase transition, using reverse Monte Carlo methods, support the
idea of phase coexistence and point to the high degree of correlation in the
dimerized low-temperature structure. No evidence for short range V--V
correlations that would be suggestive of local dimers is found in the metallic
phase.Comment: 4 pages, 5 figure
Determining conductivity and mobility values of individual components in multiphase composite Cu_(1.97)Ag_(0.03)Se
The intense interest in phase segregation in thermoelectrics as a means to reduce the lattice thermal conductivity and to modify the electronic properties from nanoscale size effects has not been met with a method for separately measuring the properties of each phase assuming a classical mixture. Here, we apply effective medium theory for measurements of the in-line and Hall resistivity of a multiphase composite, in this case Cu_(1.97) Ag_(0.03)Se. The behavior of these properties with magnetic field as analyzed by effective medium theory allows us to separate the conductivity and charge carrier mobility of each phase. This powerful technique can be used to determine the matrix properties in the presence of an unwanted impurity phase, to control each phase in an engineered composite, and to determine the maximum carrier concentration change by a given dopant, making it the first step toward a full optimization of a multiphase thermoelectric material and distinguishing nanoscale effects from those of a classical mixture
Understanding complex magnetic order in disordered cobalt hydroxides through analysis of the local structure
In many ostensibly crystalline materials, unit-cell-based descriptions do not
always capture the complete physics of the system due to disruption in
long-range order. In the series of cobalt hydroxides studied here,
Co(OH)(Cl)(HO), magnetic Bragg diffraction reveals a
fully compensated N\'eel state, yet the materials show significant and open
magnetization loops. A detailed analysis of the local structure defines the
aperiodic arrangement of cobalt coordination polyhedra. Representation of the
structure as a combination of distinct polyhedral motifs explains the existence
of locally uncompensated moments and provides a quantitative agreement with
bulk magnetic measurements and magnetic Bragg diffraction
Tuning magnetic frustration on the diamond lattice of the A-site magnetic spinels CoAlGaO: Lattice expansion and site disorder
The spinels CoBO with magnetic Co ions on the diamond lattice
A site can be frustrated because of competing near-neighbor () and
next-near neighbor () interactions. Here we describe attempts to tune the
relative strengths of these interactions by substitution on the non-magnetic
B-site. The system we employ is CoAlGaO, where Al is
systematically replaced by the larger Ga, ostensibly on the B site. As
expected, Ga substitution expands the lattice, resulting in Co atoms on the
A-site being pushed further from one other and thereby weakening magnetic
interactions. In addition, Ga distributes between the B and the A site in a
concentration dependent manner displacing an increasing amount of Co from the A
site with increasing . This increased inversion, which is confirmed by
neutron diffraction studies carried out at room temperature, affects magnetic
ordering very significantly, and changes the nature of the ground state.
Modeling of the magnetic coupling illustrates the complexity that arises from
the cation site disorder.Comment: 9 pages, 10 figure
Influence of rotational distortions on Li<sup>+</sup>-Â and Na<sup>+</sup>- intercalation in anti-NASICON Fe<sub>2</sub>(MoO<sub>4</sub>)<sub>3</sub>
Anti-NASICON
Fe<sub>2</sub>(MoO<sub>4</sub>)<sub>3</sub> (<i>P</i>2<sub>1</sub>/<i>c</i>) shows significant structural
and electrochemical differences in the intercalation of Li<sup>+</sup> and Na<sup>+</sup> ions. To understand the origin of this behavior,
we have used a combination of in situ X-ray and high-resolution neutron
diffraction, total scattering, electrochemical measurements, density
functional theory calculations, and symmetry-mode analysis. We find
that for Li<sup>+</sup>-intercalation, which proceeds via a two-phase
monoclinic-to-orthorhombic (<i>Pbcn</i>) phase transition,
the host lattice undergoes a concerted rotation of rigid polyhedral
subunits driven by strong interactions with the Li<sup>+</sup> ions,
leading to an ordered lithium arrangement. Na<sup>+</sup>-intercalation,
which proceeds via a two-stage solid solution insertion into the monoclinic
structure, similarly produces rotations of the lattice polyhedral
subunits. However, using a combination of total neutron scattering
data and density functional theory calculations, we find that while
these rotational distortions upon Na<sup>+</sup>-intercalation are
fundamentally the same as for Li<sup>+</sup>-intercalation, they result
in a far less coherent final structure, with this difference attributed
to the substantial difference between the ionic radii of the two alkali
metals
Lithium-ion conductivity in Li<sub>6</sub>Y(BO<sub>3</sub>)<sub>3</sub>:a thermally and electrochemically robust solid electrolyte
The development of new frameworks for solid electrolytes that exhibit fast Li-ion diffusion is critical for enabling new energy storage technologies. Here, we present a combined experimental and computational investigation into the ionic conductivity of Li6Y(BO3)3, a new class of solid electrolytes with a pseudo-layered structure. Temperature-dependent impedance spectroscopy shows the pristine material exhibits an ionic conductivity of 2.2×10-3 S/cm&#x100000; around 400°C, while density functional theory calculations point to multiple remarkably low-energy diffusion pathways. Our calculations indicate small energy barriers for lithium interstitials to diffuse along one-dimensional channels oriented in the c-direction, and also for lithium vacancies diffusing within ac planes. This coexistence of diffusion mechanisms indicates that Li6Y(BO3)3 is an extremely versatile host for exploring and understanding mechanisms for lithium-ion conductivity. We find no evidence for reactivity with moisture in the atmosphere and that the material is electrochemically stable when in direct contact with metallic lithium. This robust stability, alongside ionic conductivity that can be manipulated through appropriate aliovalent substitution, make Li6Y(BO3)3 an exceptionally promising new class of solid electrolyte
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