Hydration and Hydroxylation of MgO in Solution: NMR Identification of Proton-Containing Intermediate Phases
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Kinetics and intermediate phases in epitaxial growth of Fe{sub 3}O{sub 4} films from deposition and thermal reduction
We have studied the kinetics of the transitions between the Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} phases as thin epilayers (∼2.5 nm) on Al{sub 2}O{sub 3} (001) substrates using time-resolved reflection high energy electron diffraction. The different iron oxide phases were identified using a combination of in-situ and ex-situ characterizations. The transition from an α-Fe{sub 2}O{sub 3} (001) epilayer to a Fe{sub 3}O{sub 4} (111) epilayer through thermal reduction was found to be determined by the Fe-O bonding energy, resulting in a long time scale. The oxidation at high temperature converts a Fe{sub 3}O{sub 4} (111) epilayer to an α-Fe{sub 2}O{sub 3} (001) epilayer quickly; at low temperature, a γ-Fe{sub 2}O{sub 3} (111) epilayer was slowly generated instead. By repeating the deposition/thermal reduction processes, a thicker Fe{sub 3}O{sub 4} (111) film was obtained, which exhibit high crystallinity and moderate magnetic coercivity.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Numerical Study of Quantum Hall Bilayers at Total Filling ν T = 1 : A New Phase at Intermediate Layer Distances
We view the phase diagram of quantum Hall bilayer systems with total filing ν T = 1/2 + 1/2 of the lowest Landau level as a function of layer distances d . Based on numerical exact diagonalization calculations, we obtain three distinct phases, including an exciton superfluid phase with spontaneous interlayer coherence at small d , a composite Fermi liquid at large d , and an intermediate phase for 1.1 < d/l B < 1.8 (l B is the magnetic length). The transition from the exciton superfluid to the intermediate phase is identified by (i) a dramatic change in the Berry curvature of the ground state under twisted boundary conditions on the two layers and (ii) an energy level crossing of the first excited state. The transition from the intermediate phase to the composite Fermi liquid is identified by the vanishing of the exciton superfluid stiffness. Moreover, from our finite-size study, the energy cost of transferring one electron between the layers shows an even-odd effect and possibly extrapolates to a finite value in the thermodynamic limit, indicating the enhanced intralayer correlation. Our identification of an intermediate phase and its distinctive features shed new light on the theoretical understanding of the quantum Hall bilayer system at total filling ν T = 1 .
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Revealing the Conversion Mechanism of Transition Metal Oxide Electrodes during Lithiation from First-Principles
Transition metal oxides such as Co3O4 and NiO are of significant interest as conversion anode materials for lithium-ion batteries (LIBs), due to their remarkably high theoretical capacities and low cost. While many previous experiments have found that the charge/discharge reactions of Co3O4 and NiO can be highly reversible, detailed information about the mechanisms of these reactions, such as the origin of the voltage hysteresis (>1.0 V) between the charge/discharge cycles, is still poorly understood. In this work, we develop and utilize a new computational mechanistic approach that helps elucidate the hysteresis and nonequilibrium reaction pathways associated with these conversion materials. We apply this methodology to investigate a variety of lithiation reaction pathways of Co3O4 and NiO by systematically exploring the energetics of a large number of equilibrium and nonequilibrium LixCo3O4 (0 ≤ x ≤ 8) and LixNiO (0 ≤ x ≤ 2) structural configurations using first-principles calculations. The overall value of the voltages from our nonequilibrium pathway is in much better agreement with experimental lithiation than the calculated equilibrium voltage while the overall value of the latter reasonably agrees with experimental delithiation. Hence, we propose the charge and discharge processes proceed through equilibrium and nonequilibrium reaction paths, respectively, which contribute significantly to the experimentally observed voltage hysteresis in Co3O4 and NiO. Additionally, we find a low-energy, lithiated intermediate phase (Li3Co3O4) with an oxygen framework equal to that of the initial Co3O4 spinel phase. This intermediate phase represents the capacity threshold below which limited volume expansion and better reversibility can be realized and above which reactions lead to structural degradation and huge expansion.
Yao, Zhenpeng↗
Thermal properties and phase transition in the fluoride, (NH{sub 4}){sub 3}SnF{sub 7}
Calorimetric, dilatometric and differential thermal analysis studies were performed on (NH{sub 4}){sub 3}SnF{sub 7} for a wide range of temperatures and pressures. Large entropy (δS{sub 0}=22 J/mol K) and elastic deformation (δ(ΔV/V){sub 0}=0.89%) jumps have proven that the Pa-3↔Pm-3m phase transition is a strong first order structural transformation. A total entropy change of ΔS{sub 0}=32.5 J/mol K is characteristic for the order–disorder phase transition, and is equal to the sum of entropy changes in the related material, (NH{sub 4}){sub 3}TiF{sub 7}, undergoing transformation between the two cubic phases through the intermediate phases. Hydrostatic pressure decreases the stability of the high temperature Pm-3m phase in (NH{sub 4}){sub 3}SnF{sub 7}, contrary to (NH{sub 4}){sub 3}TiF{sub 7}, characterised by a negative baric coefficient. The effect of experimental conditions on the chemical stability of (NH{sub 4}){sub 3}SnF{sub 7} was observed. - Graphical abstract: Strong first order structural transformation Pa-3↔Pm-3m in (NH{sub 4}){sub 3}SnF{sub 7} is associated with very large total entropy change of ΔS{sub 0}=32.5 J/mol K characteristic for the ordering processes and equal to the sum of entropy changes in the related (NH{sub 4}){sub 3}TiF{sub 7} undergoing transformation between the same two cubic phases through the intermediate phases. - Highlights: • (NH{sub 4}){sub 3}SnF{sub 7} undergoes strong first order Pa-3↔Pm-3m phase transition. • Anomalous behaviour of ΔC{sub p} and ΔV/V exists far below phase transition temperature. • Structural distortions are accompanied by huge total entropy change ΔS≈Rln50. • High pressure strongly increases the stability of Pa-3 phase in (NH{sub 4}){sub 3}SnF{sub 7}. • Entropy of the Pa-3↔Pm-3m phase transition does not depend on pressure.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Pressure-induced phase transitions in acentric BaHf(BO{sub 3}){sub 2}
High-pressure Raman scattering studies revealed that BaHf(BO{sub 3}){sub 2} is more compressible than calcite-type orthoborates and calcite, aragonite or dolomite carbonates. It undergoes a first-order reversible pressure-induced phase transition in the 3.9–4.4 GPa pressure range. Second structural change is observed at 9.2 GPa. The intermediate phase is most likely trigonal. However, Raman results suggest increase in the number of distinct BO{sub 3} groups from two in the ambient pressure phase to at least three in the intermediate phase. This intermediate phase is also strongly compressible and strong pressure dependence of the lattice modes proves that the main changes under pressure occur within the layers built from BaO{sub 6} and HfO{sub 6} octahedra. The second phase transition leads most likely to lowering of the trigonal symmetry, as evidenced by significant increase of the number of observed bands. The pressure coefficients of the Raman bands of the high-pressure phase are relatively small, suggesting more dense arrangement of the metal–oxygen polyhedra and BO{sub 3} groups in this phase. It is worth noting that the high-pressure phase was not reached in the second compression experiment up to 10 GPa. This behavior can be most likely attributed to worse hydrostatic conditions of the first experiment. - Graphical abstract: Raman spectra of BaHf(BO{sub 3}){sub 2} recorded at different pressures during compression showing onset of pressure-induced phase transitions. - Highlights: • High-pressure Raman spectra were measured for BaHf(BO{sub 3}){sub 2.} • BaHf(BO{sub 3}){sub 2} undergoes a reversible first-order phase transition at 3.9–4.4 GPa into a trigonal phase. • The intermediate trigonal phase is strongly compressible second structural transformation is observed at 9.2 GPa under non-perfect hydrostatic conditions.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Uniform second Li ion intercalation in solid state ϵ-LiVOPO4
Full, reversible intercalation of two Li + has not yet been achieved in promising VOPO 4 electrodes. A pronounced Li + gradient has been reported in the low voltage window (i.e., second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e., first lithium reaction). Here, we employ a combination of hard and soft x–ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO 4 cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li + gradient, which combined with almost full theoretical capacity confirms that disrupted kinetics in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li + intercalation is a prerequisite for the formation of intermediate phases Li1.50VOPO 4 and Li 1.75 VOPO 4 . The evolution from LiVOPO 4 to Li 2 VOPO 4 via the intermediate phases is confirmed by direct comparison between O K–edge absorption spectroscopy and density functional theory.
25 ENERGY STORAGE↗
Computational and Experimental Characterization of Intermediate Amorphous Phases in Geological Materials
In the subsurface, MgO engineered barriers are employed at the Waste Isolation Pilot Plant (WIPP), a transuranic waste repository near Carlsbad, NM. During service, the MgO will be exposed to high concentration brine environments and may form stable intermediate phases that can alter the barriers effectiveness. Here, MgO was aged in water and three different brine solutions. X-ray diffraction (XRD) and 1 H nuclear magnetic resonance (NMR) analysis were performed to identify the formation of secondary phases. After aging, ~4% of the MgO was hydrated and fine-grained powders resulted in greater loss of crystallinity than hard granular grains. 1 H magic angle spinning (MAS) NMR spectra resolved minor phases not visible in XRD, indicating that diverse 1 H environments are present along with Mg(OH) 2 . Density functional theory (DFT) simulations for several proposed Mg-O-H, Mg-CI-O-H, and Na-O-H containing phases were performed to index peaks in the experimental 1 H MAS NMR spectra. While proposed intermediate crystal structures exhibited overlapping 1 H NMR peaks, Mg-O-H intermediates were attributed to the growth of the 1.0-0.0ppm peak while the Mg-CI-O-H structures contributed to the 2.5- 5.0ppm peak in the chloride containing brines. Overall, NMR analysis of aged MgO indicates the formation of a range of possible intermediate structures that cannot be resolved with XRD analysis alone.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Temperature-Dependent Intraband Relaxation of Hybrid Perovskites
Intraband relaxation in polycrystalline films of hybrid perovskites methylammonium lead tribromide and methylammonium lead triiodide are studied by transient absorption spectroscopy from 80 K to >350 K. This temperature range spans the transitions of these materials from the high-temperature cubic phases, intermediate tetragonal phases, and low-temperature orthorhombic phases. The organic cation undergoes a distinct transition from an ordered lattice in the orthorhombic phase to a plastic crystal in cubic and tetragonal phases, which reportedly influences many optoelectronic properties. The much larger exciton binding energy of orthorhombic MAPbI(3) (compared to cubic or tetragonal phases) or MAPbBr(3) substantially changes the transient spectral responses of the materials by reducing the number of free carriers. However, for these measurements at low fluences, both MAPbBr(3) and MAPbI(3) exhibit subpicosecond intraband relaxation over the entire temperature range studied. Intraband relaxation becomes somewhat faster at higher temperatures, but freezing of organic cations are not accompanied by a discontinuity of the intraband relaxation time. These results suggest that configurational freedom of organic cations does not screen carriers from electron-phonon coupling.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Damped spin waves in the intermediate ordered phases in Ni 3 V 2 O 8
Here, spin dynamics in the intermediate ordered phases (between 4 and 9 K) in Ni 3 V 2 O 8 have been studied with inelastic neutron scattering. It is found that the spin waves are very diffuse, indicative of short lived correlations and the coexistence of paramagnetic moments with the long-range ordered state.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Successive field-induced transitions in BiFeO 3 around room temperature
The effects of high magnetic fields applied perpendicular to the spontaneous ferroelectric polarization on single crystals of BiFeO 3 were investigated in this paper through magnetization, magnetostriction, and neutron diffraction measurements. The magnetostriction measurements revealed lattice distortion of 2 x 10 -5 during the reorientation process of the cycloidal spin order by applied magnetic fields. Furthermore, anomalous changes in magnetostriction and electric polarization at a larger field demonstrate an intermediate phase between cycloidal and canted antiferromagnetic states, where a large magnetoelectric effect was observed. Neutron diffraction measurements clarified that incommensurate spin modulation along the [110] hex direction in the cycloidal phase becomes Q = 0 commensurate along this direction in the intermediate phase. Finally, theoretical calculations based on the standard spin Hamiltonian of this material suggest an antiferromagnetic cone-type spin order in the intermediate phase.
36 MATERIALS SCIENCE↗
Topological Phase Transitions in Multicomponent Superconductors
We study the phase transition between a trivial and a time-reversal-invariant topological superconductor in a single-band system. By analyzing the interplay of symmetry, topology, and energetics, we show that for a generic normal state band structure, the phase transition occurs via extended intermediate phases in which even- and odd-parity pairing components coexist. For inversion-symmetric systems, the coexistence phase spontaneously breaks time-reversal symmetry. For noncentrosymmetric superconductors, the low-temperature intermediate phase is time-reversal breaking, while the high-temperature phase preserves time-reversal symmetry and has topologically protected line nodes. Furthermore, with approximate rotational invariance, the system has an emergent U (1) × U (1) symmetry, and novel topological defects, such as half vortex lines binding Majorana fermions, can exist. We analytically solve for the dispersion of the Majorana fermion and show that it exhibits small and large velocities at low and high energies. Finally, relevance of our theory to superconducting pyrochlore oxide Cd 2 Re 2 O 7 and half-Heusler materials is discussed.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Factors Contributing to Path Hysteresis of Displacement and Conversion Reactions in Li Ion Batteries
In this article, we investigate the thermodynamic and kinetic attributes of electrode materials that are necessary to suppress path hysteresis during displacement and conversion reactions in Li ion batteries. We focus on compounds in the Li–Cu–Sb ternary composition space, as the displacement reaction between Li 1+ϵ Cu 1+δ Sb and Li 3 Sb can be cycled reversibly. A first-principles analysis of migration barriers indicates that Cu, while not as mobile as Li in the discharged phase (Li 3 Sb), nevertheless should exhibit mobilities similar to that of Li in common intercalation compounds. A calculation of phase stability in the ternary Li–Cu–Sb system predicts that the intermediate phases along the reversible charge/discharge path are stable in a large Cu chemical potential window. This ensures that intermediate phases are not bypassed upon Li extraction even when large thermodynamic driving forces are needed to reinsert Cu into the discharged electrode. Our study suggests that the suppression of path hysteresis during displacement reactions requires (i) a high mobility of the displaced metal and (ii) the thermodynamic stability of intermediate phases along the reversible path in a wide metal chemical potential window. Even in the absence of path hysteresis, displacement and conversion reactions suffer from polarization needed to set up thermodynamic driving forces for metal extrusion and reinsertion. This polarization can be estimated with a Clausius–Clapeyron analysis.
25 ENERGY STORAGE↗
Unified phase diagram of antiferromagnetic SU( N ) spin ladders
Motivated by near-term experiments with ultracold alkaline-earth atoms confined to optical lattices, we establish numerically and analytically the phase diagram of two-leg SU ( N ) spin ladders. Two-leg ladders provide a rich and highly nontrivial extension of the single chain case on the way towards the relatively little explored two-dimensional situation. Focusing on the experimentally relevant limit of one fermion per site, antiferromagnetic exchange interactions, and 2 ≤ N ≤ 6, we show that the phase diagrams as a function of the interchain (rung) to intrachain (leg) coupling ratio, J ⊥ /J ∥ , strongly differ for even versus odd N. For even N = 4 and 6, we demonstrate that the phase diagram consists of a single valence bond crystal (VBC) with a spatial period of N/2 rungs. For odd N = 3 and 5, we find surprisingly rich phase diagrams exhibiting three distinct phases. For weak rung coupling, we obtain a VBC with a spatial period of N rungs, whereas for strong coupling we obtain a critical phase related to the case of a single chain. In addition, we encounter intermediate phases for odd N, albeit of a different nature for N = 3 as compared to N = 5. For N = 3, we find a novel gapless intermediate phase with J ⊥ -dependent incommensurate spatial fluctuations in a sizeable region of the phase diagram. For N = 5 , there are strong indications for a narrow potentially gapped intermediate phase, whose nature is not entirely clear. Lastly, our results are based on (i) field theoretical techniques, (ii) qualitative symmetry considerations, and (iii) large-scale density matrix renormalization group (DMRG) simulations keeping beyond a million of states by fully exploiting and thus preserving the SU (N) symmetry.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
A study of suppressed formation of low-conductivity phases in doped Li 7 La 3 Zr 2 O 12 garnets by in situ neutron diffraction
Doped Li 7 La 3 Zr 2 O 12 garnets, oxide-based solids with good Li + conductivity and compatibility, show great potential as leading electrolyte material candidates for all-solid-state lithium ion batteries. Still yet, the conductive bulk usually suffers from the presence of secondary phases and the transition towards a low-conductivity tetragonal phase during synthesis. Dopants are designed to stabilize the high-conductive cubic phase and suppress the formation of the low-conductivity phases. In situ neutron diffraction enables a direct observation of the doping effects by monitoring the phase evolutions during garnet synthesis. It reveals the reaction mechanism involving the temporary presence of intermediate phases. The off-stoichiometry due to the liquid Li 2 CO 3 evaporation leads to the residual of the low-conductivity intermediate phase in the as-synthesized bulk. Appropriate doping of an active element may alter the component of the intermediate phases and promote the completion of the reaction. While the dopants aid to stabilize most of the cubic phase, a small amount of tetragonal phase tends to form under a diffusion process. Lastly, the in situ observations provide the guideline of process optimization to suppress the formation of unwanted low-conductivity phases.
36 MATERIALS SCIENCE↗
Probing microstructure and phase evolution of α-MoO 3 nanobelts for sodium-ion batteries by in situ transmission electron microscopy
The fundamental electrochemical reaction mechanisms and the phase transformation pathways of layer-structured α-MoO 3 nanobelt during the sodiation/desodiation process to date remain largely unknown. In this study, to observe the real-time sodiation/desodiaton behaviors of α-MoO 3 during electrochemical cycling, we construct a MoO 3 anode sodium-ion battery inside a transmission electron microscope (TEM). Utilizing in situ TEM and electron diffraction pattern (EDP) observation, α-MoO 3 nanobelts are found to undergo a unique multi-step phase transformation. Upon the first sodiation, α-MoO 3 nanobelts initially form amorphous Na x MoO3 phase and are subsequently sodiated into intermediate phase of crystalline NaMoO 2 , finally resulting in the crystallized Mo nanograins embedded within the Na 2 O matrix. During the first desodiation process, Mo nanograins are firstly re-oxidized into intermediate phase NaMoO 2 that is further transformed into amorphous Na 2 MoO 3 , resulting in an irreversible phase transformation. Upon subsequent sodiation/desodiation cycles, however, a stable and reversible phase transformation between crystalline Mo and amorphous Na2MoO 3 phases has been revealed. In conclusion, our work provides an in-deepth understanding of the phase transformation pathways of α-MoO 3 nanobelts upon electrochemical sodiation/desodiation processes, with the hope of assistance in designing sodium-ion batteries with enhanced performance.
36 MATERIALS SCIENCE↗
Analysis of the surface of tricalcium silicate during the induction period by X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy allows the analysis of surface layers with a thickness of a few nanometers. The method is sensitive to the chemical environment of the atoms since the binding energy of the electrons depends on the chemical bonds to neighboring atoms. It has been applied to the hydration of tricalcium silicate (Ca{sub 3}SiO{sub 5}, C{sub 3}S) by analyzing a sample after 30 min of hydration. Also two references have been investigated namely anhydrous C{sub 3}S and intermediate phase in order to enable a quantitative evaluation of the experimental data. In the hydrated C{sub 3}S sample, the analyzed volume (0.2 mm{sup 2} surface by 13 nm depth) contained approximately 44 wt.% of C{sub 3}S and 56 wt.% of intermediate phase whereas C-S-H was not detected. Scanning Electron Microscopy data and geometric considerations indicate that the intermediate phase forms a thin layer having a thickness of approximately 2 nm and covers the complete surface instead of forming isolated clusters.
36 MATERIALS SCIENCE↗
Modern insights into the mechanisms of neptunium oxalate decomposition
Neptunium oxalate (Np(C 2 O 4 ) 2 ·6H 2 O) is a historically relevant solid phase used in nuclear processing as a precursor for neptunium dioxide (NpO 2 ). Although Np oxalate has been synthesized and used for NpO 2 production for decades, the thermal decomposition mechanism of this phase remains poorly understood and has not been evaluated in over 30 years. Conflicting reports in historical literature suggest either a direct conversion from anhydrous oxalate to NpO 2 or a decomposition that includes the formation of Np carbonate or oxidized Np intermediate phases. In this work, we reexamine the decomposition pathway of Np(C 2 O 4 ) 2 ·6H 2 O using thermal analysis coupled with evolved gas analysis and temperature-dependent Raman spectroscopy to elucidate decomposition mechanisms and intermediate phases using modern analytical techniques. Thermal analysis revealed a three-stage decomposition process, including dehydration below 200 °C, oxalate breakdown between 170 and 370 °C, and NpO 2 formation by 500 °C. However, an unidentified plateau in the thermal data was observed during measurements. Raman spectroscopy confirmed the stages of decomposition, and in the analysis of potential intermediate phases, no carbonate phases or Np 2 O 5 were identified. Raman data suggest that residual oxalate or nonstoichiometric oxide are present during decomposition before pure NpO 2 is formed. These findings clarify aspects of the Np oxalate decomposition mechanism and address longstanding discrepancies in the literature, with a specific focus on Np-specific materials chemistry.
Lawson, Kathryn M. [Oak Ridge National Laboratory ↗