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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 667 records · Page 37
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Phase engineering of layered anode materials during ion-intercalation in Van der Waal heterostructures

Transition metal dichalcogenides (TMDs) are a class of 2D materials demonstrating promising properties, such as high capacities and cycling stabilities, making them strong candidates to replace graphitic anodes in lithium-ion batteries. However, certain TMDs, for instance, MoS 2 , undergo a phase transformation from 2H to 1T during intercalation that can affect the mobility of the intercalating ions, the anode voltage, and the reversible capacity. In contrast, select TMDs, for instance, NbS 2 and VS 2 , resist this type of phase transformation during Li-ion intercalation. This manuscript uses density functional theory simulations to investigate the phase transformation of TMD heterostructures during Li-, Na-, and K-ion intercalation. The simulations suggest that while stacking MoS 2 layers with NbS 2 layers is unable to limit this 2H → 1T transformation in MoS 2 during Li-ion intercalation, the interfaces effectively stabilize the 2H phase of MoS 2 during Na- and K-ion intercalation. However, stacking MoS 2 layers with VS 2 is able to suppress the 2H → 1T transformation of MoS 2 during the intercalation of Li, Na, and K-ions. The creation of TMD heterostructures by stacking MoS 2 with layers of non-transforming TMDs also renders theoretical capacities and electrical conductivities that are higher than that of bulk MoS 2 .

25 ENERGY STORAGE↗
DOE OSTI2014

Calculations of single crystal elastic constants for yttria partially stabilised zirconia from powder diffraction data

Yttria Stabilised Zirconia (YSZ) is a tough, phase-transforming ceramic that finds use in a wide range of commercial applications from dental prostheses to thermal barrier coatings. Micromechanical modelling of phase transformation can deliver reliable predictions in terms of the influence of temperature and stress. However, models must rely on the accurate knowledge of single crystal elastic stiffness constants. Some techniques for elastic stiffness determination are well-established. The most popular of these involve exploiting frequency shifts and phase velocities of acoustic waves. However, the application of these techniques to YSZ can be problematic due to the micro-twinning observed in larger crystals. Here, we propose an alternative approach based on selective elastic strain sampling (e.g., by diffraction) of grain ensembles sharing certain orientation, and the prediction of the same quantities by polycrystalline modelling, for example, the Reuss or Voigt average. The inverse problem arises consisting of adjusting the single crystal stiffness matrix to match the polycrystal predictions to observations. In the present model-matching study, we sought to determine the single crystal stiffness matrix of tetragonal YSZ using the results of time-of-flight neutron diffraction obtained from an in situ compression experiment and Finite Element modelling of the deformation of polycrystalline tetragonal YSZ. The best match between the model predictions and observations was obtained for the optimized stiffness values of C11 = 451, C33 = 302, C44 = 39, C66 = 82, C12 = 240, and C13 = 50 (units: GPa). Considering the significant amount of scatter in the published literature data, our result appears reasonably consistent.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Local chemical fluctuation mediated ultra-sluggish martensitic transformation in high-entropy intermetallics

Superelasticity associated with martensitic transformation has found a broad range of engineering applications, such as in low-temperature devices in the aerospace industry. Nevertheless, the narrow working temperature range and strong temperature sensitivity of the first-order phase transformation significantly hinder the usage of smart metallic components in many critical areas. Here, we scrutinized the phase transformation behavior and mechanical properties of multicomponent B2-structured intermetallic compounds. Strikingly, the (TiZrHfCuNi) 83.3 Co 16.7 high-entropy intermetallics (HEIs) show superelasticity with high critical stress over 500 MPa, high fracture strength of over 2700 MPa, and small temperature sensitivity in a wide range of temperatures over 220 K. The complex sublattice occupation in these HEIs facilitates formation of nano-scaled local chemical fluctuation and then elastic confinement, which leads to an ultra-sluggish martensitic transformation. The thermal activation of the martensitic transformation was fully suppressed while the stress activation is severely retarded with an enhanced threshold stress over a wide temperature range. Moreover, the high configurational entropy also results in a small entropy change during phase transformation, consequently giving rise to the low temperature sensitivity of the superelasticity stress. Furthermore, our findings may provide a new paradigm for the development of advanced superelastic alloys, and shed new insights into understanding of martensitic transformation in general.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Heavy ion irradiation-induced microstructural evolution in pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} at room temperature and 723 K

Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} at room temperature and 723 K to a fluence of 4×10{sup 15} ions/cm{sup 2}, corresponding to an average ballistic damage dose of 10 displacements per atom in the peak damage region. Irradiation-induced microstructural evolution was examined by grazing incidence X-ray diffraction, and cross-sectional transmission electron microscopy. Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal which has the identical structure of pyrochlore, and the formation of nano-crystal is attributed to the mechanism of epitaxial recrystallization. However, an ordered pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Graphical Abstract: Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} to a fluence of 4×10{sup 15} ions/cm{sup 2} at room temperature and 723 K, Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal. However, an ordered pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Highlights: Pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated by heavy ions at RT and 723 K. At RT irradiation, ~75% of amorphization was achieved. The nano-crystals were formed in the damage layer at RT irradiation. The formed nano-crystals enhanced the radiation tolerance of Lu{sub 2}Ti{sub 2}O{sub 7}. A pyrochlore to fluorite phase transformation was observed at 723 K irradiation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Phases, phase equilibria, and phase rules in low-dimensional systems

We present a unified approach to thermodynamic description of one, two, and three dimensional phases and phase transformations among them. The approach is based on a rigorous definition of a phase applicable to thermodynamic systems of any dimensionality. Within this approach, the same thermodynamic formalism can be applied for the description of phase transformations in bulk systems, interfaces, and line defects separating interface phases. For both lines and interfaces, we rigorously derive an adsorption equation, the phase coexistence equations, and other thermodynamic relations expressed in terms of generalized line and interface excess quantities. As a generalization of the Gibbs phase rule for bulk phases, we derive phase rules for lines and interfaces and predict the maximum number of phases than may coexist in systems of the respective dimensionality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Influence of rapid heating and cooling combined with deformation at ultrahigh strain rates on the microstructure evolution of pure titanium shaped charge liner

Highlights: • A slug prepared from pure titanium SCL was recovered after detonation deformation at an ultrahigh strain rate over 10{sup 5} s{sup −1}. • The α → β → α phase transformation occurred in Ti SCL during the ultrahigh-strain -rate deformation. • The microstructures of the recovered slug included lamellar α grains, equiaxed α grains, and jagged α grains. - Abstract: A slug prepared from pure titanium shaped charge liners was recovered after detonation deformation at an ultrahigh strain rate over 10{sup 5} s{sup −1} and high strain over 500%. Optical microscopy, electron backscattered diffraction (EBSD), and transmission electron microscopy (TEM) were employed to investigate the microstructure of the Ti shaped charged liner before and after the detonation deformation. The microstructures of the recovered slug include lamellar α grains, equiaxed α grains within localized shear bands, and jagged α grains. EBSD results indicated that the grain orientation distribution is random and no texture was observed in the slug. TEM observation revealed that the α → β → α phase transformation occurred owing to the rapid heating and cooling combined with deformation at ultrahigh strain rates in the Ti shaped charge liner. No melting phenomenon was observed during the deformation process. The deformation process consisted of the explosive detonation stage combined with rapid heating and the subsequent penetration stage combined with rapid cooling. In the explosive detonation stage, the α → β phase transformation instantaneously occurred via a martensitic mechanism. In the penetration stage, the high-temperature slug in β state was cooled rapidly and showed different deformation behaviors in three different areas.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Influence of processing on secondary phase formation and microstructural evolution at U-10Mo alloy and Zr interlayer interfaces

Thermo-mechanical processing of uranium-10 wt. % molybdenum (U-10Mo) fuel plates leads to microstructure changes at the U-10Mo/Zr interfaces. Secondary phases formed at this interface are particularly important to interfacial bond strength, process optimization, and maintaining structural integrity of the U-10Mo fuel plates during irradiation. In this work, we determined the phases and phase transformation products occurring at the interface of the U-10Mo fuel and Zr interlayer when the fuel plate is subjected to short and long hot isostatic pressure times. Interfacial morphology, structure and composition of phases formed, and relative hardness across the U-10Mo/Zr interfaces were studied using a multi-length scale, multi-modal characterization approach involving electron microscopy, atom probe tomography, and atomic force microscopy. Here, results highlight that the extent of phase transformations, secondary phase formation, and hardness variability across interfaces can be controlled by modifying processing parameters. Phase diagram construction and thermodynamic calculations were performed using the Thermocalc software to identify expected phases formed at interfaces during the maximum hold temperature of 560 °C experienced during HIP.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2018

Modular Controllable Transformers (MCT)

Large Power Transformers (LPTs) are at the heart of the electricity infrastructure and are critical pieces in today’s grid. Aging assets, long turn-around times, transportation delays and dependence on foreign manufacturing for these components have created conditions for points of failure across the system. Moreover, there is no available dynamic control on these passive sections of the grid. For all the automation embedded on the low voltage side of the low voltage side of the system there is absolutely no flexibility on the high voltage side. Changes in power flow patterns are brought about by altering dispatch patterns for generators which requires a coordinated effort and is often time consuming. Traditional FACTS based approaches such as UPFC or HVDC light involve massive modifications to the existing infrastructure. Recent instances of physical attacks on LPTs and the slow recovery process associated with fixing or replacing these damaged units has created an increased awareness for this issue. LPT designs are highly customized owing to specific field requirements. Long lead times coupled with transportation delays make procuring and installing LPTs a lengthy process. In an attempt to minimize the recovery time following an LPT failure, transformer manufacturers have developed mobile transformer units. These units typically consist of either a single-phase or three-phase transformer mounted on a truck and characterized by compact form factors. By reducing the assembly time and transport time these units offer a fast and temporary solution to LPT failures. Several efforts led by DOE, Edison Electric Company (EEI) and North American Electric Reliability Corporation (NERC) have led to the RecX program. RecX transformers consist of single phase transformers transported on specialized assemblies to enable fast restoration and minimal installation time. NERC and EEI have instituted transformer sharing programs like Spare Equipment Database (SED) as well as Spare Transformer Equipment Database (STEP) which encourage utilities to maintain and share a fleet of LPTs. Mobile transformers are typically limited to less than 100 MVA to enable transportation on a trailer. Also, the efficiency of mobile transformer units and RecX transformers is lower since they are temporary solutions. The ideal replacement solution would be one that could utilize a set of standardized transformers while incorporating flexibility to influence metrics like power flow, apparent impedance and voltage profiles. In view of these issues the team at Georgia Tech proposed a concept called Modular Controllable Transformers (MCTs). This project was commissioned as a part of DOE’s Transformer Resiliency and Advance Component (TRAC) program. The approach consists of splitting one large unit rated upwards of 100 MVA with smaller modular, standardized units. Each of these smaller units are augmented with a converter to add power flow, voltage and impedance control. Splitting the power level into multiple units has two important implications. By making smaller units, the transportation times can be reduced drastically. Moreover, even though these units have very specific impedance and other parameters, the augmented converters can make it emulate the unit being replaced. Thus, faster replacement times and added controls are achieved making this an extremely resilient approach. In the event of one modular units failure, the other two controllable units can operate in the most resilient fashion keeping the net system overloads to a minimum. Moreover, for the same probability of failure only a fraction of the system capacity is lost. The converter is augmented on to the tertiary winding of the transformer making it retrofittable in the field without massive modifications to the system. The material proposed in this report highlights design considerations to minimize recovery time as well as results displaying overall improvement in resiliency. The cost analysis of this approach shows significant savings compared to UPFC and HVDC lite based approaches. Extensive analysis was conducted on numerous aspects of this project over the course of this project. Simulation studies were conducted to prove the 5MVA converter design. Challenging BIL constraints and transient issues were addressed over the course of this project. Simulations on EMTP platform presented in consequent sections were used to finely tune the control for the same. A final design for a back-to-back 5MVA neutral-point-clamped (NPC) converter was completed in this project. Furthermore, switching components like high power IGBTs from IXYS Westcode Press-Pack series and ABB Stackpack series were identified for this application. These devices exhibit a blocking voltage of 6.5 kV and a nominal collector current of 900 A. Potential housing options as well as existing commercial option were identified for this converter design. A 56 MVA modular transformer unit was designed with Delta Star Inc. with consultation and inputs from all project members. The transformer cooling systems were chosen to be Oil Natural Air Forced (ONAF) to optimize ease of transport. A full Product Requirement Document (PRD) for the converter and the transformer was generated. The team also investigated key aspects of resiliency and how to quantify the same. A metric was developed to analyze resiliency and numerous simulation cases were presented. Increased (N-1) resiliency and outage resistance was showcased through simulation on the Texas Large scale power system. Dynamic control capabilities were also showcased on numerous system level simulations. An IEEE 30 bus system was used to show the ability of the MCT approach to reduce line congestion. Power flow control; a part of the MCTs abilities, showcased a 29% reduction in transformer loading on the same system. Full control over tie line flows was demonstrated on a modified IEEE 13 bus system. Dynamic LTC capabilities were shown through simulation and were compared to traditional LTCs. Furthermore, the ability of the MCTs to alter apparent transformer impedance was simulated to promote standardization of modular transformer units while retaining the ability to emulate a varied range of impedance characteristics. Thus granular control over power flow, voltages, impedances and was presented. Regulatory analysis conducted by Oak Ridge National Laboratory (ORNL) further bolstered the efficacy of the MCT approach and verified the added resiliency achieved due to this approach. As a conclusion, it was proved that the resilience improvement obtained from using the MCT approach is justified by just one failure in a 30-year period. This means that the benefits obtained from using the MCT approach far outweigh the cost of setting this approach up. As a part of the future efforts, the team is proposing building a (12.47-24) kV/400 kVA scaled down unit to control 5MVA of power flows. Emphasis would be laid on using commercial components to speed up the build of these units. Further the actual transport of the modular transformer unit would be a part of this operation and would provide insight into transportation issues. The approach shows much promise and adds key dynamic control on passive sub transmission and transmission sectors.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2014

Comparison of Hydrocode Simulations with Measured Shock Wave Velocities

We have conducted detailed 1- and 2-dimensional hydrodynamics calculations to assess the quality of simulations commonly made to understand various shock processes in a sample and to design shock experiments. We began with relatively simple shock experiments, where we examined the effects of the equation of state and the viscoplastic strength models. Eventually we included spallation in copper and iron and a solid-solid phase transformation in iron to assess the quality of the damage and phase transformation simulations.

36 MATERIALS SCIENCE↗
DOE OSTI2019

“Lattice Strain Matching”‐Enabled Nanocomposite Design to Harness the Exceptional Mechanical Properties of Nanomaterials in Bulk Forms

Abstract Nanosized materials are known to have the ability to withstand ultralarge elastic strains (4–10%) and to have ultrahigh strengths approaching their theoretical limits. However, it is a long‐standing challenge to harnessing their exceptional intrinsic mechanical properties in bulk forms. This is commonly known as “the valley of death” in nanocomposite design. In 2013, a breakthrough was made to overcome this challenge by using a martensitic phase transforming matrix to create a composite in which ultralarge elastic lattice strains up to 6.7% are achieved in Nb nanoribbons embedded in it. This breakthrough was enabled by a novel concept of phase transformation assisted lattice strain matching between the uniform ultralarge elastic strains (4–10%) of nanomaterials and the uniform crystallographic lattice distortion strains (4–10%) of the martensitic phase transformation of the matrix. This novel concept has opened new opportunities for developing materials of exceptional mechanical properties or enhanced functional properties that are not possible before. The work in progress in this research over the past six years is reported.

Zhang, Junsong↗
DOE OSTI2018

The facile synthesis, crystallization behavior and magnetic property of FeNiP amorphous nanoparticles

Highlights: • A facile chemistry method was proposed to synthesize amorphous FeNiP nanoparticle. • Phase transformation happened during sintering the amorphous nanoparticle. • Ni nanospheres and monoclinic (Ni,Fe){sub 3}[PO4]{sub 2} nanorods appeared at 800 °C. • Crystallization behavior is α-FeNiP → Ni + FeNi{sub 3} + Ni{sub 3}P → Ni + (Ni,Fe){sub 3}[PO{sub 4}]{sub 2}. • Sintered powders have varied magnetic properties due to phase proportion change. - Abstract: Amorphous FeNiP nanoparticles with homogeneous composition are synthesized by reduction of aqueous Fe{sup 2 +} and Ni{sup 2 +} with sodium borohydride (NaBH{sub 4}) and hypophosphite at room temperature. These amorphous nanoparticles can be crystallized by heating up to 300 °C to form FeNi{sub 3} and Ni{sub 3}P crystals. Ni phase appeared at the sintering temperature of 500 °C, and a special net structure was formed at 700 °C due to the joining and diffusion among different nanoparticles. At a higher temperature of 800 °C, phase transformation happened and only pure Ni nanospheres and monoclinic ((Ni, Fe){sub 3}[PO{sub 4}]{sub 2}) nanorods can be observed, which should be governed by the long-range diffusion in the net structure. The amorphous FeNiP nanoparticles have excellent soft magnetic property with Ms of 13.2 emu/g and Hc of 0.7 Oe. However, the sintered mixing nanoparticles show varied magnetic properties due to the phase transformation and proportion change among different phases involved in.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Hugoniot equation of state and dynamic strength of boron carbide

Boron carbide ceramics have been particularly problematic in attempts to develop adequate constitutive model descriptions for purposes of analysis of dynamic response in the shock and impact environment. Dynamic strength properties of boron carbide ceramic differ uniquely from comparable ceramics. Furthermore, boron carbide is suspected, but not definitely shown, to undergoing polymorphic phase transformation under shock compression. In the present paper, shock-wave compression measurements conducted over the past 40 years are assessed for the purpose of achieving improved understanding of the dynamic equation of state and strength of boron carbide. In particular, attention is focused on the often ignored Los Alamos National Laboratory (LANL) Hugoniot measurements performed on porous sintered boron carbide ceramic. The LANL data are shown to exhibit two compression anomalies on the shock Hugoniot within the range of 20–60 GPa that may relate to crystallographic structure transitions. More recent molecular dynamics simulations on the compressibility of the boron carbide crystal lattice reveal compression transitions that bear similarities to the LANL Hugoniot results. The same Hugoniot data are complemented with dynamic isentropic compression data for boron carbide extracted from Hugoniot measurements on boron carbide and copper granular mixtures. Other Hugoniot measurements, however, performed on near-full-density boron carbide ceramic differ markedly from the LANL Hugoniot data. These later data exhibit markedly less compressibility and tend not to show comparable anomalies in compressibility. Alternative Hugoniot anomalies, however, are exhibited by the near-full-density data. Experimental uncertainty, Hugoniot strength, and phase transformation physics are all possible explanations for the observed discrepancies. It is reasoned that experimental uncertainty and Hugoniot strength are not likely explanations for the observed differences. The notable mechanistic difference in the processes of shock compression between the LANL data and that of the other studies is the markedly larger inelastic deformation and dissipation experienced in the shock event brought about by compaction of the substantially larger porosity LANL test ceramics. High-pressure diamond anvil cell experiments reveal extensive amorphization, reasoned to be a reversion product of a higher-pressure crystallographic phase, which is a consequence of application of both high pressure and shear deformation to the boron carbide crystal structure. A dependence of shock-induced high-pressure phase transformation in boron carbide on the extent of shear deformation experienced in the shock process offers a plausible explanation for the differences observed in the LANL Hugoniot data on porous ceramic and that of other shock data on near-full-density boron carbide.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Two-step deformation-induced martensitic transformation in additively manufactured High-Si stainless steel

Deformation-induced phase transformation in the additively manufactured (AM) Fe–18Cr–8Ni-5.5Si (in wt.%) alloy was analyzed using the in-situ electron backscattered diffraction (EBSD) record during uniaxial tensile testing in a scanning electron microscope (SEM). Analysis of EBSD data was focused to investigate phase transformation behavior during deformation with consideration of mechanical interactions among phases and grains in the ultrafine AM microstructure. The initial EBSD phase map illustrated that the as-built microstructure was a duplex structure consisting of major austenite (γ) and minor ferrite phases, some of which showed non-traditional orientation relationship since the rapid solidification in the AM process has produced non-equilibrium state in phase formation. In the deformed as-built AM alloy, the two-step martensitic transformation (γ→ε→α´) was identified as the main deformation-induced transformation mechanism. Martensitic transformation steps were found to be associated with glides of Shockley partial dislocations on closed packed (111) planes under the influence of atomic disturbance in the γ and ε phases, respectively. Using the closed-packed plane pole figures and unit cell orientations, their evolutions and mechanisms accompanying with the transformation were analyzed. Finally, the results indicate that one variant of ε-martensite forms from their parent γ phase, while two variants of α´ form from their parent ε phase.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Many-Body Quantum Catalysts for Transforming Between Phases of Matter

A catalyst is a substance that enables otherwise impossible transformations between states of a system, without being consumed in the process. In this work, we apply the notion of catalysts to many-body quantum physics. In particular, we construct catalysts that enable transformations between different symmetry-protected topological (SPT) phases of matter using symmetric finite-depth quantum circuits. We discover a wide variety of catalysts, including GHZ-like states that spontaneously break the symmetry, gapless states with critical correlations, topological orders with symmetry fractionalization, and spin-glass states. These catalysts are all united under a single framework that has close connections to the theory of quantum anomalies, and we use this connection to put strong constraints on possible pure- and mixed-state catalysts. We also show how the catalyst approach leads to new insights into the structure of certain phases of matter, and to new methods to efficiently prepare SPT phases with long-range interactions or projective measurements.

quantum many-body systems↗
DOE OSTI2015

Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material

Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for the samples prepared by hydro-thermal assistant method. It is found the transformation pathway of LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that LMR cathode prepared by HA approach experiences a phase transformation from the layered structure to a LT-LiCoO2 type defect spinel-like structure (Fd-3m space group) and then to a disordered rock-salt structure (Fm-3m space group). The voltage fade can be well correlated with the Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like structure and disordered rock-salt structure. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that can satisfy the Li percolating in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a great amount of oxygen vacancies, a significant decrease of Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn-Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change undoubtedly provides insights into a profound understanding on the voltage fade, and capacity degradation of LMR cathode. The results also inspire us to further enhance the reversibility of LMR cathode via improving its surface structural stability.

Cation redistribution↗
DOE OSTI2017

High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr) up to ~50GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B=Ti and ~16 GPa B=Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionic radii, i.e., A=Dy, proceeding faster than those with a larger ionic radii, i.e., A=Eu. These results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B=Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A=Eu than A=Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2 Zr 2 O 7 as compared with the initially defect-fluorite structured Dy 2 Zr 2 O 7 .

36 MATERIALS SCIENCE↗