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Mechanistic insight into the effects of A-site doping in perovskite nanorods on interfacial Li-ion and Na-ion transport in polymer–perovskite composite electrolytes
Composite polymer electrolytes (CPEs) offer a promising pathway to safer and higher energy density electrochemical energy storage yet optimizing interfacial ion transport remains a critical challenge due to high resistances and a lack of understanding of the complex interfacial electrostatic interactions. This work investigates the mechanistic origins of the interfacial ion transport enhancement in single-ion conducting (SIC) polymer electrolytes filled with A-site disordered perovskite LaxMyTiOz (LMTO) (M = Li, Na, K) nanorods. By integrating Density Functional Theory (DFT) with broadband dielectric spectroscopy (BDS) and pulsed-field-gradient NMR (PFG-NMR), we analyze the ion transport behavior in Li-based and Na-based SIC systems containing compositionally distinct LMTO fillers (LMTO800 and LMTO900). Specifically, we introduce the site-to-site energy difference (ΔE) descriptor, which extends beyond single-site descriptors such as adsorption energy and ion binding energies. We demonstrate that ΔE together with ion binding energies provide a more comprehensive picture of the energy landscape at the polymer–ceramic interface. The combined DFT and experimental results show that A-site doping in the ceramic filler can effectively modulate ΔE and ion binding energies, creating a favorable potential energy landscape that promotes enhanced ion transport along the interface. This comprehensive study illustrates the impact of ceramic compositional tuning on interfacial ion transport and provides materials design rules towards real-world applications.
Review of SiC material development for nuclear fusion applications: Cross-cutting research and emerging opportunities
The SiC-based materials, particularly SiC-fiber-reinforced SiC matrix (SiC/SiC) composites, show strong potential for structural and functional applications in future fusion power plants because they can operate at high temperatures with a range of coolants and breeders, thereby enabling higher energy conversion efficiency. Here, this paper presents recent advancements in the development of SiC-based materials, focusing on processing techniques and material performance and resistance under fusion-relevant environments. The processing activities have emphasized near-net-shape fabrication and the joining of SiC subcomponents, with processing methods and material compositions informed by previous irradiation experiments on various grades of SiC. Research on irradiation effects has remained focused on degradation mechanisms and the microstructural optimization of SiC/SiC composites irradiated to high neutron damage levels. Analysis of irradiation defects in SiC has advanced via the application of cutting-edge characterization methods, among which Raman spectroscopy is becoming a common tool to assess atomic-scale chemical disorder. Fusion–fission crosscutting irradiation research has explored combined effects in SiC/SiC composites with application-relevant geometries, including bowing of SiC/SiC composite channels under neutron flux gradients, stress evolution in SiC/SiC composite tubes under through-thickness temperature gradients, and irradiation-enhanced corrosion in SiC. Finally, research opportunities for component testing and assessment under fusion-relevant conditions, in support of emerging concepts from the private fusion sector, are discussed.
Prelithiated Li-Enriched Gradient Interphase toward Practical High-Energy NMC-Silicon Full Cell
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Computer Code for Nanostructure Simulation
Due to their small size, nanostructures can have stress and thermal gradients that are larger than any macroscopic analogue. These gradients can lead to specific regions that are susceptible to failure via processes such as plastic deformation by dislocation emission, chemical debonding, and interfacial alloying. A program has been developed that rigorously simulates and predicts optoelectronic properties of nanostructures of virtually any geometrical complexity and material composition. It can be used in simulations of energy level structure, wave functions, density of states of spatially configured phonon-coupled electrons, excitons in quantum dots, quantum rings, quantum ring complexes, and more. The code can be used to calculate stress distributions and thermal transport properties for a variety of nanostructures and interfaces, transport and scattering at nanoscale interfaces and surfaces under various stress states, and alloy compositional gradients. The code allows users to perform modeling of charge transport processes through quantum-dot (QD) arrays as functions of inter-dot distance, array order versus disorder, QD orientation, shape, size, and chemical composition for applications in photovoltaics and physical properties of QD-based biochemical sensors. The code can be used to study the hot exciton formation/relation dynamics in arrays of QDs of different shapes and sizes at different temperatures. It also can be used to understand the relation among the deposition parameters and inherent stresses, strain deformation, heat flow, and failure of nanostructures.
Multi-site reaction dynamics through multi-fragment density matrix embedding
The practical description of disordered chemical reactions, where the reactions involve multiple species at multiple sites, is presently a challenge using correlated electronic structure methods due to their high computational cost and steep scaling. Here, we describe the gradient theory of multi-fragment density matrix embedding theory, which potentially provides a minimal computational framework to model such processes at the correlated electron level. We present the derivation and implementation of the gradient theory, its validation on model systems and chemical reactions using density matrix embedding, and its application to a molecular dynamics simulation of proton transport in a small water cluster, a simple example of multi-site reaction dynamics.
Shear banding, intermittency, jamming, and dynamic phases for skyrmions in inhomogeneous pinning arrays
In this work, we examine driven skyrmion dynamics in systems with inhomogeneous pinning where a strip of strong pinning coexists with a region containing no pinning. For driving parallel to the strip, we find that the initial skyrmion motion is confined to the unpinned region and the skyrmion Hall angle is zero. At larger drives, a transition occurs to a phase in which motion also appears within the pinned region, creating a shear band in the skyrmion velocity, while the skyrmion Hall angle is still zero. As the drive increases further, the flow becomes disordered and the skyrmion Hall angle increases with drive until saturating at the highest drives when the system transitions into a moving crystal phase. The different dynamic phases are associated with velocity and density gradients across the pinning boundaries. We map out the dynamic phases as a function of pinning strength, skyrmion density, and Magnus force strength, and correlate the phase boundaries with features in the velocity-force curves and changes in the local and global ordering of the skyrmion structure. For large Magnus forces, the shear banding instability is replaced by large-scale intermittent flow in the pinned region accompanied by simultaneous motion perpendicular to the direction of the drive, which appears as oscillations in the transport curves. We also examine the case of a drive applied perpendicular to the strip, where we find a jamming effect in which the skyrmion flow is blocked by skyrmion-skyrmion interactions until the drive is large enough to induce plastic flow.
Bulk and Nanocrystalline Cesium Lead-Halide Perovskites as Seen by Halide Magnetic Resonance
Lead-halide perovskites increasingly mesmerize researchers because they exhibit a high degree of structural defects and dynamics yet nonetheless offer an outstanding (opto)electronic performance on par with the best examples of structurally stable and defect-free semiconductors. This highly unusual feature necessitates the adoption of an experimental and theoretical mindset and the reexamination of techniques that may be uniquely suited to understand these materials. Surprisingly, the suite of methods for the structural characterization of these materials does not commonly include nuclear magnetic resonance (NMR) spectroscopy. The present study showcases both the utility and versatility of halide NMR and NQR (nuclear quadrupole resonance) for probing the structure and structural dynamics of CsPbX 3 (X = Cl, Br, I), in both bulk and nanocrystalline forms. The strong quadrupole couplings, which originate from the interaction between the large quadrupole moments of, e.g., the 35 Cl, 79 Br, and 127 I nuclei, and the local electric-field gradients, are highly sensitive to subtle structural variations, both static and dynamic. The quadrupole interaction can resolve structural changes with accuracies commensurate with synchrotron X-ray diffraction and scattering. It is shown that space-averaged site-disorder is greatly enhanced in the nanocrystals compared to the bulk, while the dynamics of nuclear spin relaxation indicates enhanced structural dynamics in the nanocrystals. The findings from NMR and NQR were corroborated by ab initio molecular dynamics, which point to the role of the surface in causing the radial strain distribution and disorder. These findings showcase a great synergy between solid-state NMR or NQR and molecular dynamics simulations in shedding light on the structure of soft lead-halide semiconductors.
Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy
Oxygen vacancy formation and migration in ceria is critical to its electrochemical and catalytic properties in systems for chemical and energy transformation, but its quantification is rather challenging especially at atomic-scale because of disordered distribution. Here we report a rational approach to track oxygen vacancy diffusion in single grains of pure and Sm-doped ceria at -20 °C to 160 °C using in situ (scanning) transmission electron microscopy ((S)TEM). To create a gradient in oxygen vacancy concentration, a small region (~30 nm in diameter) inside a ceria grain is reduced to the C-type CeO 1.68 phase by the ionization or radiolysis effect of a high-energy electron beam. The evolution in oxygen vacancy concentration is then mapped through lattice expansion measurement using scanning nano-beam diffraction or 4D STEM at a spatial resolution better than 2 nm; this allows direct determination of local oxygen vacancy diffusion coefficients in a very small domain inside pure and Sm-doped ceria at different temperatures. Further, the activation energies for oxygen transport are determined to be 0.59, 0.66, 1.12, and 1.27 eV for pure CeO 2 , Ce 0.94 Sm 0.06 O 1.97 , Ce 0.89 Sm 0.11 O 1.945 , and Ce 0.8 Sm 0.2 O 1.9 , respectively, implying that activation energy increases due to impurity scattering. The results are qualitatively supported by density functional theory (DFT) calculations. In addition, our in situ TEM investigation reveals that dislocations impede oxygen vacancy diffusion by absorbing oxygen vacancies from the surrounding areas and pinning them locally. With more oxygen vacancies absorbed, dislocations show extended strain fields with local tensile zone sandwiched between the compressed ones. Therefore, dislocation density should be reduced in order to minimize the resistance to oxygen vacancy diffusion at low temperatures.
Ultralow thermal conductivity from transverse acoustic phonon suppression in distorted crystalline α-MgAgSb
Low thermal conductivity is favorable for preserving the temperature gradient between the two ends of a thermoelectric material, in order to ensure continuous electron current generation. In high-performance thermoelectric materials, there are two main low thermal conductivity mechanisms: the phonon anharmonic in PbTe and SnSe, and phonon scattering resulting from the dynamic disorder in AgCrSe2 and CuCrSe2, which have been successfully revealed by inelastic neutron scattering. Using neutron scattering and ab initio calculations, we report here a mechanism of static local structure distortion combined with phononanharmonic-induced ultralow lattice thermal conductivity in α-MgAgSb. Since the transverse acoustic phonons are almost fully scattered by the compound’s intrinsic distorted rocksalt sublattice, the heat is mainly transported by the longitudinal acoustic phonons. The ultralow thermal conductivity in α-MgAgSb is attributed to its atomic dynamics being altered by the structure distortion, which presents a possible microscopic route to enhance the performance of similar thermoelectric materials.
Native Defect Related Optical Properties of ZnGeP2
We present photoluminescence, photoconductivity, and optical absorption spectra for ZnGeP2 crystals grown from the melt by gradient freezing and from the vapor phase by high pressure physical vapor transport (HPVT). A model of donor and acceptor related subbands in the energy gap of ZnGeP2 is introduced that explains the experimental results. The emission with peak position at 1.2 eV is attributed to residual disorder on the cation sublattice. The lower absorption upon annealing is interpreted in terms of both the reduction of the disorder on the cation sublattice and changes in the Fermi level position. The n-type conductivity of ZnGeP2 Crystals grown under Ge-deficient conditions by the HPVT is related to the presence of additional donor states.
Magnetic phase diagram mapping in Fe 1- x Rh x composition-spread thin films
We have fabricated high-quality polycrystalline Fe 1- x Rh x composition-spread thin films by cosputtering Fe and Rh, and investigated their structural and magnetic transformations as a systematic function of composition. With increasing Rh concentration, Fe 1-x Rh x thin film undergoes from an α' phase to a disordered γ phase and also shows a magnetic transition from a ferromagnetic phase to a paramagnetic phase. Vibrating-sample magnetometry and x-ray magnetic circular dichroism measurements show an antiferromagnetic-ferromagnetic transition in the range of 0.52 < x < 0.58 in the Fe 1- x Rh x composition gradient at room temperature. Based on our structural and magnetic property mapping, we construct a thin-film phase diagram of Fe 1- x Rh x . Compared to reported results in bulk alloys, the antiferromagnetic-ferromagnetic transition in the Fe 1- x Rh x thin films was found to occur at slightly higher Rh concentrations, while the boundary between the pure γ phase and the α'/ γ mixed phase region is shifted to the lower concentration Rh.
Structural transitions of 4:1 methanol–ethanol mixture and silicone oil under high pressure
A 4:1 (volume ratio) methanol–ethanol (ME) mixture and silicone oil are two of the most widely used liquid pressure-transmitting media (PTM) in high-pressure studies. Their hydrostatic limits have been extensively studied using various methods; however, the evolution of the atomic structures associated with their emerging nonhydrostaticity remains unclear. Here, we monitor their structures as functions of pressure up to ∼30 GPa at room temperature using in situ high-pressure synchrotron x-ray diffraction (XRD), optical micro-Raman spectroscopy, and ruby fluorescence spectroscopy in a diamond anvil cell. No crystallization is observed for either PTM. The pressure dependence of the principal diffraction peak position and width indicates the existence of a glass transition in the 4:1 ME mixture at ∼12 GPa and in the silicone oil at ∼3 GPa, beyond which a pressure gradient emerges and grows quickly with pressure. There may be another liquid-to-liquid transition in the 4:1 ME mixture at ∼5 GPa and two more glass-to-glass transitions in the silicone oil at ∼10 GPa and ∼16 GPa. By contrast, Raman signals only show peak weakening and broadening for typical structural disordering, and Raman spectroscopy seems to be less sensitive than XRD in catching these structural transitions related to hydrostaticity variations in both PTM. These results uncover rich pressure-induced transitions in the two PTM and clarify their effects on hydrostaticity with direct structural evidence. The high-pressure XRD and Raman data on the two PTM obtained in this work could also be helpful in distinguishing between signals from samples and those from PTM in future high-pressure experiments.
Thermomechanical conversion in metals: dislocation plasticity model evaluation of the Taylor-Quinney coefficient
Using a partitioned-energy thermodynamic framework which assigns energy to that of atomic configurational stored energy of cold work and kinetic-vibrational, in this study we derive an important constraint on the Taylor-Quinney coefficient, which quantifies the fraction of plastic work that is converted into heat during plastic deformation. Associated with the two energy contributions are two separate temperatures – the ordinary temperature for the thermal energy and the effective temperature for the configurational energy. We show that the Taylor-Quinney coefficient is a function of the thermodynamically defined effective temperature that measures the atomic configurational disorder in the material. Finite-element analysis of recently published experiments on the aluminum alloy 6016-T4 [1], using the thermodynamic dislocation theory (TDT), shows good agreement between theory and experiment for both stress-strain behavior and temporal evolution of the temperature. The simulations include both conductive and convective thermal energy loss during the experiments, and significant thermal gradients exist within the simulation results. Computed values of the differential Taylor-Quinney coefficient are also presented and suggest a value which differs between materials and increases with increasing strain.
Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields
Organic ionic plastic crystal electrolytes, containing a plastic crystal and lithium salt, offer a potential balance between mechanical and electrochemical properties for solid state lithium-ion battery electrolytes. These electrolytes contain multiple mobile ionic species (three or four), resulting in complex transport mechanisms which have not yet been established. Plastic crystals are defined by long-range positional order and short-range rotational disorder. It is therefore necessary to quantify changes in the local crystal structure of the electrolyte as current flows through it. Herein, we examine the electrochemical properties of pyrrolidinium-based plastic crystal electrolytes containing lithium salt and zwitterion additives, including measurements of current fraction and limiting current. We obtain species-specific insight into electrolyte transport using pulsed-field gradient nuclear magnetic resonance spectroscopy and find that, while the zwitterion additive increases ionic conductivity, it decreases lithium diffusivity with respect to other ionic components. With operando spatiotemporally resolved wide-angle X-ray scattering we observe location-specific crystal rotations due to the passage of ionic current. In conclusion, we posit that reducing energy dissipation due to rotation is essential for using plastic crystal electrolytes in practical applications.
Active matter shepherding and clustering in inhomogeneous environments
Here, we consider a mixture of active and passive run-and-tumble disks in an inhomogeneous environment where only half of the sample contains quenched disorder or pinning. The disks are initialized in a fully mixed state of uniform density. We identify several distinct dynamical phases as a function of motor force and pinning density. At high pinning densities and high motor forces, there is a two-step process initiated by a rapid accumulation of both active and passive disks in the pinned region, which produces a large density gradient in the system. This is followed by a slower species phase separation process where the inactive disks are shepherded by the active disks into the pin-free region, forming a nonclustered fluid and producing a more uniform density with species phase separation. For higher pinning densities and low motor forces, the dynamics becomes very slow and the system maintains a strong density gradient. For weaker pinning and large motor forces, a floating clustered state appears, and the time-averaged density of the system is uniform. We illustrate the appearance of these phases in a dynamic phase diagram.
Turbulence in the solar wind: Kinetic effects
Although a casual look at the fluctuating magnetic and velocity fields in the solar wind may be reminiscent of a chaotic and disordered flow, there is, nonetheless. considerable organization and structure in the temporal and spatial evolution of those fluctuations. Much of that evolution is controlled by processes operating on rather large scales for example, in the inner heliosphere, the fluctuations in magnetic and velocity are highly correlated in the sense of outward propagating Alfven waves. This correlation can be destroyed both in time and distance by the velocity gradients present between fast and slow streams and by other nonlinear processes which stir the medium, producing a turbulent cascade of energy from large to small scales. Many aspects of this turbulent evolution can be described using fluid models; however, at some scale the fluid approximation breaks down and a more detailed paradigm is necessary. The breakdown is evident in the power spectrum of magnetic fluctuations at scales approaching the wavelength of ion cyclotron waves. At those scales, as evident in Mariner 10 and other magnetometer data, the spectrum bends over and the fluctuations damp, possibly heating the ambient plasma. Some evidence for heating of the solar wind is present in the Voyager data. Fluid models can be modified to some extent to incorporate aspects of a kinetic treatment. This is done by modifying the dissipation terms in the fluid equations and by including extra terms, such as the Hall term. As the scale lengths of phenomena shrink further and approach the spatial and temporal scales characteristic of electron phenomena, the fluid description must be abandoned altogether and a fully kinetic treatment is required. One example is the generation of Langmuir solitons produced by the electron beams that generate type 3 solar radio bursts.
Mapping strain and structural heterogeneities around bubbles in amorphous ionically conductive Bi 2 O 3
While amorphous materials are often approximated to have a statistically homogeneous atomic structure, they frequently exhibit localized structural heterogeneity that challenges simplified models. This study uses 4D scanning transmission electron microscopy to investigate the strain and structural modifications around gas bubbles in amorphous Bi 2 O 3 induced by argon irradiation. We present a method for determining strain fields surrounding bubbles that can be used to measure the internal pressure of the gas. Compressive strain is observed around the cavities, with higher-order crystalline symmetries emerging near the cavity interfaces, suggesting paracrystalline ordering as a result of bubble coarsening. This ordering, along with a compressive strain gradient, indicates that gas bubbles induce significant localized changes in atomic packing. By analyzing strain fields with maximum compressive strains of 3%, we estimate a lower bound on the internal pressure of the bubbles at 2.5 GPa. These findings provide insight into the complex structural behavior of amorphous materials under stress, particularly in systems with gas inclusions, and offer new methods for probing the local atomic structure in disordered materials. Although considering structural heterogeneity in amorphous systems is non-trivial, these features have crucial impacts on material functionalities, such as mechanical strength, ionic conductivity, and electronic mobility.