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Highly-­laminated, high-­saturation-flux-­density, magnetic cores for on-­chip inductors in power converter applications

The objective of this project is development of a manufacturing process to realize thick highly-laminated metallic magnetic cores with suppressed eddy current losses for power applications and demonstration of integrated magnetic components using the process. The continual reduction in size and increase in functionality of portable electronic devices drives the development of ultracompact electrical power converters and therefore their associated inductors, which typically occupy the largest volume within the converter. This inductor size reduction can be achieved by increasing both the converter switching frequency as well as inductor operating flux density by utilizing appropriate magnetic core materials. Magnetically soft metallic alloys (e.g., NiFe and CoNiFe) are good core material candidates due to their superior magnetic properties (e.g., high saturation flux density and low coercivity) compared to conventional ferrite. However, to minimize eddy current losses, the core thickness is limited to the skin depth (typically less than 3 µm for 10 MHz operation); cores of this thickness are likely insufficient for handling high power (> 10W). Therefore, there is great interest in the development of highly-laminated metallic alloy cores with single lamination thickness in the sub-micron range to achieve suppressed eddy-current losses and high power handling capacity simultaneously. During the project, highly-laminated metallic alloy cores comprising up to 2000 layers of permalloy (Ni 80 Fe 20 ) or CoNiFe materials with single lamination thickness less than 1 µm have been fabricated based on automated multilayer electrodeposition technology compatible with CMOS manufacturing. The developed highly-laminated metallic cores preserve the high saturation flux density and low coercivity characteristics of metallic alloys, while suppressing eddy-current losses less than 1 W/cm3 at operation flux density of 0.5 T and frequency over 1 MHz. The developed highly-laminated metallic alloy cores have been further integrated into microfabricated windings to realize compact, on-chip inductors. Utilizing CMOS-compatible integration techniques, circular (toroid) and bar-shape (solenoid) microinductors have been fabricated exhibiting a constant inductance higher than 1 µH up to 50 MHz with peak quality factor as high as 35 at 5 MHz. The microfabricated inductor with highly-laminated core was tested in a power converter and demonstrated a converter efficiency of 93% at 5.5 MHz and 42 W under 100V input and 35V output operation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Methods for Estimating Environmental Effects and Constraints on NexGen: High Density Case Study

This document provides a summary of the current methods developed by Metron Aviation for the estimate of environmental effects and constraints on the Next Generation Air Transportation System (NextGen). This body of work incorporates many of the key elements necessary to achieve such an estimate. Each section contains the background and motivation for the technical elements of the work, a description of the methods used, and possible next steps. The current methods described in this document were selected in an attempt to provide a good balance between accuracy and fairly rapid turn around times to best advance Joint Planning and Development Office (JPDO) System Modeling and Analysis Division (SMAD) objectives while also supporting the needs of the JPDO Environmental Working Group (EWG). In particular this document describes methods applied to support the High Density (HD) Case Study performed during the spring of 2008. A reference day (in 2006) is modeled to describe current system capabilities while the future demand is applied to multiple alternatives to analyze system performance. The major variables in the alternatives are operational/procedural capabilities for airport, terminal, and en route airspace along with projected improvements to airframe, engine and navigational equipment.

Augustine, S.↗

K-shell radiation and bright spot characteristics of high-energy-density Fe-Cr-Ni plasmas influenced by X-pinch load geometry

K-shell radiation is diagnostically advantageous for the study of high-energy-density plasmas. Here, the current work investigates the influence of load geometry on K-shell x-rays in Z-pinch plasmas produced on the 1-MA Zebra generator. Stainless steel (Fe: 69%, Cr: 20%, Ni: 9%) X-pinch wire loads are fielded with an interwire angle of 31° (small-angle) or 62.5° (large-angle), respectively and studied using various x-ray diode, imaging, and spectroscopic diagnostics. The large-angle geometry produced large, individual x-ray-emitting bright spots (> 3 keV) at the wire cross-point averaging areas ≥ 1 mm 2 , with noteworthy soft x-ray (> 0.75 keV) bursts and radiation yields ≤ 14.6 kJ. The small-angle geometry produced multiple x-ray-emitting bright spots extending the pinch axis with smaller average sizes (≤ 0.5 mm 2 ), consistent with stronger current, increased radiation yield (≥ 15.5 kJ), and notable hard x-ray (> 9 keV) bursts, which peak with largest cumulative bright spot size. Spectroscopic analysis is performed with non-LTE collisional-radiative modeling, indicating a cold, nonthermal plasma region radiating from neutral to Ne-like ions, a hot, thermal region radiating from Fe and Cr He- and Li-like ions, and an intermediate region radiating Kα satellites from Li-like to O-like ions. Modeling of the nonthermal and satellite features imply a fractional hot electron abundance ~0.1% and ~0.5% for large- and small-angle geometries, respectively. Relative intensity analysis is performed on Heα and Kα lines, revealing intensity ratios that deviate from the original wire composition. Optical depth estimates allude to optically thick, thermal K-shell plasmas with densities consistent with non-LTE modeling.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

TRANSP-based closed-loop simulations of current profile optimal regulation in NSTX-Upgrade

Active control of the toroidal current density profile is critical for the upgraded National Spherical Torus eXperiment device (NSTX-U) to maintain operation at the desired high-performance, MHD-stable, plasma regime. Initial efforts towards current density profile control have led to the development of a control-oriented, physics-based, plasma-response model, which combines the magnetic diffusion equation with empirical correlations for the kinetic profiles and the non-inductive current sources. The developed control-oriented model has been successfully tailored to the NSTX-U geometry and actuators. Moreover, a series of efforts have been made towards the design of model-based controllers, including a linear-quadratic-integral optimal control strategy that can regulate the current density profile around a prescribed target profile while rejecting disturbances. In this work, the tracking performance of the proposed current-profile optimal controller is tested in numerical simulations based on the physics-oriented code TRANSP. These high-fidelity closed-loop simulations, which are a critical step before experimental implementation and testing, are enabled by a flexible framework recentlydeveloped to perform feedback control design and simulation in TRANSP.

current profile control↗

TRANSP-based closed-loop simulations of current profile optimal regulation in NSTX-Upgrade

Active control of the toroidal current density profile is critical for the upgraded National Spherical Torus eXperiment device (NSTX-U) to maintain operation at the desired high-performance, MHD-stable, plasma regime. Initial efforts towards current density profile control have led to the development of a control-oriented, physics-based, plasma-response model, which combines the magnetic diffusion equation with empirical correlations for the kinetic profiles and the non-inductive current sources. The developed control-oriented model has been successfully tailored to the NSTX-U geometry and actuators. Moreover, a series of efforts have been made towards the design of model-based controllers, including a linear-quadratic-integral optimal control strategy that can regulate the current density profile around a prescribed target profile while rejecting disturbances. In this work, the tracking performance of the proposed current-profile optimal controller is tested in numerical simulations based on the physics-oriented code TRANSP. Furthermore, these high-fidelity closed-loop simulations, which are a critical step before experimental implementation and testing, are enabled by a flexible framework recently developed to perform feedback control design and simulation in TRANSP.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Final Project Report "Advanced Concept Exploration For Fast Ignition Science Program"

The Fast Ignition (FI) Concept for Inertial Confinement Fusion has the potential to provide a significant advance in the technical attractiveness of Inertial Fusion Energy (IFE) reactors. FI differs from conventional “central hot spot” (CHS) target ignition by decoupling compression from heating: using the laser (or heavy ion beam or Z pinch) drive pulse (10’s of ns) to create a dense fuel and a second, much shorter (~10 ps) high intensity pulse to ignite a small region of it. There are two major physics issues concerning this concept; controlling the laser-induced generation of large electron currents and their propagation through high density plasmas. This project has addressed these two significant scientific issues in Relativistic High Energy Density (RHED) physics. Learning to control relativistic laser matter interaction (and the limits and potential thereof) will enable a wide range of applications. While these physics issues are of specific interest to inertial fusion energy science, they are also important for a wide range of other HED phenomena, including high energy ion beam generation, isochoric heating of materials, and the development of high brightness x-ray sources. Generating, controlling, and understanding the extreme conditions needed to advance this science has proved to be challenging: Our studies have pushed the boundaries of physics understanding and are at the very limits of experimental, diagnostic, and simulation capabilities in high energy density laboratory physics (HEDLP). Our research strategy has been based on pursuing the fundamental physics underlying the Fast Ignition (FI) concept. We have performed comprehensive study of electron generation and transport in fast-ignition targets with experiments, theory, and numerical modeling. A major issue is that the electrons produced in these experiments cannot be measured directly—only effects due to their transport. We focused mainly on x-ray continuum photons from bremsstrahlung and x-ray line radiation from K-shell fluorescence. Integrated experiments, which combine target compression with short-pulse laser heating, yield additional information on target heating efficiency. This indirect way of studying the underlying behavior of the electrons must be validated with computational modeling to understand the physics and improve the design. This program execution required a large, well-organized team and it was managed by a joint Collaboration between General Atomics (GA), Lawrence Livermore National Laboratory (LLNL), and the Laboratory for Laser Energetics (LLE). The Collaboration was formed 8 years ago to understand the physics issues of the Fast Ignition concept, building on the strengths of each partner. GA fulfills its responsibilities jointly with the University of California, San Diego (UCSD), The Ohio State University (OSU) and the University of Nevada at Reno (UNR). Since RHED physics is pursued vigorously in many countries, international researchers have been an important part of our efforts to make progress. The division of responsibility was as follows: (1) LLE had primary leadership for channeling studies and the integrated energy transfer, (2) LLNL led the development of measurement methods, analysis, and deployment of diagnostics, and (3) GA together with UCSD, OSU and UNR studied the detailed energy-transfer physics. The experimental program was carried out using the Titan laser at the Jupiter Laser Facility at LLNL, the OMEGA and OMEGA EP lasers at LLE and the Texas Petawatt laser (TPW) at UT Austin. Modeling has been pursued on large computing facilities at LLNL, OSU, and UCSD using codes developed (by us and others) within the HEDLP program, commercial codes, and by leveraging existing supercomputer codes developed by the NNSA ICF program. This Consortium brought together all the components—resources, facilities, and personnel—necessary to accomplish its aggressive goals. The ACE Program has been strongly collaborative, taking advantage of the expertise of the participating institutions to provide a research effort that is far greater than the sum of its parts. The results of this work have firmly strengthened the scientific foundation from which the viability of FI and other applications can be evaluated. Program execution has also led to improved diagnostics for probing dense, hot plasmas, detailed understanding of high-current, relativistic electron energy generation and transport across boundaries and into dense plasmas, and greatly enhanced predictive modeling capabilities. One important aspect of this program was the involvement and training of young scientists including postdoctoral fellows and graduate students. During the entire 8 years of FI and ACE project period since 2005, more than fifteen graduate students completed their doctoral dissertations including three from OSU and two from UCSD in last three years. This project generated an impressive forty articles in high quality journals including nine (including two under review) in Physical Review Letters during the last funding period since 2011.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Synthesis of hierarchical 1D NiO assisted by microwave as anode material for lithium-ion batteries

Highlights: • Fast microwave solvothermal reaction is applied to obtain hierarchical 1 D NiO. • NiC{sub 2}O{sub 4}·2H{sub 2}O template forms within 30 min without any organic chelating agent. • High surface area of 208.8 m{sup 2} g{sup −1} is obtained due to the porous structure. • High initial capacity above 1000 mAh g{sup −1} is reached at 1.0 A g{sup −1}. • At 5.0 A g{sup −1}, high charge/discharge capacity of 574/611 mAh g{sup −1} is obtained. - Abstract: Fast solvothermal reaction assisted with microwave is performed to obtain hierarchical 1 D NiO with porous structure. First, the 1D NiC{sub 2}O{sub 4}·2H{sub 2}O precursor template grows within only 30 min without any other organic chelating agent. Then, a facile heat-treatment is carried out to get the final NiO through gas removal. High surface area of 208.8 m{sup 2} g{sup −1} is obtained due to the porous structure and small particle size of NiO. Thus, high initial charge/discharge capacity of 1020/1427 mAh g{sup −1} is obtained at 100 mA g{sup −1}. Even increasing the current density to 5.0 A g{sup −1}, high charge/discharge capacity of 574/611 mAh g{sup −1} can be obtained. Such good rate capability is attributed to the special hierarchical 1D structure which offers fast transfer of electrons and Li ions. Such facile strategy is considered as one of the most promising candidates to get anode material with remarkable electrochemical performances for application in lithium ion batteries.

36 MATERIALS SCIENCE↗

Instability of flux flow and production of vortex-antivortex pairs by current-driven Josephson vortices in layered superconductors

We report numerical simulations of the nonlinear dynamics of Josephson vortices driven by strong dc currents in layered superconductors. Dynamic equations for interlayer phase differences in a stack of coupled superconducting layers were solved to calculate a drag coefficient η(J) of the vortex as a function of the perpendicular dc current density J. It is shown that Cherenkov radiation produced by a moving vortex causes significant radiation drag increasing η(v) at high vortex velocities v and striking instabilities of driven Josephson vortices moving faster than a terminal velocity v c . The steady-state flux flow breaks down at v > v c as the vortex starts producing a cascade of expanding vortex-antivortex pairs evolving into either planar macrovortex structures or branching flux patterns propagating both along and across the layers. This vortex-antivortex pair production triggered by a rapidly moving vortex is most pronounced in a stack of underdamped planar junctions where it can occur at J > J s well below the interlayer Josephson critical current density. Both v c and J s were calculated as functions of the quasiparticle damping parameter, and the dc magnetic field was applied parallel to the layers. The effects of vortex interaction on the Cherenkov instability of moving vortex chains and lattices in annular stacks of Josephson junctions were considered. It is shown that a vortex driven by a current density J > J s in a multilayer of finite length excites self-sustained large-amplitude standing waves of magnetic flux, resulting in temporal oscillations of the total magnetic moment. We evaluated a contribution of this effect to the power W radiated by the sample and showed that W increases strongly as the number of layers increases. Furthermore, these mechanisms can result in nonlinearity of the c-axis electromagnetic response and contribute to THz radiation from the layered cuprates at high dc current densities flowing perpendicular to the ab planes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Efficient, Color-Stable, and Long-Lived White Organic Light-Emitting Diodes Utilizing Phosphorescent Molecular Aggregates

Highly efficient and stable single-stack hybrid white organic light-emitting diode (WOLED) devices are developed using two emissive layers: one with amber-colored phosphorescent molecular-aggregate emission from the Pd(II) complex, Pd(II) 7-(3-(pyridine-2-yl-κN)phenoxy-κC)(benzo-κC)([c]benzo[4,5]imidazo-κN)[1,2-a][1,5]naphthyridine, Pd3O8-Py5, and the other with blue fluorescence emission. Here, an optimized device structure achieves high color stability under various current densities, an external quantum efficiency (EQE) of 45.5%, a power efficiency of 97.4 Lm W -1 , and an estimated LT 95 (operational time to 95% of the initial luminance) of 50 744 h at an initial luminance of 1000 cd m -2 .

36 MATERIALS SCIENCE↗

Restricting the Solubility of Polysulfides in Li-S Batteries Via Electrolyte Salt Selection

Polysulfide solubility in the electrolyte has a critical role to the Li-S battery but the mechanism study on the solubility needs to be carefully carried out. In this paper we found that lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI) reveals a suppression of the polysulfide solubility in electrolytes (relative to the most widely used electrolyte formulation) and the Li-S cells achieved homogeneous stable capacity retention upon extensive cycling and Li metal deposition on the anode. Combined experimental, simulation and calculation methods suggest the dominate disproportionation product of Li2S8 is Li2S4 in the LiTDI electrolyte due to a different interaction between lithium ion and TDI anion. The Li2S4 would continuesly form a Li4S8 dimer and be fully locallized to precipitate out. The use of the electrolyte with the LiTDI salt (with polysulfide and LiNO3 additives) enabled a cell with a high sulfur (3 mg-S cm-2) loading to deliver a 1.67 mAh cm-2 areal capacity after 300 stable cycles at a high current (2.4 mA cm-2) density.

Environmental Molecular Sciences Laboratory↗

Wear and Corrosive Behaviors of Electroless Ni-LaCl{sub 3} Composites on Nanoporous ATO Surface of Ti Substrate

Ti and its alloys, because of its poor wear and oxidation resistance, have seriously restricted its industrial applications in the dry friction conditions. Herein we reported an easy-handling and effective approach for electroless Ni-LaCl{sub 3} nanocomposite films on nanoporous ATO surface of Ti substrate to modify its surface properties. Anodized titanium oxide, shorted as ATO, was designed as a template to deposit Ni-LaCl{sub 3} films on Ti surface with superior bonding interface. By adjusting the anodizing voltage from DC 60 to 240 V, the surface of ATO templates was manipulated to achieve a suitable diameter of nanopores using high voltage with low-current density state. The as-received Ni-LaCl{sub 3} film with a leaflike surface was successfully formed on to ATO surface. With an increase in LaCl{sub 3} addition from 0 to 4.0 g L{sup −1} in bath, results indicated that the diversified orientations of Ni crystals along Ni (111), (200), (220) and (311) were detected for Ni-LaCl{sub 3} films, rather than preferred directions of Ni (111) and (200) for pure Ni sample. As expected, the specific wear rate was ~ 10{sup −5} mm{sup 3} (N m){sup −1} for Ni-4.0 g L{sup −1} LaCl{sub 3} films, which was two times lower than that of the un-coated Ti substrate. Besides a lower microhardness of ~ 629 HV{sub 0.2} was detected for pure Ni, which was much lower that of ~ 752 HV{sub 0.2} for Ni-LaCl{sub 3} films, but higher than that of ~ 336 HV{sub 0.2} for Ti substrate. In addition, a superior corrosion resistance was obtained for Ni-LaCl{sub 3} composites relative to pure Ni, which was ascribed to the coexistence of La{sup 3+} ions and its La-rich insoluble products on its corroded surfaces for completing the pitting holes. In view of these, the as-deposited Ni-LaCl{sub 3} films on the surface of Ti substrate could guide an available proposal for surface modifying of Ti alloys against the wear corrosive failures, further intensifying their servicing life as subjected to harsh conditions.

36 MATERIALS SCIENCE↗

Understanding the Effect of Interlayers at the Thiophosphate Solid Electrolyte/Lithium Interface for All-Solid-State Li Batteries

All-solid-state Li-ion batteries afford possibilities to enhance battery safety while improving their energy and power densities. Current challenges for achieving high-performance all-solid-state batteries with long cycle life include shorting resulting predominantly from Li dendrite formation and infiltration through the solid electrolyte (SE) and increases in cell impedance induced by SE decomposition at the SE/electrode interface. In this work, we evaluate the electrochemical properties of two interlayer materials, Si and Li x Al (2-x/3) O 3 (LiAlO), at the Li 7 P 3 S 11 (LPS)/Li interface. Compared to the Li/LPS/Li symmetric cells in absence of interlayers, the presence of Si and LiAlO both significantly enhance the cycle number and total charge passing through the interface before failures resulting from cell shorting. In both cases, the noted improvements were accompanied by cell impedances that had increased substantially. The data reveal that both interlayers prevent the direct exposure of LPS to the metallic Li and therefore eliminate the intrinsic LPS decomposition that occurs at Li surfaces before electrochemical cycling. After cycling, a reduction of LPS to Li 2 S occurs at the interface when a Si interlayer is present; LiAlO, which functions to drop the potential between Li and LPS, suppresses LPS decomposition processes. The relative propensities toward SE decomposition follows from the electrochemical potentials at the interface, which are dictated by the identities of the interlayer materials. As a result, this work provides new insights into the phase dynamics associated with specific choices for SE/electrode interlayer materials and the requirements they impose for realizing high efficiency, long lasting all-solid-state batteries.

25 ENERGY STORAGE↗

Graphene-Modified Tin Dioxide for Efficient Planar Perovskite Solar Cells with Enhanced Electron Extraction and Reduced Hysteresis

Tin dioxide (SnO 2 ) as an efficient electron transport layer (ETL) has been demonstrated for emerging high-performance organic–inorganic hybrid perovskite solar cells (PSCs). However, the low-temperature solution-processed SnO 2 usually results in high trap-state density and current–voltage hysteresis. Here, we reported an effective strategy to solve this problem by incorporating graphene ink into the low-temperature processed SnO 2 for planar structure PSCs. The electron extraction efficiency has been significantly improved with graphene-doped SnO2 ETL coupled with attenuated charge recombination at the ETL/perovskite interface. The power conversion efficiency (PCE) of PSCs based on the graphene–SnO 2 ETL reached over 18% with negligible hysteresis. Incorporation of graphene into the ETL layer also enhanced the device stability retaining 90% of the initial PCE value after storing in ambient condition with a relative humidity of 40 ± 5% for 300 h. Our results provide an important insight into further efficiency boost in SnO 2 -based low-temperature processed PSCs.

36 MATERIALS SCIENCE↗

Low-Voltage, CMOS-Free Synaptic Memory Based on Li X TiO 2 Redox Transistors

Neuromorphic computers based on analogue neural networks aim to substantially lower computing power by reducing the need to shuttle data between memory and logic units. Artificial synapses containing nonvolatile analogue conductance states enable direct computation using memory elements; however, most nonvolatile analogue memories require high write voltages and large current densities and are accompanied by nonlinear and unpredictable weight updates. Here, we develop an inorganic redox transistor based on electrochemical lithium-ion insertion into Li X TiO 2 that displays linear weight updates at both low current densities and low write voltages. The write voltage, as low as 200 mV at room temperature, is achieved by minimizing the open-circuit voltage and using a low-voltage diffusive memristor selector. We further show that the Li X TiO 2 redox transistor can achieve an extremely sharp transistor subthreshold slope of just 40 mV/decade when operating in an electrochemically driven phase transformation regime.

42 ENGINEERING↗

Sub-Nanometer Nanoclusters of Copper Atop Single-Atom Copper Moieties toward Electrochemical CO 2 Hydrogenation to Methane

The electrochemical CO 2 reduction (eCO 2 R) offers a compelling route for converting CO 2 into value-added fuels and chemicals. Among CO 2 -derived products, methane (CH 4 ) occupies a distinct position, serving both as a key intermediate for emerging cascade electro-oxidation to oxygenates and as a strategically important extraterrestrial fuel that can be generated in situ from off-planet CO 2 resources. Although Cu-based catalysts capable of selectively producing CH 4 have been reported, they seldom sustain high selectivity at practically relevant current densities. Here, we created a single-step co-pyrolysis strategy toward generating and anchoring Cu sub-nanometer clusters (Cu SNC ) atop Cu-N x single-atom (SA) motifs embedded within N-doped carbon (NC), with controllable nanostructures through tuning of the synthesis parameters. Complementary spectroscopic analyses and density functional theory (DFT) calculations help reveal a structure−activity correlation that could guide the catalyst design. The Cu SNC @NC sample synthesized at 550 °C pyrolysis temperature (best described and modeled as Cu 3 -CuN 4 domains) represents the most effective combination of cluster size, metal-nitrogen coordination, and adsorption energetics needed to selectively promote CH 4 generation versus other eCO 2 R products. Incorporating pulsed electrolysis and hydrophobicity-modulated transport tuning at the triple-phase boundary (TPB) further enhanced CH 4 production achieving a partial CH 4 current density of ∼321 mA cm −2 , 53% Faradaic efficiency (FECH 4 ), and less than 4% combined FE for other eCO 2 R products, simplifying downstream CH 4 purification or upgrading. This work establishes generalizable principles for controlling Cu cluster atomicity and metal−nitrogen coordination, both of which are recognized determinants of CH 4 -efficient eCO 2 R.

CH4 production↗

Solution epitaxy of polarization-gradient ferroelectric oxide films with colossal photovoltaic current

Solution growth of single-crystal ferroelectric oxide films has long been pursued for the low-cost development of high-performance electronic and optoelectronic devices. However, the established principles of vapor-phase epitaxy cannot be directly applied to solution epitaxy, as the interactions between the substrates and the grown materials in solution are quite different. Here, we report the successful epitaxy of single-domain ferroelectric oxide films on Nb-doped SrTiO 3 single-crystal substrates by solution reaction at a low temperature of ~200 o C. The epitaxy is mainly driven by an electronic polarization screening effect at the interface between the substrates and the as-grown ferroelectric oxide films, which is realized by the electrons from the doped substrates. Atomic-level characterization reveals a nontrivial polarization gradient throughout the films in a long range up to ~500 nm because of a possible structural transition from the monoclinic phase to the tetragonal phase. This polarization gradient generates an extremely high photovoltaic short-circuit current density of ~2.153 mA/cm 2 and open-circuit voltage of ~1.15 V under 375 nm light illumination with power intensity of 500 mW/cm 2 , corresponding to the highest photoresponsivity of ~4.306×10 -3 A/W among all known ferroelectrics. Our results establish a general low-temperature solution route to produce single-crystal gradient films of ferroelectric oxides and thus open the avenue for their broad applications in self-powered photo-detectors, photovoltaic and optoelectronic devices.

36 MATERIALS SCIENCE↗

Structure–performance relationships of lithium-ion battery cathodes revealed by contrast-variation small-angle neutron scattering

Lithium-ion battery cathodes are porous composites of active material, conductive carbon, and polymer binder. Controlling the cathode microstructure is key to achieving high energy density and cycling stability. Current characterization techniques lack the nanoscale resolution over representative volumes necessary to relate cathode microstructure to cycling performance. To address this challenge, we utilize contrast-variation small-angle neutron scattering to quantify the chemical and structural features of cathodes wet by dimethyl carbonate, representing a relevant solvent environment. Using neutron scattering measurements, we identify an expansion in carbon and polymer structures that arises after calendering and wetting with solvent. Further, we deconvolute the carbon and binder phases to obtain the solvent-accessible carbon black surface area, which we correlate to diminished capacity retention driven by electrolyte decomposition on exposed carbon. This technique provides nanoscale insight into composite cathode microstructures and resulting cycling performance, promising future applications to a broad range of porous materials that exist in energy storage systems.

25 ENERGY STORAGE↗

Pressure-induced emergence of unusually high-frequency transverse excitations in a liquid alkali metal: Evidence of two types of collective excitations contributing to the transverse dynamics at high pressures

Unlike phonons in crystals, the collective excitations in liquids cannot be treated as propagation of harmonic displacements of atoms around stable local energy minima. The viscoelasticity of liquids, reflected in transition from the adiabatic to elastic high-frequency speed of sound and in absence of the long-wavelength transverse excitations, results in dispersions of longitudinal (L) and transverse (T) collective excitations essentially different from the typical phonon ones. Practically, nothing is known about the effect of high pressure on the dispersion of collective excitations in liquids, which causes strong changes in liquid structure. Here dispersions of L and T collective excitations in liquid Li in the range of pressures up to 186 GPa were studied by ab initio simulations. Two methodologies for dispersion calculations were used: direct estimation from the peak positions of the L/T current spectral functions and simulation-based calculations of wavenumber-dependent collective eigenmodes. It is found that at ambient pressure, the longitudinal and transverse dynamics are well separated, while at high pressures, the transverse current spectral functions, density of vibrational states, and dispersions of collective excitations yield evidence of two types of propagating modes that contribute strongly to transverse dynamics. Emergence of the unusually high-frequency transverse modes gives evidence of the breakdown of a regular viscoelastic theory of transverse dynamics, which is based on coupling of a single transverse propagating mode with shear relaxation. The explanation of the observed high-frequency shift above the viscoelastic value is given by the presence of another branch of collective excitations. With the pressure increasing, coupling between the two types of collective excitations is rationalized within a proposed extended viscoelastic model of transverse dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗