Search NASA⌕ Search

SEARCH · Search NASA

Results for “Interfacial instability”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

214 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Thermally induced PtOx interfacial layer enhances stability of Pt/β-Ga2O3 vertical Schottky diodes

This study investigates the long-term stability of Pt/β-Ga2O3 field-plated Schottky barrier diodes at high temperatures, with extended thermal cycling and soaking stress. The device characteristics reveal a strong dependence on operating temperature, leading to an ON/OFF current ratio of ∼10× at ±3 V and 600 °C. Extensive thermal cycling (25 cycles over 100 h) between room temperature and 350 °C shows that leakage currents stabilize after the initial ten cycles. This stabilization is likely due to the formation of a thin PtOx layer at the Pt/β-Ga2O3 interface, as confirmed by high-resolution scanning transmission electron microscopy. Further exposure to a constant 350 °C environment for 10 h reveals a slight increase in the leakage current from 10−7 to 10−6 A at −5 V and degradation of the forward current, due to potential thermodynamic instability of the Ohmic contacts. This study provides insights into the changes in the Pt/β-Ga2O3 diode performance with thermal stress, offering a basis for predicting the device’s operational reliability at high temperatures for sensing and power applications.

08 HYDROGEN↗
NASA NTRS1996

Influence of Thermocapillary Flow on Capillary Stability: Long Float-Zones in Low Gravity

A model problem is posed to study the influence of flow on the interfacial stability of a nearly cylindrical liquid bridge for lengths near its circumference (the Plateau-Rayleigh limit). The flow is generated by a shear stress imposed on the deformable interface. The symmetry of the imposed shear stress mimics the thermocapillary stress induced on a float-zone by a ring heater (i.e. a full zone). Principal assumptions are (1) zero gravity, (2) creeping flow, and (3) that the imposed coupling at the free surface between flow and temperature fields is the only such coupling. A numerical solution, complemented by a bifurcation analysis, shows that bridges substantially longer than the Plateau-Rayleigh limit are possible. An interaction of the first two capillary instabilities through the stress-induced flow is responsible. Time-periodic standing waves are also predicted in certain parameter ranges. Motivation comes from extra-long float-zones observed in MEPHISTO space lab experiments (June 1994).

Chen, Yi-Ju↗
NASA NTRS2023

Heat Transfer and Interfacial Flow Physics of Microgravity Flow Boiling in Single-Side-Heated Rectangular Channel with Subcooled Inlet Conditions – Experiments Onboard the International Space Station

This study is the culmination of a long-term collaborative effort between researchers from the Purdue University Boiling and Two-Phase Flow Laboratory (PU-BTPFL) and the NASA Glenn Research Center to investigate gravitational effects on flow boiling and flow condensation. The science and design concepts for this large-scale effort were initiated in 2011 and included several studies detailing various aspects of two-phase fluid physics in both Earth gravity and microgravity, culminating in construction of the large-scale experimental facility named “Flow Boiling and Condensation Experiment (FBCE)”. The experiment was launched to the International Space Station (ISS) in August 2021. Following the successful installation of FBCE, equipped with the Flow Boiling Module (FBM), onboard the ISS and completion of several safety checks, flow boiling experiments were performed for five months from February 2022 until July 2022. This resulted in a large flow boiling database covering broad ranges of operating parameters and heating configurations spanning several research objectives. This study investigates microgravity flow boiling of n-perfluorohexane with subcooled inlet in a single-side-heated rectangular channel of dimensions 114.6-mm heated length, 2.5-mm heated width, and 5.0-mm height. Key operating parameters investigated are mass velocity (199.90 – 3200.13 kg/m 2 s), inlet subcooling (0.10 – 45.76°C), and inlet pressure (113.30 – 164.29 kPa). Images and image sequences acquired via high-speed-video are presented to elucidate the interfacial flow physics. To analyze and explain the effects of various parameters in microgravity, heat transfer results are presented as flow boiling curves, streamwise profiles of wall temperature and heat transfer coefficient, and parametric trends of local and averaged heat transfer coefficient. Mass velocity and inlet subcooling significantly influenced most of the aforementioned aspects of flow boiling, whereas effects of inlet pressure were comparatively insignificant. Although the data and observed flow physics might be different, the parametric effects and trends in microgravity are similar to vertical upflow in Earth gravity. Some cases, especially low mass velocities, high heat fluxes, and large degrees of inlet subcooling, experienced temporally anomalous flow behaviors caused by two-phase flow instabilities manifesting as flow reversals and resulted in deviations in overall trends. Severe thermodynamic non-equilibrium is observed throughout the channel. Overall, FBCE’s ISS experiments were successful for subcooled inlet with single-sided heating of rectangular channel, and the collected data well established the various effects on flow boiling physics in highly controlled long-term microgravity conditions.

flow boiling↗
NASA NTRS2005

The Dynamics of Miscible Interfaces: Simulations

This research project focuses on the dynamics of interfacial regions between miscible fluids. While much attention has focused on immiscible interfaces in the past, miscible interfaces have been explored to a much lesser degree, so that there are many open questions regarding their dynamics at this time. Among the more pressing issues is the role that nonconventional stresses can play in such interfacial regions. Such stresses are typically not accounted for in efforts to model the dynamics of miscible flows. Our research aims to clarify under which circumstances these stresses do have to be taken into account, and what quantitative approaches are most suitable in this regard. In order to address these issues, we have focused on conducting linear stability analyses and nonlinear simulations for capillary tube and Hele-Shaw flows, and to compare the results with corresponding experiments performed in the labs of our co-investigators Prof. Maxworthy at USC, and Dr. Balasubramaniam at NASA. Over the duration of the project we have, among other things, focused on the effects of variable diffusion coefficients in such flows, and specifically on their influence in the growth of instabilities. Furthermore, our three-dimensional spectral element simulations have made good progress, so that we have come to a point where we can conduct more detailed comparisons with experimental observations. We are currently focusing our efforts on reproducing the tip-splitting instability observed by Maxworthy. Finally, we have discovered a new core-annular flow instability in the Stokes flow regime during the last year. This represents a significant finding, as this instability does not have an immiscible counterpart.

Meiburg, Eckart↗
NASA NTRS2014

Coupled Fluid-Structure Interaction Analysis of Solid Rocket Motor with Flexible Inhibitors

Flexible inhibitors are generally used in solid rocket motors (SRMs) as a means to control the burning of propellant. Vortices generated by the flow of propellant around the flexible inhibitors have been identified as a driving source of instabilities that can lead to thrust oscillations in launch vehicles. Potential coupling between the SRM thrust oscillations and structural vibration modes is an important risk factor in launch vehicle design. As a means to predict and better understand these phenomena, a multidisciplinary simulation capability that couples the NASA production CFD code, Loci/CHEM, with CFDRC's structural finite element code, CoBi, has been developed. This capability is crucial to the development of NASA's new space launch system (SLS). This paper summarizes the efforts in applying the coupled software to demonstrate and investigate fluid-structure interaction (FSI) phenomena between pressure waves and flexible inhibitors inside reusable solid rocket motors (RSRMs). The features of the fluid and structural solvers are described in detail, and the coupling methodology and interfacial continuity requirements are then presented in a general Eulerian-Lagrangian framework. The simulations presented herein utilize production level CFD with hybrid RANS/LES turbulence modeling and grid resolution in excess of 80 million cells. The fluid domain in the SRM is discretized using a general mixed polyhedral unstructured mesh, while full 3D shell elements are utilized in the structural domain for the flexible inhibitors. Verifications against analytical solutions for a structural model under a steady uniform pressure condition and under dynamic modal analysis show excellent agreement in terms of displacement distribution and eigenmode frequencies. The preliminary coupled results indicate that due to acoustic coupling, the dynamics of one of the more flexible inhibitors shift from its first modal frequency to the first acoustic frequency of the solid rocket motor. This insight could have profound implications for SRM and flexible inhibitor designs for current and future launch vehicles including SLS.

Yang, H. Q.↗
DOE OSTI2025

Further Development of the Tamped Richtmyer-Meshkov Instability Method and Application to Molybdenum Dynamic Strength Calibration and Tabulation

The high pressure and high strain rate dynamic strength of Mo is experimentally and computationally investigated in the 3–20 GPa stress, 50–600 C temperature, and 10 5 –10 6 /s strain rate regimes using a modified tamped Richtmyer-Meshkov instability (RMI) method. Modifications to the tamped RMI method include a method to determine loading states during strain, a new strength calibration function based on interface shape, and a robust uncertainty quantification method. These modifications improve fidelity of the tamped RMI method, allowing evaluation of the compensating effects of pressure hardening, strain rate hardening, strain hardening, and thermal softening. The new calibration function based on interface shape is not limited to sinusoidal corrugations and could be applied to additional interface shapes. Plate impact experiments are performed at Argonne National Laboratory’s Advanced Photon Source’s Dynamic Compression Sector operated by Washington State University (DCS), driving a planar shock front through a corrugated Mo-D 2 O or Mo-C 8 F 18 interface, forcing the corrugation to significantly deform. The extent of interfacial deformation, RMI growth, is experimentally observed using X-ray phase contrast imaging at the DCS. RMI jet lengths and jet shapes are extracted from the experimental radiographs, then used to calibrate numerical simulations performed with the Sandia National Laboratories (SNL) hydrocode CTH. Mo yield strength, Y, as a function of shock pressure, P, strain rate, $\dot{\varepsilon }$, accumulated strain, ϵ, relative volumetric compression, RD , and temperature, T , is determined for each impact experiment and presented. The calibrated Mo yield strength values range 1.2–1.8 GPa, with strength generally decreasing as the impact stress increases. This trend is likely caused by thermal softening or strain localization. The tabular yield strength versus loading condition data presented in this paper can be used to fit complex strength models.

Voorhees, T. J. [Sandia National Lab. (SNL-CA), Li↗
DOE OSTI2021

Pore-Scale Dynamics of Liquid CO2–Water Displacement in 2D Axisymmetric Porous Micromodels Under Strong Drainage and Weak Imbibition Conditions: High-Speed μPIV Measurements

Resolving pore-scale transient flow dynamics is crucial to understanding the physics underlying multiphase flow in porous media and informing large-scale predictive models. Surface properties of the porous matrix play an important role in controlling such physics, yet interfacial mechanisms remain poorly understood, in part due to a lack of direct observations. This study reports on an experimental investigation of the pore-scale flow dynamics of liquid CO 2 and water in two-dimensional (2D) circular porous micromodels with different surface characteristics employing high-speed microscopic particle image velocimetry (μPIV). The design of the micromodel minimized side boundary effects due to the limited size of the domain. The high-speed μPIV technique resolved the spatial and temporal dynamics of multiphase flow of CO 2 and water under reservoir-relevant conditions, for both drainage and imbibition scenarios. When CO 2 displaced water in a hydrophilic micromodel (i.e., drainage), unstable capillary fingering occurred and the pore flow was dominated by successive pore-scale burst events (i.e., Haines jumps). When the same experiment was repeated in a nearly neutral wetting micromodel (i.e., weak imbibition), flow instability and fluctuations were virtually eliminated, leading to a more compact displacement pattern. Energy balance analysis indicates that the conversion efficiency between surface energy and external work is less than 30%, and that kinetic energy is a disproportionately smaller contributor to the energy budget. This is true even during a Haines jump event, which induces velocities typically two orders of magnitude higher than the bulk velocity. These novel measurements further enabled direct observations of the meniscus displacement, revealing a significant alteration of the pore filling mechanisms during drainage and imbibition. While the former typically featured burst events, which often occur only at one of the several throats connecting a pore, the latter is typically dominated by a cooperative filling mechanism involving simultaneous invasion of a pore from multiple throats. This cooperative filling mechanism leads to merging of two interfaces and releases surface energy, causing instantaneous high-speed events that are similar, yet fundamentally different from, burst events. Finally, pore-scale velocity fields were statistically analyzed to provide a quantitative measure of the role of capillary effects in these pore flows.

Li, Yaofa↗
DOE OSTI2025

Heterogeneous catalysis: Optimal performance at a phase boundary?

Most of the industrially used heterogeneous catalysts have been discovered by trial and error, and despite decades of experience, the discovery of new catalysts continues to be extremely challenging. The drive to uncover guiding principles in catalyst design is more present than ever. We share a series of observations indicating that optimal catalysts typically function at characteristic phase boundaries (e.g., abrupt changes in adsorbate coverage, catalyst structure, etc.) accessed in the reaction conditions. The catalyst exploits the associated instability—the desire to exist in multiple states simultaneously—as a driving force for chemical transformations. In other words, phase boundaries are good places to start the catalyst search, and indeed, we should focus on at least two phases at once rather than just one. Here, we substantiate this claim with several studies that combine statistical operando modeling and experiments. Transpiring from these observations is a hitherto unrecognized vector in catalyst discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Insight into pseudo-film-boiling in supercritical water under simplified interfacial conditions

The focus of this paper is the physics of supercritical water film boiling through the simulation of natural convection of supercritical water in a rectangular cavity. It has been widely believed that above a fluid's critical point, only one phase exists. However, recent research has indicated the existence of distinct gas-like and liquid-like regions separated by the Widom line, which is the locus of the maxima of the specific heat. Along the Widom line, density decreases sixfold, viscosity drops by a factor of two, while specific heat spikes by an order of magnitude. These variations, specifically in density and viscosity, produce a thick pseudo-interface and flow dynamics behavior akin to film-boiling, denoted here as pseudo-two-phase flow dynamics. When the cavity is heated from the bottom, a pseudo-film of gas-like fluid is formed at the heated wall, and the flow complexity evolves, characterized by the formation of multiple vortices. Results demonstrate the ability of modern conjugate heat transfer computational fluid dynamics to capture the pseudo two-phase regime, with the formation of a pseudo-film at the heated wall. Further, the boiling curve is studied, showing an increase in heat flux with an increase in the temperature differential between the wall and the pseudo-critical temperature. Furthermore, results also show a previously uncharacterized instability, where the convection cells in the cavity oscillate and can flip directions under certain conditions.

Computational fluid dynamics↗
NASA NTRS2023

Effects of Heating Configuration and Operating Parameters on Heat Transfer and Interfacial Physics of Microgravity Flow Boiling With Subcooled Inlet Conditions –Experiments Onboard the International Space Station

This study is part of the Flow Boiling and Condensation Experiment (FBCE), a collaborative effort between the Purdue University Boiling and Two-Phase Flow Laboratory (PU-BTPFL) and the NASA Glenn Research Center. The FBCE fitted with the Flow Boiling Module (FBM) was launched to the International Space Station (ISS) in August 2021 and experiments were successfully performed from February to July 2022 to amass a large microgravity-flow-boiling database. This study is focused on heat transfer and flow visualization of microgravity flow boiling of n-Perfluorohexane in a rectangular channel of 5.0 mm height, 2.5 mm width (heated), and 114.6 mm length, with subcooled inlet conditions. High-speed-video photography is utilized to present flow patterns and temporal interfacial behavior. Heat transfer results are presented in the form of flow boiling curves and both parametric curves and streamwise profiles of wall temperature and heat transfer coefficient. Firstly, the parametric effects of mass velocity (199.4 – 3200.0 kg/m 2 s), inlet subcooling (0.2 – 46.0°C), and inlet pressure (124.2 – 176.7 kPa), on the aforementioned aspects are assessed for double-sided heating to establish them for a microgravity environment. Of these three parameters, mass velocity and inlet subcooling mostly determine the microgravity flow boiling behavior, while inlet pressure plays an insignificant role. Flow patterns for double-sided heating are more complex than those for single-sided heating due to interaction between the two vapor layers. Vapor interaction is minimized at high subcoolings and high mass velocities due to strong condensation offered by the subcooled bulk liquid layer separating them. Despite the different flow patterns, both single- and double-sided heating generally result in similar parametric trends and local heat transfer coefficients for similar operating conditions. Flow instabilities manifest as temporal flow anomalies and temperature oscillations, and their severity increases with increasing boiling number. Secondly, the effects of heating configuration are analyzed by comparing and contrasting several aspects of single- and double-sided heating data. The heat fluxes at which onset of nucleate boiling degradation (ONBD) and critical heat flux (CHF) occur are distinctly different for single- and double-sided heating. There exists a threshold inlet subcooling demarcating the dominance of flow acceleration and condensation effects in vapor removal from the near-wall region and replenishment of fresh liquid for boiling. Above the threshold, condensation from the near-wall region is dominant and single-sided heating yields higher heat fluxes, and below it, acceleration is dominant and double-sided yields higher heat fluxes. At mass velocity in the range of 200 – 2400 kg/m 2 s, the threshold inlet subcooling lies in the approximate range of 20 – 30°C (corresponding inlet quality of roughly -0.40 – -0.20).

Microgravity↗
DOE OSTI2025

Interface instabilities in hafnium hydride entrained iron metal matrix composites

The chemical interactions in Fe–HfH 2 metal matrix composites (MMCs) are studied across multiple length scales to elucidate the decomposition of the parent phases and corresponding reaction zone physics during direct current sintering. Fe–HfH 2 composites were synthesized with increasing as-mixed hydride contents of Fe–25% HfH 2 , Fe–40% HfH 2 , Fe–55% HfH 2 , and Fe–70% HfH 2 (all in vol. %) to demonstrate the ability to achieve sintered MMCs with target hydride contents. Samples were probed across multiple length scales through a multi-modal workflow employing x-ray diffraction, scanning electron microscopy and segmentation analysis, and synchrotron techniques including hard x-ray fluorescence mapping and nanoprobe x-ray absorption near-edge structure measurements. Under the selected sintering temperature and pressure conditions, hydrogen evolution is seen to evolve through parallel paths: thermal decomposition from during the transformation of HfH 2 to HfH x<2 and through subsequent reaction with the Fe matrix leading to intermetallic phase formation. Specifically, HfFe and HfFe 2 intermetallic formation accelerates the release of hydrogen with a subsequent HfO 2 phase forming at grain boundaries. For this MMC, the consumption or loss of hydrogen can be considerable in compacts with initial hydride loading of 25%–40% HfH 2 approaching 83% hydrogen loss for the lower volume fraction composites. Increasing the volume fraction of HfH 2 to 70% enhanced the retained hydrogen content to 53% and attributed to the reduced interfacial area intrinsic to the increased HfH 2 loading in this MMC.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Development of an Atomization Methodology for Spray Combustion

In liquid rocket propulsion, the knowledge and the understanding of liquid-gas interfacial phenomena are very important. This is important for predicting the onset of cavitation occurring in swirl injection elements used in STME, as well as atomization processes in shear-induced injectors (co-axial) and impinging injector elements. From the fact that all the physical processes including droplet size distribution, droplet dispersion, mixing and combustion are controlled by atomization processes, it is expected that the successful incorporation of the volume of fraction (VOF) will greatly enhance the analytical capability of predicting spray combustion processes in liquid-fueled engines. In this paper, a methodology is developed to define and track interfaces between two fluids in non-orthogonal, body-fitted grids using a single fractional volume of fluid (VOF) variable to describe the distribution of the liquid phase in a gas-liquid flow field. This method was implemented in a mature CFD code MAST (Multiphase All-Speed Transient) utilizing the general PISO-C algorithm. For the preliminary study on the analysis of spray combustion and tracking of the interface between two phases, we will report on the progress of the simulation of the instability on the liquid column; the surface wave instability and the droplet breakup from the liquid surface.

Seung, S. P.↗
DOE OSTI2020

Exploration of Electrochemical Reactions at Organic–Inorganic Halide Perovskite Interfaces via Machine Learning in In Situ Time-of-Flight Secondary Ion Mass Spectrometry

The instability of hybrid organic–inorganic perovskite (HOIP) devices is one of the significant challenges preventing commercialization. Exploring these phenomena is severely limited by the complexity of the intrinsic electrochemistry of HOIPs, the presence of multiple volatile and mobile ionic species, and the possible role of environmentally induced reactions at surfaces and triple-phase junctions. Here, in situ studies of the electrochemistry of methylammonium lead bromide perovskite with the Au electrode interface are reported via light- and voltage-dependent time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging of lateral perovskite heterostructures. While ToF-SIMS allows for the visualization of the chemical composition along the surface and its evolution with light and electrical bias, the interpretation of the multidimensional data obtained is often limited due to strong correlations between chemical signatures and the need to track multiple peaks at once. Here, a machine learning workflow combining the Hough transform and non-negative matrix factorization and no-negative tensor decomposition is developed to avoid this limitation and extract salient features of associated chemical changes and to separate the light- and voltage-dependent dynamics. Finally, combining these in situ characterizations and the machine learning workflow provides comprehensive information on the chemical nature of moving species, ion accumulation, and interfacial electrochemical reactions in HOIP devices.

36 MATERIALS SCIENCE↗
NASA NTRS2002

Length Scale and Gravity Effects on Microgravity Boiling Heat Transfer

Boiling is a complex phenomenon where hydrodynamics, heat transfer, mass transfer, and interfacial phenomena are tightly interwoven. An understanding of boiling and critical heat flux in microgravity environments is of importance to space based hardware and processes such as heat exchange, cryogenic fuel storage and transportation, electronic cooling, and material processing due to the large amounts of heat that can be removed with relatively little increase in temperature. Although research in this area has been performed in the past four decades, the mechanisms by which heat is removed from surfaces in microgravity are still unclear. In earth gravity, buoyancy is an important parameter that affects boiling heat transfer through the rate at which bubbles are removed from the surface. A simple model describing the bubble departure size based on a quasistatic force balance between buoyancy and surface tension is given by the Fritz [I] relation: Bo(exp 1/2) = 0.0208 theta where Bo is the ratio between buoyancy and surface tension forces. For small, rapidly growing bubbles, inertia associated with the induced liquid motion can also cause bubble departure. In microgravity, the magnitude of effects related to natural convection and buoyancy are small and physical mechanisms normally masked by natural convection in earth gravity such as Marangoni convection can substantially influence the boiling and vapor bubble dynamics. CHF (critical heat transfer) is also substantially affected by microgravity. In 1 g environments, Bo has been used as a correlating parameter for CHF. Zuber's CHF model for an infinite horizontal surface assumes that vapor columns formed by the merger of bubbles become unstable due to a Helmholtz instability blocking the supply of liquid to the surface. The jets are spaced lambda(sub D) apart, where lambda(sub D) = 2pi square root of 3[(sigma)/(g(rho(sub l) - rho(sub v)](exp 1/2) = 2pi square root of 3 L Bo(exp -1/2) = square root of 3 lambda(sub c) and is the wavelength that amplifies most rapidly. The critical wavelength, lambda(sub c), is the wavelength below which a vapor layer underneath a liquid layer is stable. For heaters with Bo smaller than about 3 (heaters smaller than lambda(sub D)), the above model is not applicable, and surface tension effects dominate. Bubble coalescence is thought to be the mechanism for CHF under these conditions. Small Bo can result by decreasing the size of a heater in earth gravity, or by operating a large heater in a lower gravity environment. In the microgravity of space, even large heaters can have low Bo, and models based on Helmholtz instability should not be applicable. The macrolayer model of Haramura and Katto is dimensionally equivalent to Zuber's model and has the same dependence on gravity, so it should not be applicable as well. The goal of this work is to determine how boiling heat transfer mechanisms in a low-g environment are altered from those at higher gravity levels. Boiling data using a microheater array was obtained under gravity environments ranging from 1.8 g to 0.02 g with heater sizes ranging from 2.7 mm to 1 mm. The boiling behavior for 2.7 mm at 0.02 g looked quite similar to boiling on the 1 mm heater at 1 g-the formation of a large primary bubble surrounded by smaller satellite bubbles was observed under both conditions. The similarity suggests that for heaters smaller than some fraction of I(sub c), coalescence and surface tension dominate boiling heat transfer. It also suggests that microgravity boiling can be studied by studying boiling on very small heaters.

Kim, Jungho↗
DOE OSTI2021

Effect of Surface Ionic Screening on Polarization Reversal and Phase Diagrams in Thin Antiferroelectric Films for Information and Energy Storage

Emergent behaviors in antiferroelectric thin films due to a coupling between surface electrochemistry and intrinsic polar instabilities are explored within the framework of the modified 2-4-6 Landau-Ginzburg-Devonshire (LGD) thermodynamic approach. By using phenomenological parameters of the LGD potential for a bulk antiferroelectric and a Stephenson-Highland (SH) approach, we study the role of surface ions with a charge density proportional to the relative partial oxygen pressure on the dipole states and their reversal mechanisms in antiferroelectric thin films. The combined LGDSH approach allows the boundaries of antiferroelectric, ferroelectriclike antiferroionic, and electretlike paraelectric states as a function of temperature, oxygen pressure, surface-ion formation energy and concentration, and film thickness to be delineated. This approach also allows the characterization of the polar and antipolar orderings dependence on the voltage applied to the antiferroelectric film, as well as the analysis of their static and dynamic hysteresis loops. Furthermore, the applications of the antiferroelectric films covered with a surface-ion layer for energy and information storage are explored and discussed.

25 ENERGY STORAGE↗
DOE OSTI2023

Electrolyte Reactivity on the MgV 2 O 4 Cathode Surface

Predictive understanding of the solvation-dependent reactivity and molecular interaction of electrolyte ions and solvent molecules on reactive electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at electrode-electrolyte interface (EEI) of multivalent Mg batteries. In this work, the isolated intrinsic reactivities of prominent chemical species present in magnesium bis(trifluoromethanesulfonimide) (Mg(TFSI) 2 ) in diglyme (G2) electrolytes, including ionic (TFSI - , [Mg(TFSI)] + , [Mg(TFSI):G2] + , [Mg(TFSI):2G2] + ) as well as neutral molecules (G2) on magnesium vanadate cathode (MgV 2 O 4 ) surface has been studied using a combination of first-principles calculations and multimodal analysis of well-defined cathode electrolyte interphase (CEI) layers. Here, our calculations show that non-solvated [Mg(TFSI)] + is the strongest adsorbing species on the MgV 2 O 4 surface compared to all other ions while fully solvated [Mg(TFSI):2G2] + are least favorable to decomposition. The cleavage of C-S bonds in TFSI - to form CF 3 - is predicted to be most desired pathway for all ionic species, which is followed by the cleavage of C-O bonds of G2 to yield CH 3 + or OCH 3 - species. The strong stabilization and electron transfer between ionic electrolyte species and MgV 2 O 4 is found to significantly favor these decomposition reactions on the surface compared to intrinsic gas phase dissociation. Experimentally, we used state-of-the-art ion soft landing to selectively deposit mass-selected TFSI - , [Mg(TFSI):G2] + and [Mg(TFSI):2G2] + on MgV 2 O 4 thin film to form well-defined electrolyte-MgV 2 O 4 interface. Analysis of soft-landed interphase using X-ray photoelectron, X-ray absorption near edge structure, electron energy-loss spectroscopies as well as transmission electron microscopy confirmed the presence of decomposition species (e.g., MgFx, carbonates) formed in the interfacial region and the higher amount of MgFx with [Mg(TFSI):G2] + , which corroborates the theoretical observation. Overall, we established the mechanistic pathway for the electrolyte-induced formation of passivating fluorides on MgV 2 O 4 cathode facilitated by the surface adsorption and charge transfer, which provided essential knowledge for rational design of stable electrolytes for multivalent cathodes.

Cathode-electrolyte interphase formation↗