Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “surface engineering”

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.

At least 1,603 records · Page 89
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

The effect of longer-range waviness on X-ray reflectivity measurements

A model for calculating the X-ray reflectivity (XRR) of surfaces to extract both roughness and waviness features is presented. Expressions of reflectivity intensity are derived as a function of root-mean-square (RMS) roughness σ, RMS waviness σ L , and the cut-off frequency between the features ω 0 . Experiments were conducted at the Advanced Light Source at Lawrence Berkeley National Laboratory, beamline 8.3.2, on BK7 glass manufactured with a multi-step polishing process to validate the model, and were compared with atomic force microscopy (AFM), Fizeau interferometry and surface profilometry measurements. Here, the parameter results and their deviations for XRR measurements were σ = 2.9 ± 0.2 nm and σ L = 14.6 ± 0.5 nm with a wavelength cut-off of 1/(18 ± 2) µm –1 , while the results from the AFM, Fizeau and profilometry measurements were σ AFM = 3.4 ± 0.4 nm, σ L,Fizeau = 21.6 nm, σ prof = 4.0 ± 0.1 nm, and σ L,prof = 21.4 ± 0.1 nm with cut-offs for the profilometry and Fizeau measurements limited to frequencies of (1/16) µm –1 to (1/4) mm –1 .

42 ENGINEERING↗
DOE OSTI2022

Bridging knowledge gaps in liquid- and vapor-fed CO 2 electrolysis through active electrode area

Increased use of gas diffusion electrodes for CO 2 electroreduction widens the experimental phase space that was previously inaccessible using foil electrodes, raising fundamental questions over the impacts of key variables that translate between liquid- and vapor-fed CO 2 electrolysis systems. This work focuses on studying the interplay of current-potential profiles and electrochemically active surface area (ECSA) by implementing a Cu nanoflower catalyst morphology. The results show decreased overpotentials as much as 460 and 174 mV for foil and gas diffusion electrodes, respectively, while maintaining or improving multi-carbon product current density. Furthermore, these overpotential shifts and product activities normalized by ECSA lead to current-potential relationships akin to those of the Tafel description, which are found through a continuum model to be useful for describing the roughness dependence for both liquid- and vapor-fed systems. This analysis establishes a holistic approach for establishing catalyst design criteria to improve materials development for CO 2 .

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2017

Simulating Bubble Deformations Using the Intersection Marker (ISM) Front-Tracking method

Surface and volume tracking methods have been under continuous development over the last 50+ years since the first MAC (Marker and Cell) and SLIC (Simple Line Interface Calculation) methods appeared in the 1960's. The sustained interest in simulating multiphase flow stem from their many practical applications in the physical world; from biological systems, to chemical systems, to boiling dynamics and atmospheric heat and mass transfer. The ability to capture the details of interface evolution as well as the physics of interfacial heat and mass transfer has thus been a tempting goal for many numerical researchers. Numerical analysts, apart from the well-established and popular VOF PLIC (Volume of Fluid, Piecewise Linear Interface Construction) method, can now call upon even more computationally intensive options such as the LS (Level Set) method, the FT (Front Tracking) method, the MoF (Moment of Fluid) method and hybrid methods.

42 ENGINEERING↗
DOE OSTI2020

In Situ Chemical Monitoring and Imaging of Contents within Microfluidic Devices Having a Porous Membrane Wall Using Liquid Microjunction Surface Sampling Probe Mass Spectrometry

The ability to observe dynamic chemical processes (e.g., signaling, transport, etc.) in vivo or in situ using nondestructive chemical imaging opens a new door to understanding the complex dynamics of developing biological systems. With the advent of “biology-on-a-chip” devices has come the ability to monitor dynamic chemical processes in a controlled environment, using these engineered habitats to capture key features of natural systems while allowing visual observation of system development. Having the capability to spatially and temporally map the chemical signals within these devices may yield new insights into the forces that drive biosystem development. Here, a porous membrane sealed microfluidic device was designed to allow normal microfluidic operation while enabling continuous, location specific sampling and chemical characterization by liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS). LMJ-SSP was used to extract fluids with nL-to-μL/min flow rates directly from selected areas of the microfluidic device without negatively impacting the device function. These extracts were subsequently characterized using MS. This technique was used to acquire MS images of the entirety of several multi-input microfluidic devices having different degrees of fluid mixing. LMJ-SSP MS imaging visualized the spatial distribution of chemical components within the microfluidic channels and could visualize chemical reactions occurring in the device. These microfluidic devices with a porous membrane wall are wholly compatible with the construction of biology-on-a-chip devices. This ultimately would enable correlation of biosystem physical structure with an evolving chemical environment

47 OTHER INSTRUMENTATION↗
DOE OSTI2016

Spatial atomic layer deposition of ZnO/TiO{sub 2} nanolaminates

Spatial atomic layer deposition (S-ALD) is a potential high-throughput manufacturing technique offering fast and large scale ultrathin films deposition. Here, an S-ALD system with modular injectors is introduced for fabricating binary oxides and their nanolaminates. By optimizing the deposition conditions, both ZnO and TiO{sub 2} films demonstrate linear growth and desired surface morphology. The as-deposited ZnO film has high carrier mobility, and the TiO{sub 2} film shows suitable optical transmittance and band gap. The ZnO/TiO{sub 2} nanolaminates are fabricated by alternating substrate movement between each S-ALD modular units of ZnO and TiO{sub 2}. The grazing incidence x-ray diffraction spectra of nanolaminates demonstrating the signature peaks are weaker for the same thickness nanolaminates with more bilayers, suggesting tuning nanolaminates from crystalline to amorphous. Optical transmittances of ZnO/TiO{sub 2} laminates are enhanced with the increase of the bilayers' number in the visible range. Refractive indices of nanolaminates increase with the thickness of each bilayer decreasing, which demonstrates the feasibility of obtaining desired refractive indices by controlling the bilayer number. The electronic properties, including mobility, carrier concentration, and conductivity, are also tunable with different bilayers.

42 ENGINEERING↗
DOE OSTI2021

Defining Computational Emissivity Uncertainty Over Large Temperature Scales Due to Surface Evolution

There is a dearth in the literature on how to capture the uncertainty generated by material surface evolution in thermal modeling. This leads to inadequate or highly variable uncertainty representations for material properties, specifically emissivity when minimal information is available. Inaccurate understandings of prediction uncertainties may lead decision makers to incorrect conclusions, so best engineering practices should be developed for this domain. In order to mitigate the aforementioned issues, this study explores different strategies to better capture the thermal uncertainty response of engineered systems exposed to fire environments via defensible emissivity uncertainty characterizations that can be easily adapted to a variety of use cases. Here, two unique formulations (one physics-informed and one mathematically based) are presented. The formulations and methodologies presented herein are not exhaustive but more so are a starting point and give the reader a basis for how to customize their uncertainty definitions for differing fire scenarios and materials. Lastly, the impact of using this approach versus other commonly used strategies and the usefulness of adding rigor to material surface evolution uncertainty is demonstrated.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Roughness generation during Si etching in Cl{sub 2} pulsed plasma

Pulsed plasmas are promising candidates to go beyond limitations of continuous waves' plasma. However, their interaction with surfaces remains poorly understood. The authors investigated the silicon etching mechanism in inductively coupled plasma (ICP) Cl{sub 2} operated either in an ICP-pulsed mode or in a bias-pulsed mode (in which only the bias power is pulsed). The authors observed systematically the development of an important surface roughness at a low duty cycle. By using plasma diagnostics, they show that the roughness is correlated to an anomalously large (Cl atoms flux)/(energetic ion flux) ratio in the pulsed mode. The rational is that the Cl atom flux is not modulated on the timescale of the plasma pulses although the ion fluxes and energy are modulated. As a result, a very strong surface chlorination occurs during the OFF period when the surface is not exposed to energetic ions. Therefore, each energetic ion in the ON period will bombard a heavily chlorinated silicon surface, leading to anomalously high etching yield. In the ICP pulsed mode (in which the ion energy is high), the authors report yields as high as 40, which mean that each individual ion impacts will generate a “crater” of about 2 nm depth at the surface. Since the ion flux is very small in the pulsed ICP mode, this process is stochastic and is responsible for the roughness initiation. The roughness expansion can then be attributed partly to the ion channeling effect and is probably enhanced by the formation of a SiClx reactive layer with nonhomogeneous thickness over the topography of the surface. This phenomenon could be a serious limitation of pulsed plasma processes.

42 ENGINEERING↗
DOE OSTI2022

Legacy surface change analyses of the 1993 Rock Valley earthquake sequence for direct comparison to planned NA-22 underground conventional high-explosive experiments (Source Physics Experiment 3 (SPE3) - RV/DC Task 1.3 FY22 Final Report)

Recent work under two previous phases of the NNSA NA-22 Source Physics Experiment (SPE) have shown that underground chemical high-explosive experiments can produce detectable surface changes that differ in spatial extent and vertical magnitude depending on the geologic media at the site (Schultz-Fellenz et al., 2018; 2020; Crawford et al., 2021). Neither of these two prior phases of SPE identified natural earthquake-related surface effects in the same region that occurred at a similar depth as the explosive experiments for direct comparison. While earthquakes can also produce surface changes that are detectable using remote sensing data analyses, it is expected that the pattern and spatial extent of surface changes would vary between earthquakes and explosions. However, no direct-observed surface-change signature comparison between earthquakes and explosions has ever been performed. The SPE Phase 3 Rock Valley/Direct Comparison (RV/DC) program presents a unique opportunity to investigate and characterize co-occurrence of both earthquakes and explosions. In this project, we worked to address five tasks in a workflow, as follows: 1. Identify and obtain existing high-resolution legacy satellite and aerial imagery as close in time before and after the 1993 Rock Valley earthquake sequence to temporally constrain the analyses. 2. Transform these pre-earthquake and post-earthquake datasets into digital elevation models (DEMs) using geospatial analysis software packages (e.g., ArcGIS, Agisoft Metashape, and Google Earth Engine). 3. Perform DEM differencing analyses to assess and quantify earthquake-related changes from the 1993 sequence, and develop map products that visualize these analyses. 4. Use the analyses from (3) to: (a) assess spatial distribution and magnitude of surface changes due to the 1993 Rock Valley earthquake sequence, and (b) determine parameters of forthcoming, planned explosion-related surface change data collection from sensors mounted on unmanned aerial vehicles (UAVs) (e.g., spatial extent of collection, design and density of survey control, sensors to deploy, forward speed and line spacing of UAV flight lines, flight altitude). 5. Develop a summary report on the analyses, including how the analyses define parameters and identify focus areas for any future surface change analytical field campaigns related to the explosive experiment. Analyzing these legacy data and identifying whether they can detect any surface changes related to the earthquake sequence facilitates opportunities for direct signature comparison of surface change from explosions at one location, which has never previously been performed. Comparing the surface change signatures from a co-located and depth-equivalent earthquake and an explosion could help to advance remote sensing event discrimination techniques. This report summarizes the work completed toward this ambitious goal.

42 ENGINEERING↗
DOE OSTI2018

Passivation and thickness control of highly efficient kesterite solar cells

Kesterite Cu 2 ZnSn(S x Se 1-x ) 4 (CZTSSe) is an attractive photovoltaic absorber material because of its tunable bandgap, earth abundance, and low toxicity. However, efficiency and open circuit voltage remain significantly below theoretical limits. We recently showed that back-contact engineering with MoO 3 /Au on exfoliated vapor-deposited kesterite solar cells can improve device performance. In this work, we demonstrate more promising results, which translate into high power conversion efficiencies of up to 12.2% for solution-deposited CZTSe with thicknesses as low as 1.1 μm. Time-resolved terahertz spectroscopy of exfoliated films showed significantly faster recombination at the back surface than at the front. When atomic layer deposited Al 2 O 3 was used to passivate the exposed back surface of exfoliated films, front and back surfaces showed nearly identical recombination dynamics. After thermally depositing high work function MoO 3 and reflective Au as the back contact on the Al 2 O 3 -passivated absorber, we obtained devices with efficiencies of up to 11.6%. Applying the same strategy of exfoliating working devices and engineering the back contact resulted in efficiencies of up to 12.2% for passivation with a 10 nm layer of Se instead of Al 2 O 3 . Lastly, further development of such passivation and back-contact engineering approaches may lead to higher efficiency devices with absorber thicknesses below 1 μm.

36 MATERIALS SCIENCE↗
DOE OSTI2017

A Panchromatic View of Brown Dwarf Aurorae

Stellar coronal activity has been shown to persist into the low-mass star regime, down to late M-dwarf spectral types. However, there is now an accumulation of evidence suggesting that at the end of the main sequence, there is a transition in the nature of the magnetic activity from chromospheric and coronal to planet-like and auroral, from local impulsive heating via flares and MHD wave dissipation to energy dissipation from strong large-scale magnetospheric current systems. We examine this transition and the prevalence of auroral activity in brown dwarfs through a compilation of multiwavelength surveys of magnetic activity, including radio, X-ray, and optical. We compile the results of those surveys and place their conclusions in the context of auroral emission as a consequence of large-scale magnetospheric current systems that accelerate energetic electron beams and drive the particles to impact the cool atmospheric gas. We explore the different manifestations of auroral phenomena, like H α , in brown dwarf atmospheres and define their distinguishing characteristics. We conclude that large-amplitude photometric variability in the near-infrared is most likely a consequence of clouds in brown dwarf atmospheres, but that auroral activity may be responsible for long-lived stable surface features. We report a connection between auroral H α emission and quiescent radio emission in electron cyclotron maser instability pulsing brown dwarfs, suggesting a potential underlying physical connection between quiescent and auroral emissions. We also discuss the electrodynamic engines powering brown dwarf aurorae and the possible role of satellites around these systems both to power the aurorae and seed the magnetosphere with plasma.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Fast rise breakdown in dielectric filled air gap for surge protection

Electric discharge across an air gap can be self-healing, providing a unique capability for repetitive, fast, high-voltage/current switching applications through arc conduction. Furthermore, incorporating dielectric granules in the air gap stimulates gas ionization, which lowers the breakdown voltage and narrows breakdown voltage distribution, thereby enabling engineered surge protection from multiple lightning strikes on aerospace vehicles and sensitive solid-state electronics in critical systems. This study investigates the effect of the permittivity of dielectric granules, gap filling, surface roughness, and metal work function on fast-rising, high-voltage breakdowns. In addition to the air gap width, these factors play important roles in gas ionization, field concentration, and initiation of electrical discharge and arcing. Therefore, they could potentially be used to control and narrow operational breakdown voltages for practical applications. Additionally, a modified Langevin–Debye model is developed to correlate the breakdown voltage and the permittivity of the dielectric filler. These investigations identify and highlight key underpinning mechanisms governing the gas discharge behavior across a dielectric filled air gap during voltage surge events.

42 ENGINEERING↗
DOE OSTI2024

Hierarchically Structured Catalysts Toward Sustainable Hydrogen Economy: Electro‐ and Thermo‐Chemical Pathways

Abstract Hydrogen, as an important clean energy source, plays a more and more crucial role in decarbonizing the planet and meeting the global climate challenge due to its high energy density and zero‐emission. The demand for sustainable hydrogen is increasing drastically worldwide as driven by the global shift towards low‐carbon energy solutions. Thermochemical catalysis process dominates hydrogen production at scale given its relatively mature technology and commercialization status, as well as the established manufacturing infrastructure. While due to its environmentally friendly nature and growing abundant sources of renewable electricity, the electrochemical path for hydrogen production is rising as a major alternative to the thermochemical means. Nevertheless, hierarchically structured catalysts and devices have gradually taken the center stage toward replacing the traditional counterparts, especially with the rapid advancement of the design and manufacture of such ordered nanostructure assemblies toward high activity, efficient mass transport, and superb stability. In this review, the latest progress of the hierarchically structured catalysts for hydrogen production have been surveyed on electro‐ and thermo‐ chemical pathways comparatively. It covers the structure designs of atomic dispersion, nanoscale surfaces and interfaces for achieving highly active and durable catalysts, components, and devices. Both electrochemical and thermochemical approaches are reviewed in terms of the vast design details, engineered benefits, and understandings of various Pt‐group metal (PGM) and non‐PGM based transition metal catalysts for hydrogen production. As the growing trend, brief discussions are also presented toward the high‐level assembly and manufacture of complexly structured components and devices at scale in the electrochemical and thermochemical energy systems.

Deng, Chenxin↗
DOE OSTI2022

Effect of PVD-coated chromium on the subcooled flow boiling performance of nuclear reactor cladding materials

Here we elucidate the separate effect of a thin Cr coating deposited by physical vapor deposition (PVD) on the subcooled flow boiling performance of zircaloy-4. First, we run flow boiling experiments on prototypical zircaloy-4 surfaces mimicking the scratch pattern and surface roughness of nuclear reactor claddings. Then, we PVD-coat a 0.3 µm thick chromium layer on the same exact surface and repeat the same flow boiling investigations. All experiments are run using deionized water at atmospheric pressure, flowing on a 1 × 3 cm 2 rectangular cross section channel at a rate of 1000 kg/m 2 /s and a subcooling of 10 K. We measure the average temperature of the boiling surface at increasing surface heat fluxes, covering a wide range of heat transfer regimes, from single-phase forced convection to the boiling crisis. We also record high-speed videos of the boiling process, which we postprocess to measure bubble nucleation site density, growth time, departure diameter and frequency. The surface analysis reveals that, while the chromium coating does not seem change the surface roughness and morphology, it improves surface wettability. However, it decreases the critical heat flux. The chromium coating causes an increase of nucleation temperature, bubble departure diameter and growth time, and a reduction of the nucleation site density. The concurrence of these observations indicates that a size reduction of the nucleation sites, conformally covered by the chromium coating, may be the cause of the boiling performance deterioration. We confirm this hypothesis repeating the same analysis on a FeCrAl sample prepared and tested using the same protocol as the zircaloy-4 sample, but with a different initial surface texture.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2018

Dielectric-barrier-discharge plasma-assisted hydrogen diffusion flame. Part 1: Temperature, oxygen, and fuel measurements by one-dimensional fs/ps rotational CARS imaging

One-dimensional hybrid fs/ps CARS imaging provides single-laser-shot measurements of temperature, oxygen, and hydrogen in a plasma-assisted hydrogen diffusion flame. The coaxial dielectric-barrier-discharge burner collapses the Re ~50 hydrogen diffusion flame to within ~5 mm of the burner surface at an applied AC potential of 8.75 kV at 18 kHz, coinciding nicely with the full spatial extent of the 1D CARS measurements. Translating the burner through the measurement volume allowed for measurements at numerous radial locations in increments of 1 mm with a resolution of 140 µm × 30 µm × 600 µm, sufficient to resolve spatial gradients in this unsteady flame. Longer probe delays, required for improved dynamic range in regions of high temperature fluctuations, proved difficult to model as a result of a nontrivial decay in the O 2 Raman coherence arising from complexities associated with the triplet ground electronic state of the O 2 molecule. Oxygen linewidths were treated empirically using the observed O 2 coherence decay in spectra acquired from the product gases of lean, near-adiabatic H 2 /air flames stabilized on a Hencken flat-flame burner. While still leading to errors up to 10% at worst, the empirically determined Raman linewidth factors eliminated any systematic error in the O 2 /N 2 measurements with probe delay. Temperature measurements in the Hencken Burner flames proved to be insensitive to probe pulse delay, providing robust thermometry. Here, demonstration of this technique in both the canonical Hencken burner flames and a new DBD burner validates its effectiveness in producing multiple spatially resolved measurements in combustion environments. Measurements in the DBD burner revealed an unsteady, counterflow flattened flame structure near the fuel orifice which became unsteady as the reaction zone curves towards the surface for larger radial positions. Lastly, fluctuations in the fuel concentration were largest at the source, as the large, plasma-generated, unsteady external toroidal vortex that dominates the transport in this flame provides enhanced ventilation of the flame surface in close proximity to the fuel tube.

42 ENGINEERING↗
DOE OSTI2022

Carrier control in Sn–Pb perovskites via 2D cation engineering for all-perovskite tandem solar cells with improved efficiency and stability

All-perovskite tandem solar cells are promising for achieving photovoltaics with power conversion efficiencies above the detailed balance limit of single-junction cells, while retaining the low cost, light weight and other advantages associated with metal halide perovskite photovoltaics. However, the efficiency and stability of all-perovskite tandem cells are limited by the Sn-Pb-based narrow-bandgap perovskite cells. Here we show that the formation of quasi-two-dimensional (quasi-2D) structure (PEA) 2 GAPb 2 I 7 from additives based on mixed bulky organic cations phenethylammonium (PEA+) and guanidinium (GA+) provides critical defect control to substantially improve the structural and optoelectronic properties of the narrow-bandgap (1.25 eV) Sn-Pb perovskite thin films. Additionally, this 2D additive engineering results in Sn-Pb-based absorbers with low dark carrier density (~1.3 x 10 14 cm -3 ), long bulk carrier lifetime (~9.2 us) and low surface recombination velocity (~1.4 cm s -1 ), leading to 22.1%-efficient single-junction Sn-Pb perovskite cells and 25.5%-efficient all-perovskite two-terminal tandems with high photovoltage and long operational stability.

14 SOLAR ENERGY↗
DOE OSTI2026

Aperture and roughness govern iron oxide passivation in olivine fractures during carbon mineralization

Efficient carbon dioxide mineralization in silicate-rich formations depends on reaction rates within fracture networks, yet the role of fracture microstructure remains poorly constrained. We investigated how fracture aperture and surface roughness influence mineralization by reacting synthetic forsteritic olivine fractures with controlled apertures (0.5–1.6 millimeters) and roughness (6–16 micrometers) with supercritical carbon dioxide at 13.7 megapascals and 185 degrees Celsius. Optical microscopy and Raman spectroscopy showed that rougher fracture surfaces promoted iron oxide precipitation, which passivated olivine surfaces, limiting magnesium availability for carbonate formation while removing iron as a reactant. These effects were more pronounced in smaller-aperture fractures. A geochemical model incorporating surface topography and passivation reproduced the observed trends, confirming that increased roughness can reduce reactivity despite greater surface area. Our results demonstrate that fracture microstructure strongly influences iron oxide passivation and carbon dioxide mineralization, with important implications for predicting long-term performance of engineered carbon dioxide storage systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Patterning non-equilibrium morphologies in stimuli-responsive gels through topographical confinement

Stimuli-responsive “smart” polymers have generated significant interest for introducing dynamic control into the properties of antifouling coatings, smart membranes, switchable adhesives and cell manipulation substrates. Switchable surface morphologies formed by confining stimuli-responsive gels to topographically structured substrates have shown potential for a variety of interfacial applications. Beyond patterning the equilibrium swelling behavior of gels, subjecting stimuli-responsive gels to topographical confinement could also introduce spatial gradients in the various timescales associated with gel deformation, giving rise to novel non-equilibrium morphologies. In this work, we show how by curing poly(N-isopropylacrylamide) (pNIPAAm)-based gel under confinement to a rigid, bumpy substrate, we can not only induce the surface curvature to invert with temperature, but also program the transient, non-equilibrium morphologies that emerge during the inversion process through changing the heating path. Finite element simulations show that the emergence of these transient morphologies is correlated with confinement-induced gradients in polymer concentration and position-dependent hydrostatic pressure within the gel. To illustrate the relevance of such morphologies in interfacial applications, we show how they enable us to control the gravity-induced assembly of colloidal particles and microalgae. Finally, we show how more complex arrangements in particle assembly can be created through controlling the thickness of the temperature-responsive gel over the bumps. Patterning stimuli-responsive gels on topographically-structured surfaces not only enables switching between two invertible topographies, but could also create opportunities for stimuli ramp-dependent control over the local curvature of the surface and emergence of unique transient morphologies. Harnessing these features could have potential in the design of multifunctional, actuatable materials for switchable adhesion, antifouling, cell manipulation, and liquid and particle transport surfaces.

42 ENGINEERING↗
DOE OSTI2026

Unraveling interphase-driven failure pathways in LiMn0.6Fe0.4PO4/graphite pouch cells

LiMnxFe1−xPO4 (LMFP) is a promising high-voltage, thermally stable, and earth-abundant cathode material, yet its practical application is limited by interphase instability and Mn dissolution. In this work, we systematically evaluate LiMn0.6Fe0.4PO4/graphite pouch cells using three electrolyte formulations including control carbonate electrolyte, control + 2 wt% vinylene carbonate (VC), and control + 2 wt% VC + 1 wt% 1,3,2-dioxathiolane 2,2-dioxide (DTD), to establish how electrolyte composition governs interphase chemistry and long-term degradation. Electrochemical testing shows that both additives are preferentially reduced prior to ethylene carbonate (EC) during cell formation, generating robust cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI) layers that suppress gas evolution and raise the first-cycle coulombic efficiency to 89.3%. Additionally, the dual-additive electrolyte delivers the most stable performance, retaining over 85% capacity after 600 cycles while minimizing impedance growth under long-term cycling at C/3 and 40 °C. Soft X-ray absorption spectroscopy confirms that VC + DTD effectively suppresses electrolyte oxidation at the cathode surface, and micro-X-ray fluorescence shows substantially reduced Mn dissolution and deposition on the graphite anode. Density functional theory simulations further provided insights into the structural and energetic influences of alkoxide species on the cathode surface, proposing a Mn2+ extraction mechanism. The combined experimental and computational findings establish a mechanistic link between electrolyte composition and interphase evolution, highlighting the effectiveness of electrolyte engineering for extending the operational lifetime of LMFP-based lithium-ion batteries.

Chak, Chanmonirath Michael↗