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

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Acid-Base Equilibrium and Dielectric Environment Regulate Charge in Supramolecular Nanofibers

Peptide amphiphiles are a class of molecules that can self-assemble into a variety of supramolecular structures, including high-aspect-ratio nanofibers. It is challenging to model and predict the charges in these supramolecular nanofibers because the ionization state of the peptides are not fixed but liable to change due to the acid-base equilibrium that is coupled to the structural organization of the peptide amphiphile molecules. Here, we have developed a theoretical model to describe and predict the amount of charge found on self-assembled peptide amphiphiles as a function of pH and ion concentration. In particular, we computed the amount of charge of peptide amphiphiles nanofibers with the sequence C 16 − V 2 A 2 E 2 . In our theoretical formulation, we consider charge regulation of the carboxylic acid groups, which involves the acid-base chemical equilibrium of the glutamic acid residues and the possibility of ion condensation. The charge regulation is coupled with the local dielectric environment by allowing for a varying dielectric constant that also includes a position-dependent electrostatic solvation energy for the charged species. We find that the charges on the glutamic acid residues of the peptide amphiphile nanofiber are much lower than the same functional group in aqueous solution. There is a strong coupling between the charging via the acid-base equilibrium and the local dielectric environment. Our model predicts a much lower degree of deprotonation for a position-dependent relative dielectric constant compared to a constant dielectric background. Furthermore, the shape and size of the electrostatic potential as well as the counterion distribution are quantitatively and qualitatively different. These results indicate that an accurate model of peptide amphiphile self-assembly must take into account charge regulation of acidic groups through acid–base equilibria and ion condensation, as well as coupling to the local dielectric environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Spin-1 Kitaev-Heisenberg model on a honeycomb lattice

We study the Kitaev-Heisenberg model with spin-1 local degree of freedom on a honeycomb lattice numerically by the infinite density matrix renormalization group method on a cylinder geometry. By tuning the relative value of the Kitaev and Heisenberg exchange couplings, we obtain the phase diagram with two spin liquid phases and four symmetry-broken phases. Here, we identify that the spin liquid phases are gapless by calculating the central charge at the pure Kitaev points without the Heisenberg interactions. Comparing to its spin-1/2 counterpart, the position and number of gapless modes of the spin-1 case are quite different. Due to the approximate Z 2 local conservations, the expectation value of the Wilson loop operator measuring the flux of each plaquette stays near to 1, and the static spin-spin correlations remain short range in the entire spin liquid phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Powering the Blue Economy: A Survey of Station-Keeping Methods for Mooringless Platforms

The term “ocean platform” is used to reference everything from stationary, typically moored, buoys to mobile water vehicles, whether they operate on the ocean’s surface or underwater. For certain applications for which relatively stationary station-keeping conditions are desired, the use of mooring systems is not always a viable alternative either for economic, environmental, regulatory, or otherwise practical reasons, or a combination thereof, (e.g., short deployments, sensitive ecosystems, very deep project sites). Maintaining a platform at a single waypoint or reference location without being moored would require additional control systems and a power source to counteract the drift forces that would naturally displace it. Mobile platforms, which are usually untethered except for remotely operated vehicles, typically require energy input to power their station-keeping capabilities so that they hold or control their location in the ocean. Currently, most of these platforms use combustion engines or batteries for this purpose, which, depending on the specific systems, may be costly, pollute the environment, or create limitations on the length of the deployment. However, powering this kind of platforms with surrounding renewable resources (waves, currents, winds, or sun) has been identified as a promising solution to expand their application. The intent of this report is to investigate station-keeping methods for various ocean platforms that are not moored or otherwise anchored to the ocean floor, or another platform or vessel, paying particular interest to technologies that use marine renewable resources to power their operation, because that is of particular interest to the U.S. Department of Energy’s Powering the Blue Economy (PBE) initiative. As a first step, 72 articles and technical reports related to mooringless station-keeping methods were collected for review. The preliminary literature review provided a broad overview of common themes across the literature from which a descriptive methodology for analyzing various platforms was developed. That is, station-keeping methods were categorized based on their predominant energy source and consumption (renewable, nonrenewable, or hybrid if the platform uses renewable and nonrenewable resources equally), and their localization strategy (drift reduction, “path-planning or “waypoint-holding”). In addition, platform types were segregated into the following groups: buoys, surface drifters, and unoccupied surface vehicles (USVs); offshore renewable energy systems; and unoccupied underwater vehicles (UUVs). The main types of station-keeping methods encountered in this report achieve their intended localization strategy by means of drift mitigation, steering, and/or propulsion. Drift mitigation is commonly accomplished via drogues and sea anchors. Stand-along steering subsystems use control surfaces (e.g., ship rudder, wing sail, etc.) that react to ocean currents, waves, or winds to provide varying-degrees of course adjustments. Combined steering and propulsion subsystems include differential thrusters, directional thrusters separate from a primary thruster that cause the platform to pitch up/down or yaw clockwise/counterclockwise, or vectored thrusters that direct the propulsion in a range of directions relative to the platform’s local coordinate system. Propulsion is often achieved by running a motor and applying active control strategies but can also involve buoyancy shifts and using sails to generate lifting forces that propel a platform in a desired direction. Future research is primarily expected to take place in the form of a technoeconomic analysis that would aim to determine the technological viability, cost, and added value of mooringless station-keeping use cases identified through this research, including docking for UUV recharging or for georeferencing drifter buoys, deep-sea floating wind farms, U.S. Navy sonar arrays, and a Pacific Ocean wave buoy network.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Characterizing the Spread of COVID-19 from Human Mobility Patterns and SocioDemographic Indicators

Mobility is an indicator of human movement through space and time. With the increasing availability of geolocated data (from GPS, accelerometers, etc.), it is now possible to examine individual as well as group human mobility patterns. Human mobility is influenced by both intrinsic (i.e. personal motivations) and extrinsic (i.e., events like natural hazards or a pandemic like the COVID-19) factors. However, the intricate relationships between human mobility patterns and sociodemographic characteristics in the context of a pandemic are yet to be fully explored. Our goal is to overcome this gap by using human mobility data at the census block group level from mobile phones and combining those with social vulnerability indicators to examine the overall spread of COVID-19 at local spatial scales. We used 585,878 weekly visits to 37,871 points of interests (POIs) from Safegraph to quantify mobility indices and social distancing metrics in 2,820 census block groups in the city of Los Angeles (LA) - before and during lockdown as well as during the phase1 and phase 2 reopening. Finally, using supervised machine learning algorithms, we classified the census block groups in LA into High, Medium and Low categories that represented the vulnerability of these block groups based on the cumulative number of occurrences of COVID-19 cases till July 24, 2020. Our results indicate that the tree-based classifiers performed well in comparison to the Support Vector Machines and Multinomial Logit models. Gradient Boosting had the highest classification accuracy of 97.4% COVID-19 with an AUC score of 0.987. The block groups with high COVID-19 cases also had a high concentration of socially vulnerable populations, high human mobility index and a low social distancing index.

Roy, Avipsa↗
NASA NTRS1991

The potential for crustal resources on Mars

Martian resources pose not only an interesting scientific challenge but also have immense astronautical significance because of their ability to enhance mission efficiency, lower launch and program costs, and stimulate the development of large Mars surface facilities. Although much terrestrial mineralization is associated with plate tectonics and Mars apparently possesses a thick, stationary lithosphere, the presence of crustal swells, rifting, volcanism, and abundant volatiles indicates that a number of sedimentary, hydrothermal, dry-magma mineral concentration processes may have operated on Mars. For example, in Colorado Plateau-style (roll-front) deposits, uranium precipitation is localized by redox variations in groundwater. Also, evaporites (either in salt pans or even interstitially in pore spaces) might concentrate Cl, Li, and K. Many Martian impact craters have been modified by volcanism and probably have been affected by rising magma bodies interacting with ground ice or water. Such conditions might produce hydrothermal circulations and element concentrations. If the high sulfur content found by the Viking landers typifies Martian abundances, sulfide ore bodies may have been formed locally. Mineral-rich Africa seems to share many volcanic and tectonic characteristics with portions of Mars and may suggest Mars' potential mineral wealth. For example, the rifts of Valles Marineris are similar to the rifts in east Africa, and may both result from a large mantle plume rising from the interior and disrupting the surface. The gigantic Bushveld complex of South Africa, an ancient layered igneous intrusion that contains ores of chromium and Pt-group metals, illustrates the sort of dry-magma processes that also could have formed local element concentrations on Mars, especially early in the planet's history when heat flow was higher.

Cordell, Bruce M.↗
NASA NTRS2013

The Utility of the Real-Time NASA Land Information System Data for Drought Monitoring Applications

Measurements of soil moisture are a crucial component for the proper monitoring of drought conditions. The large spatial variability of soil moisture complicates the problem. Unfortunately, in situ soil moisture observing networks typically consist of sparse point observations, and conventional numerical model analyses of soil moisture used to diagnose drought are of coarse spatial resolution. Decision support systems such as the U.S. Drought Monitor contain drought impact resolution on sub-county scales, which may not be supported by the existing soil moisture networks or analyses. The NASA Land Information System, which is run with 3 km grid spacing over the eastern United States, has demonstrated utility for monitoring soil moisture. Some of the more useful output fields from the Land Information System are volumetric soil moisture in the 0-10 cm and 40-100 cm layers, column-integrated relative soil moisture, and the real-time green vegetation fraction derived from MODIS (Moderate Resolution Imaging Spectroradiometer) swath data that are run within the Land Information System in place of the monthly climatological vegetation fraction. While these and other variables have primarily been used in local weather models and other operational forecasting applications at National Weather Service offices, the use of the Land Information System for drought monitoring has demonstrated utility for feedback to the Drought Monitor. Output from the Land Information System is currently being used at NWS Huntsville to assess soil moisture, and to provide input to the Drought Monitor. Since feedback to the Drought Monitor takes place on a weekly basis, weekly difference plots of column-integrated relative soil moisture are being produced by the NASA Short-term Prediction Research and Transition Center and analyzed to facilitate the process. In addition to the Drought Monitor, these data are used to assess drought conditions for monthly feedback to the Alabama Drought Monitoring and Impact Group and the Tennessee Drought Task Force, which are comprised of federal, state, and local agencies and other water resources professionals.

White, Kristopher D.↗
NASA NTRS1994

The global atmospheric response to low-frequency tropical forcing: Zonally averaged basic states

The extratropical response to localized, low-frequency tropical forcing is examined using a linearized, non-divergent barotropic model on a sphere. Zonal-mean basic states characterized by solid-body rotation or critical latitudes are considered. An analytical analysis based on WKB and ray tracing methods shows that, in contrast to stationary Rossby waves, westward moving, low-frequency Rossby waves can propagate through the tropical easterlies into the extratropics. It is shown analytically that the difference between the stationary and low-frequency ray paths is proportional to the forcing frequency and inversely proportional to the zonal wavenumber cubed. An expression for the disturbance amplitude is derived that shows the ability of the forced waves to maintain their strength well into middle latitudes depends on their meridional wave scale and northward group velocity, both of which are functions of the slowly varying background flow. A local energetics analysis shows that the combination of energy dispersion from the forcing region and energy extraction from the equatorward flank of the midlatitude jet produces disturbances that have the greatest impact on the extratropical circulation. Under the assumption that the forcing amplitude is independent of frequency, this impact is largest when the tropical forcing period is in the range 10-20 days.

Li, Long↗
DOE OSTI2022

Possible quadrupole-order-driven commensurate-incommensurate phase transition in B20 CoGe

For this study, the B20-type cobalt germanide CoGe was investigated by measuring the specific heat, resistivity, and 59 Co nuclear magnetic resonance (NMR). We observed a phase transition at T Q = 13.7 K, evidenced by a very narrow peak of the specific heat and sharp changes of the nuclear spin-spin (T 2 –1 ) and spin-lattice ( T 1 – 1 ) relaxation rates. The fact that the entropy release is extremely small and the Knight shift is almost independent of temperature down to low temperatures as anticipated in a paramagnetic metal indicates that the T Q transition is of nonmagnetic origin. In addition, we detected a crossover scale T 0 ~ 30 K below which the resistivity and the NMR linewidth increase, and T 1 –1 is progressively distributed in space, that is, a static and dynamical spatial inhomogeneity develops. While the order parameter for the T Q transition remains an open question, a group-theoretical analysis suggests that the finite electric quadrupole density arising from the low local site symmetry at cobalt sites could drive the crystal symmetry lowering from the P2 1 3 symmetry that is commensurate to the R3 symmetry with an incommensurate wave vector, which fairly well accounts for the T Q transition. The quadrupole-order-driven commensurate-incommensurate phase transition may be another remarkable phenomenon arising from the structural chirality inherent in the noncentrosymmetric B20 family.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

An Analysis of the Spatial Variations in the Relationship Between Built Environment and Severe Crashes

Traffic crashes significantly contribute to global fatalities, particularly in urban areas, highlighting the need to evaluate the relationship between urban environments and traffic safety. This study extends former spatial modeling frameworks by drawing paths between global models, including spatial lag (SLM), and spatial error (SEM), and local models, including geographically weighted regression (GWR), multi-scale geographically weighted regression (MGWR), and multi-scale geographically weighted regression with spatially lagged dependent variable (MGWRL). Utilizing the proposed framework, this study analyzes severe traffic crashes in relation to urban built environments using various spatial regression models within Leon County, Florida. According to the results, SLM outperforms OLS, SEM, and GWR models. Local models with lagged dependent variables outperform both the global and generic versions of the local models in all performance measures, whereas MGWR and MGWRL outperform GWR and GWRL. Local models performed better than global models, showing spatial non-stationarity; so, the relationship between the dependent and independent variables varies over space. The better performance of models with lagged dependent variables signifies that the spatial distribution of severe crashes is correlated. Finally, the better performance of multi-scale local models than classical local models indicates varying influences of independent variables with different bandwidths. According to the MGWRL model, census block groups close to the urban area with higher population, higher education level, and lower car ownership rates have lower crash rates. On the contrary, motor vehicle percentage for commuting is found to have a negative association with severe crash rate, which suggests the locality of the mentioned associations.

Alisan, Onur (ORCID:0000000193113984)↗
DOE OSTI2020

Temperature drives local contributions to beta diversity in mountain streams: stochastic and deterministic processes

Community variation (i.e. beta diversity) in geographical coenoclines is of substantial interest in ecology, yet the elevational patterns in beta diversity are still understudied, and no general conclusions have been reached. Here, we explored local contributions to beta diversity (LCBD) of stream bacteria, diatoms and macroinvertebrates on mountainsides. Across all taxa, we revealed a general U-shaped LCBD-elevation relationships (LCBDer), suggesting higher uniqueness of community composition at the two ends of the elevational gradients. This pattern was confirmed by coenocline simulations based on observed communities, and supported by the dominance of species replacement in total beta diversity. Across mountains and taxonomic groups, temperature was the main environmental factor underlying elevational patterns in LCBD and its metric relatives, which were also mediated by local environmental variables. The observed magnitudes of U-shaped LCBDer across mountains and taxonomic groups were specifically related to the heterogeneity of stream morphology, and the mean annual temperature on each mountain. U-shaped LCBDer were strengthened by the occurrence of generalist species with large elevational ranges, while rare species had a lesser effect on the patterns. Raup-Crick beta diversity indicated that both stochastic and deterministic processes drove the community assembly, and the latter one was positively related to the magnitudes of LCBDer. Our synthesis across mountains and taxonomic groups clearly shows that there are consistent elevational patterns in LCBD among taxonomic groups, and that these patterns are explained by similar ecological mechanisms, producing a more complete picture in understanding and bridging the spatial variation in biodiversity under changing climate.

Wang, Jianjun↗
NASA NTRS2000

Sunspots and Giant-Cell Convection

From analysis of Doppler velocity images from SOHO/MDI, Hathaway et al (2000, Solar Phys., in press) have found clear evidence for giant convection cells that fill the solar surface, have diameters 3 - 10 times that typical of supergranules, and have lifetimes approx. greater than 10 days. Analogous to the superposition of the granular convection on the supergranular convection, the approx. 30,000 km diameter supergranules are superposed on these still larger giant cells. Because the giant cells make up the large-scale end of a continuous power spectrum that peaks at the size scale of supergranules, it appears that the giant cells are made by the same mode of convection as the supergranules. This suggests that the giant cells are similar to supergranules, just longer-lived, larger in diameter, and deeper. Here we point out that the range of lengths of large bipolar sunspot groups is similar to the size range of giant cells. This, along with the long lives (weeks) of large sunspots, suggests that large sunspots sit in long-lived, deep downflows at the corners of giant cells, and that the distance from leader to follower sunspots in large bipolar groups is the distance from one giant-cell corner to the next. By this line of reasoning, an unusually large and strong downdraft might pull in both legs of a rising spot-group magnetic flux loop, resulting in the formation of a delta sunspot. This leads us to suggest that a large, strong giant-cell corner downdraft should be present at the birthplaces of large delta sunspots for some time (days to weeks) before the birth. Thus, early detection of such downdrafts by local helioscismology might provide an early warning for the formation of those active regions (large delta sunspot groups) that produce the Sun's most violent flares and coronal mass ejections. This work is supported by NASA's Office of Space Science through the Solar Physics Branch of its Sun-Earth Connection Program.

Moore, Ron L.↗
DOE OSTI2025

A Type II Hamiltonian Variational Principle and Adjoint Systems for Lie Groups

We present a novel Type II variational principle on the cotangent bundle of a Lie group which enforces Type II boundary conditions, i.e., fixed initial position and final momentum. In general, such Type II variational principles are only globally defined on vector spaces or locally defined on general manifolds; however, by left translation, we are able to define this variational principle globally on cotangent bundles of Lie groups. Type II boundary conditions are particularly important for adjoint sensitivity analysis, which is our motivating application. As such, we additionally discuss adjoint systems on Lie groups, their properties, and how they can be used to solve optimization problems subject to dynamics on Lie groups.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

Strain-Modulated Exciton Localization and Enhanced Emission in Multilayer GaSe

Strain engineering is one of the most effective routes for tuning the electrical and optical properties of two-dimensional layered materials. Besides reproducing the results of other groups on the tunability and photoluminescence (PL) enhancement of free and bound excitons under mechanical deformation or thermal effects, we systematically studied the mechanical strain (wrinkle) and local thermal strain (laser heating) effects on the PL lifetime and polarization in GaSe multilayers and their interplay, revealing their coupled impact on excitonic dynamics. Here, the PL intensity of localized excitons in the wrinkle region of GaSe increases superlinearly with the excitation laser power. The polarization effect has been observed for the bound exciton in GaSe under mechanical strain, but not in GaSe under thermal strain. Fluorescence lifetime imaging (FLIM) measurements reveal strain-tunable lifetimes for both free and bound excitons, and the lifetime of the bound exciton is longer than the free exciton in the mechanical strain region, correlating with the enhanced emission of the bound exciton. These results highlight previously uncharacterized optoelectronic tunability in GaSe and broaden the design space for strain (or thermally)-controlled 2D layered devices.

, GaSe, Exciton localization↗
DOE OSTI2025

Chemical Functional Groups Regulate Ion Concentrations and pHs in Nanopores

Understanding ion behaviors in functionalized nanopores is essential to deciphering reactions in both natural and engineered systems, such as sediments, biological ion channels, and membranes. While many efforts have shown the modified ion behaviors in the functionalized nanopores, a direct measurement and analysis to show how chemical functional groups affect ion concentrations in nanopores are critically needed. In this work, we present a plasmonic nanosensor that can measure the local concentrations of protons, anions (phosphate, nitrate, sulfate, and arsenate), and cations (mercury, lead, and copper) in functionalized nanopores, and we compare their concentrations in nanopores with the corresponding bulk concentrations. Notably, chemical functional groups induced ion concentrations differently in nanopores. In pristine nanopores and methyl- and phenyl-functionalized nanopores, we discovered an unexpected concurrence of an enhanced anion concentration and a suppressed cation concentration. In addition, the nanopore pH is dependent on bulk solution compositions and can be lower by 2.5 units, even when the bulk solution is well-buffered. In contrast, for hydrophilic (amine, thiol, and carboxyl) nanopores, pH depended on the p K a of the functional groups, and the heavy metal concentrations depended on chemical interactions with the functional groups. Our findings provide a better understanding of water chemistry in nanopores and can help precisely control ions in nanopores to benefit the design of membrane-based desalination techniques, CO 2 storage, and porous catalysts.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Exploring the Spatial Relationship Between Demographic Indicators and the Built Environment of a City

In addition to global and regional drivers of urbanization, neighborhood development in urban areas across the United States has been shown to be influenced by various local socio-economic factors. These factors, despite varying across socio-economic groups, have large implications regarding a population’s vulnerability to extreme climate events, including heat waves resulting in adverse health impacts. Additionally, the demographics of an urban area can shape its infrastructural characteristics, causing different populations groups to face varying levels of risks and benefits. As a result, the urban morphology and socio-economic characteristics of a city are deeply intertwined; however, their interactions on a finer scale are not yet fully understood. This research aims to better understand the relationships between various socio-economic factors and the built environment of a city, considering variability in building types, and temperature patterns. This research focuses on the city of Las Vegas, NV, and uses spatial data analysis to understand the correlation between of socio-economic characteristics, building morphology, building characteristics, and temperature data to understand the correlation between these various factors. Results of these research shows there is a distinct pattern of clustering of socio-economic characteristics with the city and there is a distinct correlation between age and cost, socio-economic characteristics, and locations of high heat distribution within the city.

Singh, Ridhima↗
DOE OSTI2020

Electrochemical Reduction Selectivity of Crotonaldehyde on Copper

Lignocellulosic waste is a potential feedstock for the generation of fuels and commodity chemicals, but existing conversion methods are too cost-intensive to be viable long-term solutions. Electrochemical reductions are promising for decentralized biomass valorization due to their modular scaling and capacity to run intermittently and without high temperatures or pressures. Using crotonaldehyde as a multi-functional model compound for the many partially unsaturated oxygenates found in processed biomass, we here demonstrate the production of butanal, butanol, butene, and butane (variously useful as commodity chemicals and major components of liquified petroleum gas) under ambient conditions by reductive bulk electrolysis with a copper mesh working electrode. We identify an optimum potential for reduced organic production under the reaction conditions and compare product distributions from reductions of intermediate species to further propose branching reaction pathways. Though butanal is typically the most abundant product from crotonaldehyde reduction, most of the butene and butane appear to result from a pathway involving initial reduction of the aldehyde group. We discuss evidence that selectivity is driven by interplay between crotonaldehyde reduction, local pH shifts due to the hydrogen evolution reaction, and changes in site reactivity and availability due to electrode fouling. This demonstration of model electrochemical biomass valorization also serves to inform further exploration into reduction of multi-functional molecules and electrochemical biomass processing in general.

biomass↗
DOE OSTI2025

Energy Transfer Mechanisms in Large Low-Bandgap Polymers from Time-Resolved Experiments and Nonadiabatic Molecular Dynamics Calculations

Conjugated polymers offer unprecedented chemical tunability for modulating energy transfer in a multitude of infrared light applications. In this work, we use a combination of time-resolved spectroscopic experiments and nonadiabatic molecular dynamics calculations to probe the photochemistry and nonradiative transitions in a recently synthesized narrow bandgap donor–acceptor conjugated polymer based on alternating cyclopentadithiophene and electronegative benzothiadiazole heterocycles. Using large-scale semi-empirical nonadiabatic molecular dynamics, which can treat a large 260-atom hexamer, we calculate an S 5 → S 1 lifetime of 34.75 fs, which is consistent with our time-resolved spectroscopic data. Our simulations suggest that vibronic motions of the central carbons in the cyclopentadithiophene functional groups are predominantly involved in the nonradiative transitions, and the excitation becomes more localized on a monomer fragment over time. The combined use of time-resolved experiments and nonadiabatic molecular dynamics calculations in this work provides mechanistic insight into chemical functionalities that can be tuned to enhance energy transfer in other prospective low-bandgap polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Transition Metal Dissolution Mechanisms and Impacts on Electronic Conductivity in Composite LiNi 0.5 Mn 1.5 O 4 Cathode Films

The high-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode material offers high energy density storage capabilities without the use of costly Co that is prevalent in other Li-ion battery chemistries (e.g., LiNi x Mn y Co z O 2 (NMC)). Unfortunately, LNMO-containing batteries suffer from poor cycling performance because of the intrinsically coupled processes of electrolyte oxidation and transition metal dissolution that occurs at high voltage. In this work, we use operando electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies to demonstrate that transition metal dissolution in LNMO is tightly coupled to HF formation (and thus, electrolyte oxidation reactions as detected with operando and in situ solution NMR), indicative of an acid-driven disproportionation reaction that occurs during delithiation (i.e., battery charging). Leveraging the temporal resolution (s-min) of magnetic resonance, we find that the LNMO particles accelerate the rate of LiPF 6 decomposition and subsequent Mn 2+ dissolution, possibly due to the acidic nature of terminal Mn-OH groups. X-ray photoemission electron microscopy (XPEEM) provides surface-sensitive and localized X-ray absorption spectroscopy (XAS) measurements, in addition to X-ray photoelectron spectroscopy (XPS), that indicate disproportionation is enabled by surface reconstruction upon charging, which leads to surface Mn 3+ sites on the LNMO particle surface that can disproportionate into Mn 2+ (dissolved) and Mn 4+ (s) . During discharge of the battery, we observe high quantities of metal fluorides (in particular, MnF 2 ) in the cathode electrolyte interphase (CEI) on LNMO as well as the conductive carbon additives in the composite. Electronic conductivity measurements indicate that the MnF 2 decreases film conductivity by threefold compared to LiF, suggesting that this CEI component may impede both the ionic and electronic properties of the cathode. Ultimately, to prevent transition metal dissolution and the associated side reactions in spinel-type cathodes (particularly those that operate at high voltages like LNMO), the use of electrolytes that offer improved anodic stability and prevent acid byproducts will likely be necessary.

36 MATERIALS SCIENCE↗