Search NASA⌕ Search

SEARCH · Search NASA

Results for “thermodynamic cycles”

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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Kinetically Dormant Ni‐Rich Layered Cathode During High‐Voltage Operation

Abstract The degradation of Ni‐rich cathodes during long‐term operation at high voltage has garnered significant attention from both academia and industry. Despite many post‐mortem qualitative structural analyses, precise quantification of their individual and coupling contributions to the overall capacity degradation remains challenging. Here, by leveraging multiscale synchrotron X‐ray probes, electron microscopy, and post‐galvanostatic intermittent titration technique, the thermodynamically irreversible and kinetically reversible capacity loss is successfully deconvoluted in a polycrystalline LiNi 0.83 Mn 0.1 Co 0.07 O 2 cathode during long‐term charge/discharge cycling in full cell configuration. Contradicting the dramatic capacity loss, the layered structure remains highly alive even after 1000 cycles at 4.6 V while undergoing a three‐order of magnitude reduction in the mass transfer kinetics, leading to almost fully recoverable capacity under kinetic‐free conditions. Such kinetic dormant behavior after cycling is not simply ascribed to poor chemical diffusion by reconstructed cathode surface but highly synchronizes with the lattice strain evolution stemming from the structural heterogeneity between deeply delithiated layered and degraded rock‐salt phases at high voltage. These findings deepen the degradation mechanism of high‐voltage cathodes to achieve long‐cycling and fast‐charging performance.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Sorption of rare-earth elements onto a ligand-associated media for pH-dependent extraction and recovery of critical materials

Toward recovering rare-earth elements, we prepared a solid-phase media that binds and elutes metals for extraction and enrichment. We report the synthesis and methodology for a solid-phase media that exhibits pH-dependent binding of aqueous rare-earth elements. The media shows pH-dependent binding of Nd III and retains efficiency over at least six cycles of binding and elution. Mixed solutions of rare-earth elements demonstrated a preference for mid and heavy rare-earth elements based on thermodynamic binding preferences of the ligand, and selectivity for rare-earth elements over iron and aluminum were observed with coal fly ash leachate. In conclusion, we expect this new recovery method to be a significant step towards aqueous-based extraction and enrichment of critically important rare-earth elements.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2026

The impact of metastability on the high-pressure behavior of cerium

The structures adopted by solids under pressure are often assumed to reflect thermodynamic equilibrium, yet in many materials phase selection is strongly influenced by kinetic pathways and microstructural inheritance. Elemental cerium (Ce) exemplifies this challenge, with decades of conflicting reports describing different high-pressure crystal structures emerging under nominally identical conditions. Here we use neutron diffraction from large ( ~ 60 mm 3 ) sample volumes to follow the structural evolution in ultra-high-purity Ce during controlled pressure-temperature cycling between 85 and 295 K and up to 8 GPa. We find that the crystal structure formed at high pressure depends on the compression pathway: slow compression ( ~ 0.25 GPa hr −1 ) at room temperature favors an orthorhombic phase (α'), whereas slow ( ~ 0.25 GPa hr −1 ) and also moderately faster ( ~ 0.5 GPa hr −1 ) compression at low temperature stabilizes a pure monoclinic phase (α"). The low-temperature phase persists metastably over a wide temperature range but transforms irreversibly upon heating above ~ 280 K, or modest pressure cycling. Remarkably, the lower-pressure γ phase remains trapped far beyond the expected stability field, persisting to the highest pressures studied. These observations show that phase selection in Ce is governed by kinetics and microstructural memory rather than equilibrium thermodynamics or sample morphology alone, establishing path dependence as a defining feature of its high-pressure behavior.

Ridley, Christopher J. [Oak Ridge National Laborat↗
DOE OSTI2026

Scalable Solar Fuels Production in A Reactor Train System by Thermochemical Redox Cycling of Novel Nonstoichiometric Perovskites

Hydrogen production via two-step thermochemical water splitting redox cycles using nonstoichiometric redox-active metal oxides has the potential to dramatically increase fuel production rates. At moderate-to-low water splitting temperatures, surface reaction kinetics co-limit the process. In such cases, stable and high surface area microstructures that allow exploitation of the full thermodynamic potential of the materials are essential as is tight thermal integration of the reactor module. This project’s goals were the development of novel nonstoichiometric perovskite oxides with high stability and favorable thermodynamic and kinetic properties, to optimize their microstructure for maximizing the fuel productivity, and to build a prototype reactor train system (RTS) comprising at least one reactor to meet specific performance targets: (1) capable of an in-house solar thermochemical hydrogen (STCH) productivity ≥ 12 mL g -1 for stable continuous operation ≥ 20 cycles; and (2) demonstration of scalable solar fuels production at practical solar reactor level in an industrial-scale concentrated solar tower (CST) using developed perovskites to achieve a hydrogen production rate ≥ 1 g h -1 .

08 HYDROGEN↗
DOE OSTI2020

Observational Study of the Thermodynamics and Morphological Characteristics of a Midlatitude Continental Cold Pool Event

Abstract Convectively generated cold pools are important to the Earth system as they exert strong controls on deep convective-storm initiation, intensity, and life cycle. Despite their importance, efforts to introduce such cold pool controls into weather and climate models lack guidance and/or physical constraints from cold pool observations. This work presents a detailed, purely observational analysis of a cold pool event that took place on 23–24 May 2011 in north-central Oklahoma. The characteristics of the cold pool, and the spatiotemporal evolution of the hydrometeors and dynamics in the proximity of the cold pool, are studied with high-resolution observations. The unprecedented dataset used in this work to study cold pool characteristics includes an enhanced network of surface weather stations, a high-temporal-frequency sounding array, and the NEXRAD and Atmospheric Radiation Measurement (ARM) Southern Great Plains radar networks. The potential use of NEXRAD surveillance scans to estimate height and propagation speed of the leading edge of the cold pool (LECP) is presented in this work. Manual identification and tracking of the LECP from NEXRAD imagery shows a spatial and temporal heterogeneity of the LECP properties. Surprisingly, over its detected life cycle, the LECP speed remains almost constant, even though the strength of the cold pool diminishes in time and its height varies. Radar analysis shows that pulses of graupel and hail within downdrafts in the convective system generating the cold pool appeared to be related to temporary increases in the LECP height.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Life cycle assessment of novel heat exchanger for dry cooling of power plants based on encapsulated phase change materials

Cooling systems in power plants account for approximately 40% of total freshwater withdrawals in the U.S. Due to dwindling access to freshwater resources worldwide, continued operation of wet cooling systems poses a significant engineering challenge. To reduce water consumption, a novel air-cooled heat exchanger has been developed using encapsulated phase change material (EPCM) for dry cooling of power plants. Compared to traditional finned-tube air-cooled condensers, this novel EPCM heat exchanger improves the heat transfer coefficient and power plant efficiency while reducing the pressure drop and cooling system cost. Life cycle assessment (LCA) and techno-economic analysis (TEA) are used to evaluate the environmental and economic performance of EPCM heat exchangers from cradle-to-grave and to compare them to wet cooling and traditional air-cooled condensers. A thermodynamic model is developed to predict the EPCM heat exchanger performance for plant-scale operations. Equipment and construction costs for heat exchangers are estimated based on design parameters obtained from the thermodynamic model. Both process-LCA and economic-input–output LCA are used to simulate and test the sensitivity of EPCM alternatives with commercial wet and dry cooling technologies. We investigate options for EPCM end-of-life management upon retiring the heat exchanger and construct a process-based LCA model to estimate a greenhouse gas (GHG) emissions credit for recycling the EPCM. The life cycle GHG emission of the novel dry cooling technology is 1.16 kg CO 2 eq. /MWh compared with the 1.1–4.3 kg CO 2 eq. /MWh reported for commercial dry cooling technologies and consumes 9.5 L/MWh e of water for cradle-to-gate life cycle, which is significantly lower than that of wet cooling systems. The TEA shows many advantages of EPCM cooling technology over the state-of-art dry cooling solutions. Overall, the EPCM heat exchanger provides a better alternative compared to existing dry cooling and wet cooling technologies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Ionic Interdiffusion at Cathode|Solid-Electrolyte Interface: A Machine Learning–Assisted Multiscale Investigation and Mitigation Strategies

Future lithium batteries are expected to use solid electrolytes to achieve higher energy density and fast charge capabilities. However, most solid electrolytes are thermodynamically unstable against layered oxide cathodes. In this study, the stability of LiCoO2 (LCO) cathode with Li10GeP2S12 (LGPS) solid electrolyte is investigated using ab initio molecular dynamics (AIMD) and machine learning molecular dynamics (MLMD). The propensity of ionic interdiffusion, formation of a passivating interphase layer, and corresponding decay in cell performance is addressed using a continuum model. Large-scale MLMD simulations confirm that the LCO|LGPS interface permits interdiffusion of cobalt (Co) and other ionic species, leading to the formation and growth of a resistive interphase and to dramatic capacity fade even in the first cycle. We examine the literature evidence that incorporating a thin layer of LiNb0.5Ta0.5O3 (LNTO) between LCO and LGPS prevents the interdiffusion of ions. Atomistic simulations suggest that substituting lithium (Li) in LNTO with Co is thermodynamically unfavorable, thereby inhibiting ionic interdiffusion. The stable Nb5+/Ta5+ states form a rigid metal-oxide framework, which consequently also prevents the substitution of niobium (Nb) or tantalum (Ta). However, continuum-level analysis suggests that the higher mechanical stiffness of LNTO can lead to interfacial delamination between the LCO and LNTO. This phenomenon reduces the effectiveness of the protective layer. This paper, therefore, highlights the need to develop novel interlayers that balance low ionic interdiffusion with low mechanical stiffness.

Ncube, Musawenkosi K.↗
DOE OSTI2020

Kinetic versus Thermodynamic Stability of LLZO in Contact with Lithium Metal

Li 7 La 3 Zr 2 O 12 (LLZO) garnet-based oxides are a promising class of solid electrolytes used as the separator in all-solid-state batteries (ASSBs). While LLZO is considered to have a wide electrochemical stability window, its intrinsic stability in contact with lithium metal is not sufficiently well understood, and there is still a debate on the key question of whether LLZO does or does not form passivation layers before and during cycling. Utilizing both in situ and operando X-ray photoelectron spectroscopy techniques, in this work we reveal the presence of a kinetic barrier to the reduction of LLZO by Li metal, with the extent of oxygen-deficient interphase (ODI) formation depending sensitively on the energetics of Li metal arriving at the Li vertical bar LLZO interface. Despite the clear presence of a kinetic barrier to reduction, the electrochemical response of the Li vertical bar LLZO interface is unchanged by the presence of the ODI, indicating that ODI formation during electrochemical cycling does not hinder charge transfer across the Li vertical bar LLZO interface. Overall, these results reveal that the reactivity of LLZO with Li metal depends not only on the material properties of the adjoining phases (i.e., surface purity and active contact) and their resulting thermodynamic stability but also on the energy input at the interface and the resulting reaction kinetics. Furthermore, the presence of a kinetic barrier to reduction highlights the additional complexities governing the reactivity of solid-state interfaces in ASSBs and underscores the importance of operando characterization of interfacial stability to design more robust, high-performance protection strategies for solid electrolytes in contact with reactive electrodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Coupling plant litter quantity to a novel metric for litter quality explains C storage changes in a thawing permafrost peatland

Abstract Permafrost thaw is a major potential feedback source to climate change as it can drive the increased release of greenhouse gases carbon dioxide (CO 2 ) and methane (CH 4 ). This carbon release from the decomposition of thawing soil organic material can be mitigated by increased net primary productivity (NPP) caused by warming, increasing atmospheric CO 2 , and plant community transition. However, the net effect on C storage also depends on how these plant community changes alter plant litter quantity, quality, and decomposition rates. Predicting decomposition rates based on litter quality remains challenging, but a promising new way forward is to incorporate measures of the energetic favorability to soil microbes of plant biomass decomposition. We asked how the variation in one such measure, the nominal oxidation state of carbon (NOSC), interacts with changing quantities of plant material inputs to influence the net C balance of a thawing permafrost peatland. We found: (1) Plant productivity (NPP) increased post‐thaw, but instead of contributing to increased standing biomass, it increased plant biomass turnover via increased litter inputs to soil; (2) Plant litter thermodynamic favorability (NOSC) and decomposition rate both increased post‐thaw, despite limited changes in bulk C:N ratios; (3) these increases caused the higher NPP to cycle more rapidly through both plants and soil, contributing to higher CO 2 and CH 4 fluxes from decomposition. Thus, the increased C‐storage expected from higher productivity was limited and the high global warming potential of CH 4 contributed a net positive warming effect. Although post‐thaw peatlands are currently C sinks due to high NPP offsetting high CO 2 release, this status is very sensitive to the plant community's litter input rate and quality. Integration of novel bioavailability metrics based on litter chemistry, including NOSC, into studies of ecosystem dynamics, is needed to improve the understanding of controls on arctic C stocks under continued ecosystem transition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Observed Variability in Convective Cell Characteristics and Near-Storm Environments across the Sea- and Bay-Breeze Fronts in Southeast Texas

Abstract During the DOE Atmospheric Radiation Measurement (ARM) Tracking Aerosol Convection Interactions Experiment (TRACER) IOP spanning June–September 2022, two fixed ARM sites and a mobile team concurrently sampled the airmass heterogeneity across sea- and bay-breeze fronts around the greater Houston metropolitan region. Here, we quantify the spatiotemporal variability between maritime (coastal/bay side of breeze fronts) and continental (inland side of breeze fronts) air masses over 15 IOP days characterized by strong sea-breeze forcing. We analyze environmental profile data from 177 radiosondes and use S- and C-band radar data to track and quantify the variability in attributes of more than 2300 shallow and transitioning cells across different air masses. The composite analysis of environmental profiles indicates that during the early afternoon, the sea-breeze maritime air mass exhibits lower convective available potential energy (CAPE) than the bay-breeze maritime air mass. As the sea breeze advances inland with time, CAPE within the maritime air mass exceeds that of the continental air mass to the north of the breeze fronts. In general, maritime cells have a larger mean composite reflectivity and cell widths than continental cells; however, the response varies between shallow and transitioning cells. Mean composite 20-dB Z echo-top heights, however, are similar across air masses for both shallow and transitioning cells. The continental and maritime inflow air mass for transitioning cells has significantly different mean values for mixed-layer entrainment CAPE, lifted condensation level, level of free condensation, boundary layer depth, and diluted equilibrium level. For shallow cells, only total precipitable water shows a significant difference. Significance Statement The greater Houston metropolitan area is a natural laboratory for understanding the individual impacts of background meteorology and aerosols on convective clouds. Due to its proximity to the Gulf Coast and Galveston Bay, the Houston region experiences a diurnal precipitation cycle in the summer, driven by convection triggered from sea- and bay-breeze fronts. These fronts act as a boundary between air masses with distinct thermodynamic and environmental characteristics. Convergence along these fronts and interactions between storm outflow and the fronts facilitate convection initiation in different mesoscale air masses. This study quantifies the heterogeneity among these air masses while investigating their influence on cloud microphysics. We find that the effect of airmass heterogeneity is more pronounced for the bulk microphysical properties in shallow clouds.

Sharma, Milind↗
DOE OSTI2026

Final DOE-ASR Report for the Project “Using LASSO to bridge the gap between model and observations and to learn about atmospheric convection”

Atmospheric convection spans a wide range of spatial and temporal scales and involves complex interactions with the surrounding dynamic and thermodynamic environment, particularly over tropical continental regions. These processes remain a major source of uncertainty in weather and climate models, including persistent biases in the diurnal cycle of convective precipitation that directly affect estimates of climate sensitivity. Addressing these challenges requires the combined use of high-resolution observations and cloud-resolving modeling frameworks. In this context, the DOE Atmospheric Radiation Measurement (ARM) program’s Large-Eddy Simulation ARM Symbiotic Simulation and Observation (LASSO) activity provides a powerful platform that pairs comprehensive observations with numerical simulations to enable process-level understanding of atmospheric convection. Within this context, this Research and Development Partnership Pilot (RDPP) project was designed to initiate and expand DOE ARM/ASR research capacity at minority-serving institutions, while advancing scientific understanding of convective processes over the Amazon rainforest. Consistent with the RDPP mission, the project emphasized partnership development, training, and workforce capacity building alongside exploratory research activities. On the scientific side, the project produced two peer-reviewed journal articles, and one manuscript currently under review (see list in section 3.1). Together, these studies combine long-term ARM observations and cloud-resolving and convection-permitting modeling to investigate the environmental controls on the shallow-to-deep convective transition during the Amazon wet season. The results demonstrate the central role of early-day moisture preconditioning and large-scale dynamical forcing in regulating isolated deep convection, provide mechanistic insight into convective evolution, and establish physically informed modeling frameworks for future sensitivity experiments. These scientific outcomes are described in sections 2.1 to 2.3 and were disseminated in 8 conference presentations (see section 3.2) and 5 invited talks (see section 3.3), reflecting broad engagement with our community. Equally important, the project achieved its RDPP capacity-building objectives (see section 2.4). A sustained research partnership was established among the University of Maryland, Baltimore County (UMBC), Morgan State University (MSU), and Howard University (HU), and extended to include collaboration with Pacific Northwest National Laboratory (PNNL). The project organized multiple multi-day training events focused on ARM data, LASSO simulations, and quantitative analysis methods, directly engaging students, postdoctoral researchers, and faculty across institutions. These activities broadened participation in ASR research and led to independent adoption of LASSO workflows by students beyond the immediate project team. Finally, the project successfully positioned the participating institutions to pursue future DOE research. Preliminary scientific results, coupled with strengthened partnerships and technical capacity, enabled the submission of follow-on proposals to DOE ASR funding opportunities. In this way, the project fulfilled the RDPP goal of seeding durable research capacity and laying the foundation for larger-scale, sustained engagement with DOE ARM and ASR programs.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Electrorefiner Speciation and Phase Model for Prediction of Operation Lifetime

The Mk IV electrorefiner (ER) at Idaho National Laboratory has recovered uranium metal from used nuclear fuels for 27 years. Thus, large quantities of fission product chlorides more electropositive than uranium have accumulated in the ER salt, increasing the complexity of phase equilibria and salt speciation. Importantly, the melt temperature of the salt increases with ER operation and will ultimately exceed design limits without intervention. Methods to remove fission products from molten chloride salt are known, but their implementation at scale is not yet demonstrated. In this work, historical ER composition and differential scanning calorimetry (DSC) are utilized to develop coupled speciation and chloride salt solution thermochemistry models, which enable accurate present-day analysis of ER salt as well as forecast its future disposition. The developed thermochemical models are applicable to chloride salts generally and have been made available in the Molten Salt Thermal Properties Database – Thermochemical.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Minimum conditions for accurate modeling of urea production via co-electrolysis

Co-electrolysis of carbon oxides and nitrogen oxides promise to simultaneously help restore the balance of the C and N cycles while producing valuable chemicals such as urea. However, co-electrolysis processes are still largely inefficient and numerous knowledge voids persist. Here, we provide a solid thermodynamic basis for modelling urea production via co-electrolysis. First, we determine the energetics of aqueous urea produced under electrochemical conditions based on experimental data, which enables an accurate assessment of equilibrium potentials and overpotentials. Next, we use density functional theory (DFT) calculations to model various co-electrolysis reactions producing urea. The calculated reaction free energies deviate significantly from experimental values for well-known GGA, meta-GGA and hybrid functionals. These deviations stem from errors in the DFT-calculated energies of molecular reactants and products. In particular, the error for urea is approximately -0.25 ± 0.10 eV. Finally, we show that all these errors introduce large inconsistencies in the calculated free-energy diagrams of urea production via co-electrolysis, such that gas-phase corrections are strongly advised.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Molten‐Salt‐Mediated Chemical Looping Oxidative Dehydrogenation of Ethane with In‐Situ Carbon Capture and Utilization

Abstract The molten‐salt‐mediated oxidative dehydrogenation (MM‐ODH) of ethane (C 2 H 6 ) via a chemical looping scheme represents an effective carbon capture and utilization (CCU) method for the valorization of ethane‐rich shale gas and concurrent mitigation of carbon dioxide (CO 2 ) emissions. Here, stepwise experimentation with Li 2 CO 3 ‐Na 2 CO 3 ‐K 2 CO 3 (LNK) ternary salts (i) assessed how each component of the LNK mixture impacted ethane MM‐ODH performance and (ii) explored physicochemical and thermodynamic mechanisms behind melt‐induced changes to ethylene (C 2 H 4 ) and carbon monoxide (CO) yields. Of fifteen screened LNK compositions, nine exhibited ethylene yields greater than 50 % at 800 °C while maintaining C 2 H 4 selectivities of 85 % or higher. LNK salts rich in Li 2 CO 3 content yielded more ethylene and CO on average than their counterparts, and net CO 2 capture per cycle reached a maximum of ~75 %. Extended MM‐ODH cycling also demonstrated long‐term stability of a high‐performing LNK medium. Density functional theory (DFT) calculations andab initiomolecular dynamics (AIMD) simulations suggested that the molten salt does not directly activate C 2 H 6 . Meanwhile, an empirical model informed by experimental data and reaction thermodynamics adequately predicted overall MM‐ODH performance from LNK composition and provided insights into the system′s primary drivers.

Chemistry↗
DOE OSTI2023

Thermal Stability of Schottky Contacts and Rearrangement of Defects in β ‐Ga 2 O 3 Crystals

Abstract The thermal stability of different Schottky contacts (Au, Pt, and Ni) on (100) β ‐Ga 2 O 3 single crystals grown by the Czochralski method is investigated. Besides the examination of the Schottky barrier parameters, contact‐dependent defect levels are investigated by deep‐level transient spectroscopy (DLTS) in a 100–650 K (ramp‐up) and 650–100 K (ramp‐down) temperature cycle. Several defect levels are detected below the conduction band minimum at 0.41, 0.60, 0.77, 0.96, and 1.17 eV. In the temperature ramp‐down DLTS, the 1.17 eV level disappears, and the 0.60 eV level appears for all Schottky contacts. DFT calculations suggest that rearrangement and dissociation of a single hydrogen from a doubly‐hydrogenated Ga─O divacancy complex occurs during the temperature sweep under bias. The trap level at 0.96 eV only appears after the thermal load for the Ni contact, in contrast to Au and Pt, where it is present without a thermal budget. Temperature‐dependent leakage current (at −4 V) measurements indicate oxidation of Ni, and further thermodynamic analysis suggests alloying of Au‐Ga atoms at the Au/ β ‐Ga 2 O 3 interface. These studies provide insight into the behavior induced by these common Schottky contacts and the alteration associated with temperature cycling.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Multimodal Analysis of Reaction Pathways of Cathode Materials for Lithium Ion Batteries

Conversion mechanism in lithium ion batteries provides higher capacity than intercalation mechanism since multiple numbers of electrons and lithium ions are associated. However, poor cycling stability, large voltage hysteresis, and low energy efficiency have been great challenges of conversion reaction. To address those issues, conversion-type electrode materials have been reformed via doping or substituting other elements. For example, iron fluorides (FeF 2 , FeF 3 ) have modified as iron oxyfluorides (FeF 1-x O x ), showing enhanced long-term stability. Furthermore, co-substituted (both anion and cation substituted) Fe 0.9 Co 0.1 OF (FeCoOF) was demonstrated excellent cycling stability. (capacity of 350 mAh g -1 at a current of 500 mA g -1 for 1000 cycles). Substituting anion and cation in iron fluoride has been suggested as an effective method to achieve better reversibility but understanding of lithiation reactions in co-substituted FeCoOF is not clear. This work takes advantage of ex-situ/ in-situ synchrotron X-ray based techniques and transmission electron microscopy to elucidate structural changes with lithium ion, which may provide fundamental insights into modifying conversion-type materials. Figure 1 presents discharge-charge curves and pair distribution function patterns acquired at each potential. As lithium ions were inserted, structural changes were noticed both at short-range and long-range. However, long-range ordering was nearly maintained even at 1 V, indicating absence of conversion reaction. Figure 2 shows lithiation induced structural evolution of a single FeCoOF nanorod observed in real time. As lithiation proceeds, the width of nanorods shows a stepwise increase, particularly A in figure 2d, which may indicate multiple steps of lithiation occur. Considering that conversion reaction takes place around 2 V in FeF 3 , co-substitution Co and O into iron fluoride may change thermodynamic features of lithiation reactions by lowering the initiation potential for conversion reaction. Instead, phase transformations occur at long-range order, which may help maintaining structural integrity during operation, eventually, achieving cycling stability.

25 ENERGY STORAGE↗
DOE OSTI2022

Exploring the Origin of Anionic Redox Activity in Super Li-Rich Iron Oxide-Based High-Energy-Density Cathode Materials

Super alkali-rich materials (alkali:transition metal ratio of ≥2:1), such as Li 5 FeO 4 , exhibit the potential to realize anionic redox upon deep delithiation. Li 5 FeO 4 was shown to undergo reversible cycling between Li 4 FeO 3.5 and Li 3 FeO 3.5 with combined cation/anion redox, a remarkable capacity of 189 mAh/g, and no O 2 release. However, the impact of phase transformations on the reaction thermodynamics and the correlation between the structural changes and reaction reversibility remain unclear. In this study, we use first-principles calculations to examine the delithiation and (re)lithiation reactions of Li 5 FeO 4 . We show that the experimentally observed charge and discharge processes go through non-equilibrium pathways. Upon delithiation, the compound undergoes a phase transformation from Li 5 FeO 4 , with tetrahedrally coordinated (T d ) Fe ions, to a delithiated disordered rocksalt structure, with octahedral (O h ) Fe ions. Fe-ion migration has an asymmetric kinetic barrier that makes T d → O h migration facile, whereas the reverse process has a much larger barrier, explaining the difficulties in reaction reversibility. We further elucidate the transition metal and O redox sequences during the charge cycle and identify the complex electrochemistry associated with the dual participation of cationic redox (Fe 3+ /Fe 4+ ) and anionic redox (O 2– /O – /O o ). Armed with this knowledge, we conduct high-throughput screening of known alkali-rich transition metal oxides by evaluating their potential to enable reversible anionic redox, with multiple candidates proposed for further experimental trials. Furthermore, our work provides a useful guide for the further development of super alkali-rich anionic-redox-active electrodes for high-energy-density batteries.

25 ENERGY STORAGE↗