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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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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Confinement effects on the solvation structure of solvated alkaline metal cations in a single-digit 1T-MoS 2 nanochannel: A first-principles study

Confinement plays an important role in determining ion transport in porous materials, which, in turn, may influence the performance of many energy storage and desalination devices. In this work, we combined density functional theory (DFT) with an implicit solvation model and ab initio molecular dynamics (AIMD) to investigate the effects of nanoconfinement on several solvated alkaline metal cations in a single-digit 1T-MoS 2 nanochannel. Our DFT calculations with a solvation model indicated that cations with stronger hydration energy introduce a higher number of co-intercalated water molecules into the channel, consistent with early experimental observation obtained for MXene (2D transition metal carbide) channels. The predicted optimal water numbers for the cations were then used for AIMD simulations that explicitly include the effects of the solvent. When compared with the cations in bulk solution, our simulations showed that the hydration structure and coordination number (CN) of the solvated cations confined in the MoS 2 channel can be significantly altered. Further, we found that larger cations with weaker hydration energy (K + , Rb + , and Cs + ) exhibited a distinctive CN decrease under confinement, while smaller cations (Li + and Na + ) retained a similar hydration shell as in the bulk solution. More specifically, the hydration shell of large cations (K + , Rb + , and Cs + ) in MoS 2 showed similar features of the coordination angle to the bulk, which suggests the partially broken hydration shell with no geometry change under confinement. Our simulations provided insights into the change of the hydration structure of alkaline metal cations under confinement, which may have important implications on their transport in the 1T-MoS 2 channel.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hydrolysis of Metal Dioxides Differentiates d-block from f-block Elements: Pa(V) as a 6d Transition Metal; Pr(V) as a 4f “Lanthanyl”

Gas-phase reactions of pentavalent metal dioxide cations M V O 2 + with water were studied experimentally for M = V, Nb, Ta, Pr, Pa, U, Pu, and Am. Addition of two H 2 O can occur by adsorption to yield hydrate (H 2 O) 2 M V O 2 + or by hydrolysis to yield hydroxide M V (OH) 4 + . Displacement of H 2 O by acetone indicates hydrates for Pr V , U V , Pu V , and Am V , whereas nondisplacement indicates hydroxides for Nb V , Ta V , and Pa V . Computed potential energy profiles agree with the experimental results and furthermore indicate that acetone unexpectedly induces dehydrolysis and displaces two H 2 O from (H 2 O)VO(OH) 2 + to yield (acetone) 2 VO 2 + . Structures and energies for several M V , as well as for Th IV and U VI , indicate that hydrolysis is governed by the involvement of valence f versus d orbitals in bonding: linear f-element dioxides are more resistant to hydrolysis than bent d-element dioxides. Accordingly, for early actinides, hydrolysis of Th IV is characteristic of a 6d-block transition metal; hydration of U V and U VI is characteristic of 5f actinyls; and Pa V is intermediate between 6d and 5f. The praseodymium oxide cation Pr V O 2 + is assigned as an actinyl-like lanthanyl with properties governed by 4f bonding.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Enabling Facile Anionic Kinetics through Cationic Redox Mediator in Li-Rich Layered Cathodes

Anionic oxygen redox has aroused great interests in developing high-capacity Li-ion battery cathode materials. The fundamental understanding of this concept, compared to cationic redox, has promoted extensive studies on lithium transition metal oxides including those of 4d and 5d transition metals. Lithium ruthenium oxide has been found to exhibit a reversible anionic redox upon cycling. However, lithium-rich layered oxide with anionic redox is still facing great challenges such as sluggish kinetics. Here we investigate the effect of cationic redox on the kinetics of anionic reaction when they are strongly coupled. We report the cobalt substituted lithium ruthenium oxide, where all Ru, Co and O redox participate in the charge compensation mechanism in relatively defined voltage regions. Additionally, the improved anionic kinetics is attributed to the fast cationic Co redox process that serves as a redox mediator. Our work sheds light into the potential direction to address the commonly believed sluggish anionic kinetics in high-capacity oxygen-redox cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Electronic properties of epitaxial La 1- x Sr x RhO 3 thin films

Here, we report on the synthesis and electronic properties of epitaxial perovskite La 1- x Sr x RhO 3 thin films. Thin films with a Sr content ranging from $\textit{x}$ = 0 to 0.5 have been grown using molecular beam epitaxy. Transport and x-ray photoemission spectroscopy data reveal an insulator-metal-insulator transition, accompanied by a $\textit{p-}$ to $\textit{n}-$ type carrier change observed in Hall measurements. Combined with theoretical calculations, we find that the addition of Sr does not directly dope carriers into the conduction band, but rather induces localized Rh 4$\textit{d}$ states within the LaRhO 3 band gap. The bandwidth of the impurity band increases with Sr content, eventually causing the valence band (VB) and the localized Rh 4$\textit{d}$ band to overlap, which explains the first insulator-to-metal transition occurring at $\textit{x}$ = 0.35. For Sr content $\textit{x}$ > 0.4, possible cation ordering results in an increase of the gap between the VB and the Rh 4$\textit{d}$ band, leading to the second metal-to-insulator transition. We map out the electronic phase diagram of the Sr-doped LaRhO 3 system and suggest strategies to engineer the electronic states in rhodate systems via delocalizing the Rh 3+ states.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Unusual electrical conductivity driven by localized stoichiometry modification at vertical epitaxial interfaces

Precise control of lattice mismatch accommodation and interfacial cation diffusion is critical to modulate correlated functionalities in epitaxial heterostructures, particularly when the interface composition is positioned near a compositional phase transition boundary. Here we select La 1-x Sr x MnO 3 (LSMO) as a prototype phase transition oxide and establish vertical epitaxial interfaces with NiO for exploring the strong interplay between strain accommodation, stoichiometry modification, and localized electron transport across the interface. It is found that localized stoichiometry modification overcomes the dead layer problem plaguing LSMO and leads to strongly directional conductivity, as manifested by a more than three orders of magnitude difference between out-of-plane and in-plane conductivity. Comprehensive atomic scale structural characterization and transport measurements reveal that this emerging behavior is created by a compositional change produced by preferential cation diffusion that pushes the LSMO phase transition from insulating into metallic within an ultrathin interface region. This study explores the nature of unusual electrical conductivity at vertical epitaxial interfaces and highlights the beneficial role of controllable cation diffusion that enables emerging functionalities for a broad range of potential applications such as memristors, spintronic devices, and novel nanoelectronic devices using strongly correlated materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Cation Vacancies Enable Anion Redox in Li Cathodes

Conventional Li-ion battery intercalation cathodes leverage charge compensation that is formally associated with redox on the transition metal. Employing the anions in the charge compensation mechanism, so-called anion redox, can yield higher capacities beyond the traditional limitations of intercalation chemistry. Here, we aim to understand the structural considerations that enable anion oxidation and focus on processes that result in structural changes, such as the formation of persulfide bonds. Using a Li-rich metal sulfide as a model system, we present both first-principles simulations and experimental data that show that cation vacancies are required for anion oxidation. First-principles simulations show that the oxidation of sulfide to persulfide only occurs when a neighboring vacancy is present. To experimentally probe the role of vacancies in anion redox processes, we introduce vacancies into the Li 2 TiS 3 phase while maintaining a high valency of Ti. When the cation sublattice is fully occupied and no vacancies can be formed through transition metal oxidation, the material is electrochemically inert. Upon introduction of vacancies, the material can support high degrees of anion redox, even in the absence of transition metal oxidation. The model system offers fundamental insights to deepen our understanding of structure–property relationships that govern reversible anion redox in sulfides and demonstrates that cation vacancies are required for anion oxidation, in which persulfides are formed.

25 ENERGY STORAGE↗
DOE OSTI2025

Designing Advanced Electrolytes for High-Voltage High-Capacity Disordered Rocksalt Cathodes

Lithium (Li)-excess transition metal oxide materials which crystallize in the cation-disordered rock salt (DRX) structure are promising cathodes for realizing low-cost, high-energy-density Li batteries. However, the state-of-the-art electrolytes for Li-ion batteries cannot meet the high-voltage stability requirement for high-voltage DRX cathodes, thus new electrolytes are urgently demanded. It has been reported that the solvation structures and properties of the electrolytes critically influence the performance and stability of the batteries. In this study, the structure–property relationships of various electrolytes with different solvent-to-diluent ratios are systematically investigated through a combination of theoretical calculations and experimental tests and analyses. This approach guides the development of electrolytes with unique solvation structures and characteristics, exhibiting high voltage stability, and enhancing the formation of stable electrode/electrolyte interphases. These electrolytes enable the realization of Li||Li 1.094 Mn 0.676 Ti 0.228 O 2 (LMTO) DRX cells with improved performance compared to the conventional electrolyte. Specifically, Li||LMTO cells with the optimized advanced controlled-solvation electrolyte deliver higher specific capacity and longer cycle life compared to cells with the conventional electrolyte. Additionally, the investigation into the structure–property relationship provides a foundational basis for designing advanced electrolytes, which are crucial for the stable cycling of emerging high-voltage cathodes.

25 ENERGY STORAGE↗
DOE OSTI2026

Elucidating the Structural and Electronic Effects of Ni and Mn Cationic Incorporation on CoOOH for Efficient Benzyl Alcohol Electrooxidation

Transition-metal oxyhydroxides such as CoOOH are promising low-cost electrocatalysts for the selective electrooxidation of organic molecules, yet the influence of ubiquitous transition-metal impurities on their performance and durability remains poorly understood. Here, we experimentally probed the individual and synergistic electrochemical and structural effects of Ni and Mn incorporations into model CoOOH electrocatalysts toward an efficient benzyl alcohol oxidation reaction (BAOR). Comprehensive electrochemical, microscopic, and spectroscopic analyses reveal that Ni incorporation enhances charge-transfer kinetics and overall activity through the formation of catalytically active Ni 3+ sites, whereas Mn exhibited a more complex but interesting role. At the early stages of operation, Mn 4+ acts as a stabilizing surface layer that mitigates catalyst degradation but partially blocks Co sites before they undergo gradual leaching. The concurrent incorporation of both Ni and Mn yields a trimetallic 2NMC@NF electrocatalyst that integrates the activity benefits of Ni with the stability conferred by Mn, achieving 92.9% benzyl alcohol conversion and 91.4% Faradaic efficiency after 24 h at 1.5 V vs RHE. These findings elucidate how trace Ni and Mn impurities, often introduced from electrolytes or external sources, can modulate the lattice and electronic structure of CoOOH, offering a design strategy for enhancing both activity and long-term stability in electrocatalytic organic oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Operando X-ray Diffraction Studies of the Mg-Ion Migration Mechanisms in Spinel Cathodes for Rechargeable Mg-Ion Batteries

A promising high-voltage spinel oxide cathode material MgCrMnO 4 with 18% Mg/Mn inversion was synthesized successfully. A new custom operando battery device was designed to study the cation migration mechanisms of the MgCrMnO 4 cathode using 0.1 M Mg(TPFA) 2 electrolyte dissolved in triglyme and activated carbon as the anode. For the first time in multivalent batteries, high-quality operando diffraction data enabled the accurate quantification of cation contents in the host structure. Besides the exceptional reversibility of 12% Mg 2+ insertion in Mg 1- x CrMnO 4 ( x ≤ 1), a partially reversible insertion of excess Mg 2+ during overdischarging was also observed. Moreover, the insertion/extraction reaction was experimentally shown to be accompanied by a series of cation redistributions in the spinel framework, which were further supported by density functional theory calculations. Furthermore, the inverted Mn is believed to be directly involved in the cation migrations, which would cause voltage hysteresis and irreversible structural evolution after overdischarging. Tuning the Mg/Mn inversion rate could provide a direct path to further optimize spinel oxide cathodes for Mg-ion batteries, and more generally, the operando techniques developed in this work should play a key role in understanding the complex mechanisms involved in multivalent ion insertion systems.

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

Prospects for n -type doping of (Al x Ga 1– x ) 2 O 3 alloys

Here we systematically explore the properties of group-IV (C, Si, Ge, and Sn) and transition metal (Hf, Zr, and Ta) dopants substituting on the cation site in (Al x Ga 1– x ) 2 O 3 (AlGO) alloys using first-principles calculations with a hybrid functional. In Ga 2 O 3 , each of these dopants acts as a shallow donor. In Al 2 O 3 , they are deep defects characterized by the formation of either DX centers or positive- U (+/0) levels. Combining our calculations of dopant charge-state transition levels with information of the AlGO alloy band structure, we estimate the critical Al composition at which each dopant transitions from being a shallow to a deep donor. We identify Si to be the most efficient dopant to achieve n -type conductivity in high Al-content AlGO alloys, acting as a shallow donor over the entire predicted stability range for AlGO solid solution alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Inhibiting collective cation migration in Li-rich cathode materials as a strategy to mitigate voltage hysteresis

Lithium-rich cathodes are promising energy storage materials due to their high energy densities. However, voltage hysteresis, which is generally associated with transition metal migration, limits their energy efficiency and implementation in practical devices. Here we reveal that voltage hysteresis is related to the collective migration of metal ions, and that isolating the migration events from each other by creating partial disorder can create high-capacity reversible cathode materials, even when migrating transition metal ions are present. In this study, we demonstrate this on a layered Li-rich chromium manganese oxide that in its fully ordered state displays a substantial voltage hysteresis (>2.5 V) associated with collective transition metal migration into Li layers, but can be made to achieve high capacity (>360 mAh g –1 ) and energy density (>1,100 Wh kg –1 ) when the collective migration is perturbed by partial disorder. This study demonstrates that partially cation-disordered cathode materials can accommodate a high level of transition metal migration, which broadens our options for redox couples to those of mobile cations.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Promoting the water dissociation of nickel sulfide electrocatalyst through introducing cationic vacancies for accelerated hydrogen evolution kinetics in alkaline media

Developing cost-effective non-precious electrocatalysts with excellent HER performance in alkaline media is of significance for industrial hydrogen production. Herein, we successfully endow Ni 3 S 2 with unprecedentedly enhanced alkaline HER activities by introducing nickel vacancies. The Ni 3 S 2 catalyst with nickel vacancies exhibits an ultralow overpotential of 35 mV at 10 mA cm –2 in 1 M KOH electrolyte, outperforming commercial Pt/C (56 mV) and most reported non-precious electrocatalysts. The electron paramagnetic resonance and X-ray absorption fine structure etc. validates the formation of Ni vacancies and the change of the geometric/electronic structure of Ni 3 S 2 . Additionally, the theoretical calculations reveal that the Ni sites with higher valence state neighbouring the Ni vacancies can promote the water dissociation, playing a vital role in accelerating HER kinetics in alkaline media. Finally, this work may provide a universal strategy to enhance the HER activity of transition-metal compound catalysts in alkaline media by means of cationic defect engineering.

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

Impact of Synthetic Parameters on Structure and Electrochemistry of High-Entropy Layered Oxide LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2

Here, this study explored a high-entropy layered oxide (HELO), LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2 , prepared by coprecipitation followed by heat treatment. Coprecipitation yielded a kinetically favored product, and the subsequent heat treatment under various temperatures and times allowed tuning the material toward more thermodynamically favored structures. Refinement of X-ray powder diffraction (XRD) revealed that after 450 °C treatment, ~12% of the Ni 2+ in the structure was located within the lithium cation layer. After heat treatment at 600, 700, and 800 °C, there was a continued decrease of Ni 2+ in the lithium cation layer to 9.3, 6.3, and 3.7%, respectively. Longer heat treatment times at 800 °C decreased the level to 2.5%. Electrochemical behavior was evaluated by cyclic voltammetry, galvanostatic cycling, rate capability testing, and electrochemical impedance spectroscopy, where increased loaded voltage, functional capacity, rate capability, and decreased impedance were observed for samples treated at higher temperatures with lower cation mixing. X-ray absorption near edge spectroscopy (XANES) data indicated that the redox activity of Ni and Co was dominant in the electrochemistry, while the participation of Mn or Fe was minimal. The level of Ni oxidation state change between charge and discharge related to the heat treatment temperature where the samples with high cation mixing showed lower capacity consistent with some Ni 3+ in the transition metal layer inaccessible for electron transfer. Longer heat treatment times at 800 °C did not continue to provide a benefit in electrochemical function even with some additional reduction in cation mixing.

25 ENERGY STORAGE↗
DOE OSTI2021

Non-topotactic reactions enable high rate capability in Li-rich cathode materials

High-rate cathode materials for Li-ion batteries require fast Li transport kinetics, which typically rely on topotactic Li intercalation/de-intercalation because it minimally disrupts Li transport pathways. In contrast to this conventional view, here we demonstrate that the rate capability in a Li-rich cation-disordered rocksalt cathode can be significantly improved when the topotactic reaction is replaced by a non-topotactic reaction. The fast non-topotactic lithiation reaction is enabled by facile and reversible transition metal octahedral-to-tetrahedral migration, which improves rather than impedes Li transport. Using this concept, we show that high-rate performance can be achieved in Mn- and Ni-based cation-disordered rocksalt materials when some of the transition metal content can reversibly switch between octahedral and tetrahedral sites. Overall, this study provides a new perspective on the design of high-performance cathode materials by demonstrating how the interplay between Li and transition metal migration in materials can be conducive to fast non-topotactic Li intercalation/de-intercalations.

25 ENERGY STORAGE↗
DOE OSTI2022

Correlation of Oxygen Anion Redox Activity to In‐Plane Honeycomb Cation Ordering in Na x Ni y Mn 1− y O 2 Cathodes

Sodium‐ion batteries (SIBs) are one of the most promising next‐generation energy storage systems because of their abundant and low‐cost component materials. However, the lower energy density of SIBs compared with lithium‐ion batteries diminishes their practical value proposition. Among the many sodium‐based cathodes, layered transition metal oxides with high sodium content have energy densities comparable with the lithium‐ion battery technology. When charged above 4.1 V, the sodium‐based cathodes often undergo transformations because the activation of oxygen anion redox causes irreversible oxygen release, transition metal ion migration, lattice distortion, and rapid capacity decay. Here, in situ gas analysis is performed to evaluate the lattice oxygen anion redox activity in Na x Ni y Mn 1− y O 2 cathodes with P2 and O3 structural orderings. Operando X‐ray diffraction and neutron diffraction are performed to assess the structural changes related to lattice oxygen redox and transition metal ion migration in Na x Ni y Mn 1− y O 2 cathodes. The results unveil that in‐plane honeycomb cationic ordering can help suppress oxygen anion redox activity, which is critical for the future design of layered transition metal oxide cathodes that are prone to achieve high‐energy for durable SIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Synthesis of Eu(HCOO) 3 and $\mathrm{Eu(HCOO)_3}$ • $\mathrm{(HCONH_2)_2}$ crystals and observation of their 5 D 0 → 7 F 0 transition for quantum information systems

Two stoichiometric metal-organic frameworks containing Eu 3+ cations are probed as candidates for photon-based quantum information storage. Synthesis procedures for growing 0.2 mm, rod-shaped Eu(HCOO) 3 and 1–3 mm, rhombohedral $\mathrm{Eu(HCOO)_3}$ • $\mathrm{(HCONH_2)_2}$ single crystals are presented with visible precipitation as soon as 1 h into heating for Eu(HCOO) 3 and 24 h for $\mathrm{Eu(HCOO)_3}$ • $\mathrm{(HCONH_2)_2}$. Room temperature and 1.4 K photoluminescence measurements of the 5 D 0 → 7 F J transitions of Eu 3+ are analyzed for both compounds. Comparisons of peak width and intensity are discussed along with the notable first report for both of the 5 D 0 → 7 F 0 transition, the hyperfine structure of which has potential use in quantum memory applications. Furthermore, the air instability of $\mathrm{Eu(HCOO)_3}$ • $\mathrm{(HCONH_2)_2}$ and the transformation of its photoluminescence properties are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Increasing Capacity in Disordered Rocksalt Cathodes by Mg Doping

Using both computations and experiments, we demonstrate that the performance of Li-excess cation-disordered rocksalt cathodes can be improved by Mg substitution. Furthermore we find that Mg reduces the amount of Li in the compound that is strongly bound to F and thereby increases the capacity. This enables the use of fluorination as a tool to improve stability of the compounds without significant loss of capacity. Mg emerged as the most optimal substitution element from a systematic computational study aimed at identifying inactive doping elements with a strong enough bonding strength to fluorine to displace Li from the F environments. Our results also show that capacity can be traded for cycle life depending on whether Mg is substituted for Li or for the redox metal. This design strategy should be considered in fluorinated cathodes, which will facilitate the design of optimized disordered rocksalt oxyfluoride cathodes.

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

Coupling of organic cation and inorganic lattice in methylammonium lead halide perovskites: Insights into a pressure-induced isostructural phase transition

Organic-inorganic hybrid metal-halide perovskite (OIHP) materials provide a tunable platform for engineering their optoelectronic properties. Although several high-pressure studies have been conducted from the OIHP family of single crystals and films, the exact nature of the dynamic coupling of the CH 3 NH 3 (MA) cation with the octahedral lattice framework and the mechanisms responsible for the structural phase transformation under pressure are not well captured. By combined photoluminescence (PL), synchrotron-based x-ray diffraction, and Raman-scattering studies as a function of pressure from methylammonium lead bromide (MAPbBr 3 ), we shed light on an isostructural phase transition due to the coupling of the MA cation and the PbBr 6 lattice through hydrogen bonding. The sharp discontinuities at ~ 1 GPa and ~ 3 GPa in the PL peak positions correlate with the structural changes observed in high-pressure XRD and Raman-scattering studies. The electronic band edge as a function of pressure is calculated within density-functional theory. The PL peak position, intensity and width of the excitonic peak show significant changes at 2 GPa, which corroborate the changes observed in high-pressure Raman-scattering studies. The frequencies of the lattice modes and the C-H/N-H bending and stretching modes of the MA cation show anomalous changes and other nuances at 2 GPa. The suppression of rotational and orientational disorder of the organic moiety is initiated at 2 GPa and the ordering is completed by 3.0 GPa, leading to an order-disorder type cubic II (Im$\overline{3}$) to orthorhombic ( Pnma ) phase transition. Along with the revelation of an isostructural transformation at 2 GPa, this paper highlights the impact of molecular vibrations on the electronic properties of MAPbBr 3 under pressure.

36 MATERIALS SCIENCE↗