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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 1,351 records · Page 75
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Importance of Superstructure in Stabilizing Oxygen Redox in P3‐Na 0.67 Li 0.2 Mn 0.8 O 2

Abstract Activation of oxygen redox represents a promising strategy to enhance the energy density of positive electrode materials in both lithium and sodium‐ion batteries. However, the large voltage hysteresis associated with oxidation of oxygen anions during the first charge represents a significant challenge. Here, P3‐type Na 0.67 Li 0.2 Mn 0.8 O 2 is reinvestigated and a ribbon superlattice is identified for the first time in P3‐type materials. The ribbon superstructure is maintained over cycling with very minor unit cell volume changes in the bulk while Li ions migrate reversibly between the transition metal and Na layers at the atomic scale. In addition, a range of spectroscopic techniques reveal that a strongly hybridized Mn 3d–O 2p favors ligand‐to‐metal charge transfer, also described as a reductive coupling mechanism, to stabilize reversible oxygen redox. By preparing materials under three different synthetic conditions, the degree of ordering between Li and Mn is varied. The sample with the maximum cation ordering delivers the largest capacity regardless of the voltage windows applied. These findings highlight the importance of cationic ordering in the transition metal layers, which can be tuned by synthetic control to enhance anionic redox and hence energy density in rechargeable batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Insight into the Fast-Rechargeability of a Novel Mo 1.5 W 1.5 Nb 14 O 44 Anode Material for High-Performance Lithium-Ion Batteries

Wadsley–Roth phased niobates are promising anode materials for lithium-ion batteries, while their inherently low electrical conductivity still limits their rate-capability. Herein, a novel doped Mo 1.5 W 1.5 Nb 14 O 44 (MWNO) material is facilely prepared via an ionothermal-synthesis-assisted doping strategy. The detailed crystal structure of MWNO is characterized by neutron powder diffraction and aberration corrected scanning transmission electron microscope, unveiling the full occupation of Mo 6+ -dopant at the t1 tetrahedral site. In half-cells, MWNO exhibits enhanced fast-rechargeability. In this work, the origin of the improved performance is investigated by ultraviolet–visible diffuse reflectance spectroscopy, density functional theory (DFT) computation, and electrochemical impedance spectroscopy, revealing that bandgap narrowing improves the electrical conductivity of MWNO. Furthermore, operando X-ray diffraction elucidates that MWNO exhibits a typical solid-solution phase conversion-based lithium-ion insertion/extraction mechanism with reversible structural evolution during the electrochemical reaction. The boosted lithium-ion diffusivity of MWNO, due to the Mo 6+ /W 6+ doping effect, is confirmed by a galvanostatic intermittent titration technique and DFT. With the simultaneously enhanced electrical conductivity and lithium-ion diffusivity, MWNO successfully demonstrates its fast-rechargeability and practicality in the LiNi 0.5 Mn 1.5 O 4 -coupled full-cells. Therefore, this work illustrates the potential of ionothermal synthesis in energy storage materials and provides a mechanistic understanding of the doping effect on improving material's electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Contact Resistance of Carbon–Li x (Ni,Mn,Co)O 2 Interfaces

Abstract Electronic resistance in lithium‐ion battery positive electrodes is typically attributed to the bulk resistance of the active material and the network resistance of the carbon additive. Expected overpotentials from these bulk components are minimal relative to that from charge‐transfer resistance. However, literature reports show that cell overpotentials are often much more sensitive to conductive additives than the expected level from bulk or percolating‐network transport. This discrepancy motivated a detailed examination of the contact resistance between the active material and conductive additive. The contact and bulk resistances are simultaneously measured using dense bar samples of lithium‐layered oxides (Li x Ni 1 /3 Mn 1/3 Co 1/3 O 2 and Li x Ni 0.5 Mn 0.3 Co 0.2 O 2 ) in contact with carbon black. It is found that the contact resistance dominates the overall electronic resistance when the length scale is smaller than millimeters; after correcting for contact effects, bulk conductivity of layered oxides is determined to be orders‐of‐magnitude higher than previously reported. In porous electrodes, it is found from three‐electrode electrochemical impedance spectroscopy that the carbon content most heavily influences the low‐frequency regime (≈0.01 Hz), as opposed to the high frequency (>10 3 Hz) regime expected from electronic percolating properties. Constriction effects within the layered oxide are identified as the dominant mechanism for contact resistance and its implication is investigated for porous electrodes.

Kuo, Jimmy Jiahong↗
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 OSTI2024

T–x diagrams for the CO 2 –H 2 O system: The importance of water content in CO 2 transportation for carbon capture and storage

Abstract When water is present in a CO 2 pipeline, corrosion or plugging can occur due to the formation of liquid water or gas hydrate, respectively. Understanding how corrosion and hydrate plugging can be avoided is important for enhanced oil recovery and carbon dioxide capture and storage processes. If the CO 2 is sufficiently dried prior to transportation, the formation of these problematic free‐water phases can be avoided. In this work, isobaric T–x diagrams were developed from the P–T diagram for the CO 2 –H 2 O binary system. Pressures ranging from just below the lower quadruple point to above the lower critical end point were studied. These diagrams are meant to give the reader a better conceptual understanding of how the water composition in CO 2 –H 2 O mixtures will influence phases that form at different temperatures and pressures. The diagrams are analyzed from the perspective of flow assurance in CO 2 transportation.

Wadsworth, Lindsey A.↗
DOE OSTI2020

From K‐O 2 to K‐Air Batteries: Realizing Superoxide Batteries on the Basis of Dry Ambient Air

Abstract Although using an air cathode is the goal for superoxide‐based potassium‐oxygen (K‐O 2 ) batteries, prior studies were limited to pure oxygen. Now, the first K‐air (dry) battery based on reversible superoxide electrochemistry is presented. Spectroscopic and gas chromatography analyses are applied to evaluate the reactivity of KO 2 in ambient air. Although KO 2 reacts with water vapor and CO 2 to form KHCO 3 , it is highly stable in dry air. With this knowledge, rechargeable K‐air (dry) batteries were successfully demonstrated by employing dry air cathode. The reduced partial pressure of oxygen plays a critical role in boosting battery lifespan. With a more stable environment for the K anode, a K‐air (dry) battery delivers over 100 cycles (>500 h) with low round‐trip overpotentials and high coulombic efficiencies as opposed to traditional K‐O 2 battery that fails early. This work sheds light on the benefits and restrictions of employing the air cathode in superoxide‐based batteries.

Qin, Lei↗
DOE OSTI2021

Structural and Spectroscopic Comparison of Soft‐Se vs. Hard‐O Donor Bonding in Trivalent Americium/Neodymium Molecules

Covalency is often considered to be an influential factor in driving An 3+ vs. Ln 3+ selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An 3+ /Ln 3+ covalency differences prevail and manifest as the f-block is traversed, and the effects of periodic breaks beyond Pu. Herein, two Am complexes, [Am{N(E=PPh 2 ) 2 } 3 ] (1-Am, E=Se; 2-Am, E=O) are compared to isoradial [Nd{N(E=PPh 2 ) 2 } 3 ] (1-Nd, 2-Nd) complexes. Covalent contributions are assessed and compared to U/La and Pu/Ce analogues. In conclusion, through ab initio calculations grounded in UV-vis-NIR spectroscopy and single-crystal X-ray structures, we observe differences in f orbital involvement between Am–Se and Nd–Se bonds, which are not present in O-donor congeners.

Goodwin, Conrad A. P.↗
DOE OSTI2022

High‐Field NMR, Reactivity, and DFT Modeling Reveal the γ‐Al 2 O 3 Surface Hydroxyl Network**

Abstract Aluminas are strategic materials used in many major industrial processes, either as catalyst supports or as catalysts in their own right. The transition alumina γ‐Al 2 O 3 is a privileged support, whose reactivity can be tuned by thermal activation. This study provides a qualitative and quantitative assessment of the hydroxyl groups present on the surface of γ‐Al 2 O 3 at three different dehydroxylation temperatures. The principal [AlOH] configurations are identified and described in unprecedented detail at the molecular level. The structures were established by combining information from high‐field 1 H and 27 Al solid‐state NMR, IR spectroscopy and DFT calculations, as well as selective reactivity studies. Finally, the relationship between the hydroxyl structures and the molecular‐level structures of the active sites in catalytic alkane metathesis is discussed.

Merle, Nicolas↗
DOE OSTI2024

Influence of Ti‐incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H 2 O 2

Abstract Vapor‐phase propylene (C 3 H 6 ) epoxidation kinetics with hydrogen peroxide (H 2 O 2 ) strongly reflects the physical properties of Ti‐incorporated zeolite catalysts and the presence of spectating molecules (“solvent”) near active sites even without a bulk liquid phase. Steady‐state turnover rates of C 3 H 6 epoxidation and product selectivities vary by orders of magnitudes, depending on the zeolite silanol ((SiOH) x ) density, pore topology (MFI, *BEA, FAU), and the quantity of condensed acetonitrile (CH 3 CN) molecules nearby active sites, under identical reaction mechanisms sharing activated H 2 O 2 intermediates on Ti surfaces. Individual kinetic analyses for propylene oxide (PO) ring‐opening, homogeneous diol oxidative cleavage, and homogeneous aldehyde oxidation reveal that secondary reaction kinetics following C 3 H 6 epoxidation responds more sensitively to the changes in zeolite physical properties and pore condensation with CH 3 CN. Thus, higher PO selectivities achieved in hydrophilic Ti‐MFI at steady‐state reflect the preferential stabilization of transition states for C 3 H 6 epoxidation (a primary reaction) relative to PO ring‐opening and oxidative cleavage (secondary reactions) that solvation effects that reflect interactions among condensed CH 3 CN within pores and the extended pore structure.

Kwon, Ohsung↗
DOE OSTI2020

Caught in the H inact : Crystal Structure and Spectroscopy Reveal a Sulfur Bound to the Active Site of an O 2 -stable State of [FeFe] Hydrogenase

[FeFe] hydrogenases are the most active H 2 converting catalysts in nature, but their extreme oxygen sensitivity limits their use in technological applications. The [FeFe] hydrogenases from sulfate reducing bacteria can be purified in an O 2 -stable state called H inact . To date, the structure and mechanism of formation of H inact remain unknown. Our 1.65 Å crystal structure of this state reveals a sulfur ligand bound to the open coordination site. Furthermore, in-depth spectroscopic characterization by X-ray absorption spectroscopy (XAS), nuclear resonance vibrational spectroscopy (NRVS), resonance Raman (RR) spectroscopy and infrared (IR) spectroscopy, together with hybrid quantum mechanical and molecular mechanical (QM/MM) calculations, provide detailed chemical insight into the Hinact state and its mechanism of formation. This may facilitate the design of O 2 -stable hydrogenases and molecular catalysts.

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

Structural and Spectroscopic Comparison of Soft-Se vs. Hard-O Donor Bonding in Trivalent Americium/Neodymium Molecules

Covalency is often considered to be an influential factor in driving An 3+ vs. Ln 3+ selectivity invoked by soft donor ligands. This is intensely debated, particularly the extent to which An 3+ /Ln 3+ covalency differences prevail and manifest as the f-block is traversed, and the effects of periodic breaks beyond Pu. In this work, two Am complexes, [Am{N(E=PPh 2 ) 2 } 3 ] ( 1-Am , E=Se; 2-Am , E=O) are compared to isoradial [Nd{N(E=PPh 2 ) 2 } 3 ] ( 1-Nd , 2-Nd ) complexes. Covalent contributions are assessed and compared to U/La and Pu/Ce analogues. Through ab initio calculations grounded in UV-vis-NIR spectroscopy and single-crystal X-ray structures, we observe differences in f orbital involvement between Am–Se and Nd–Se bonds, which are not present in O-donor congeners.

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

High‐Field NMR, Reactivity, and DFT Modeling Reveal the γ‐Al 2 O 3 Surface Hydroxyl Network**

Abstract Aluminas are strategic materials used in many major industrial processes, either as catalyst supports or as catalysts in their own right. The transition alumina γ‐Al 2 O 3 is a privileged support, whose reactivity can be tuned by thermal activation. This study provides a qualitative and quantitative assessment of the hydroxyl groups present on the surface of γ‐Al 2 O 3 at three different dehydroxylation temperatures. The principal [AlOH] configurations are identified and described in unprecedented detail at the molecular level. The structures were established by combining information from high‐field 1 H and 27 Al solid‐state NMR, IR spectroscopy and DFT calculations, as well as selective reactivity studies. Finally, the relationship between the hydroxyl structures and the molecular‐level structures of the active sites in catalytic alkane metathesis is discussed.

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

Influence of Ti‐incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H 2 O 2

Vapor-phase propylene (C 3 H 6 ) epoxidation kinetics with hydrogen peroxide (H 2 O 2 ) strongly reflects the physical properties of Ti-incorporated zeolite catalysts and the presence of spectating molecules (“solvent”) near active sites even without a bulk liquid phase. Steady-state turnover rates of C 3 H 6 epoxidation and product selectivities vary by orders of magnitudes, depending on the zeolite silanol ((SiOH) x ) density, pore topology (MFI, *BEA, FAU), and the quantity of condensed acetonitrile (CH 3 CN) molecules nearby active sites, under identical reaction mechanisms sharing activated H 2 O 2 intermediates on Ti surfaces. Individual kinetic analyses for propylene oxide (PO) ring-opening, homogeneous diol oxidative cleavage, and homogeneous aldehyde oxidation reveal that secondary reaction kinetics following C 3 H 6 epoxidation responds more sensitively to the changes in zeolite physical properties and pore condensation with CH 3 CN. Thus, higher PO selectivities achieved in hydrophilic Ti-MFI at steady-state reflect the preferential stabilization of transition states for C 3 H 6 epoxidation (a primary reaction) relative to PO ring-opening and oxidative cleavage (secondary reactions) that solvation effects that reflect interactions among condensed CH 3 CN within pores and the extended pore structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Large Enhancements in Optical and Piezoelectric Properties in Ferroelectric Zn 1- x Mg x O Thin Films through Engineering Electronic and Ionic Anharmonicities

Multifunctionality as a paradigm requires materials exhibiting multiple superior properties. Integrating second-order optical nonlinearity and large bandgap with piezoelectricity can, for example, enable broadband, strain-tunable photonics. Though very different phenomena at distinct frequencies, both second-order optical nonlinearity and piezoelectricity are third-rank polar tensors present only in acentric crystal structures. However, simultaneously enhancing both phenomena is highly challenging since it involves competing effects with tradeoffs. Recently, a large switchable ferroelectric polarization of ≈80 μC cm –2 was reported in Zn 1-x Mg x O films. Here, ferroelectric Zn 1-x Mg x O is demonstrated to be a platform that hosts simultaneously a 30% increase in the electronic bandgap, a 50% enhancement in the second harmonic generation (SHG) coefficients, and a near 200% improvement in the piezoelectric coefficients over pure ZnO. These enhancements are shown to be due to a 400% increase in the electronic anharmonicity and a ≈200% decrease in the ionic anharmonicity with Mg substitution. Precisely controllable periodic ferroelectric domain gratings are demonstrated down to 800 nm domain width, enabling ultraviolet quasi-phase-matched optical harmonic generation as well as domain-engineered piezoelectric devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Understanding the Benefit of Hybrid Electrolytes towards Vanadium Dissolution Suppression and Improved Capacity Retention in Zinc‐Aqueous Batteries Using NaV 3 O 8 Cathodes

Vanadate cathodes used in aqueous Zn-ion batteries with ZnSO 4 are hindered by capacity loss from V dissolution into the electrolyte. However, studies pinpointing the onset of dissolution as a function of electrochemical redox state and quantifying the amount of associated active material are lacking. To prevent dissolution of the NaV 3 O 8 active material, Na + ions are introduced into the electrolyte. Specifically, a hybrid ZnSO 4 + Na 2 SO 4 electrolyte is investigated in concert with NaV 3 O 8 (NVO) cathodes of varied crystallinity to determine the resulting impacts on cathode dissolution and functional electrochemistry. The use of Na + -containing hybrid electrolyte shows no significant change in Zn 2+ diffusion coefficients yet improved capacity retention. Time-resolved quantitative optical emission spectroscopy demonstrates the suppression of V dissolution with the hybrid electrolyte in both pristine and cycled electrodes. Operando synchrotron X-ray diffraction and absorption provide mechanistic insights. Hydrated NVO with wider interplanar spacing exhibits much higher H + /Zn 2+ capacity, while the Na 2 SO 4 mitigates the formation of irreversible side products. Furthermore, this study demonstrates that the use of hybrid electrolytes and control of crystallite size in the parent material can significantly improve electrochemical behavior of layered V-based cathodes in Zn-ion batteries, providing a general strategy toward safe and resilient aqueous battery systems.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Global Optimization of Adsorbate Covered Supported Cluster Catalysts: The Case of Pt 7 H 10 CH 3 on α-Al 2 O 3

Determining structures of supported sub-nanometer catalytic clusters is important for finding binding sites, active sites, and reaction mechanisms. In realistic conditions, the cluster may be covered with adsorbed reactants and intermediates, which strongly affect the structure of the cluster compared to the low coverage regime. The global optimization of supported adsorbate-covered clusters is not possible with existing methods. In this paper, we present a customized Basin Hopping (BH) approach, with a core (metal cluster) – shell (adsorbates) separation scheme, and perform first applications to the search of low-energy isomers of Pt 7 /α-Al 2 O 3 at high hydrogen coverage (10H). The presence of adsorbates significantly alters the low-energy isomers compared to bare Pt 7 /α-Al 2 O 3 . Molecular dynamics simulations additionally show the different time-scales associated with the mobility of H and Pt atoms. The revised BH method with core-shell separation presents key advantages for the structural exploration of adsorbate-covered supported catalysts, relevant to realistic catalytic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Revealing the Chemical State of Palladium in Operating In 2 O 3 Gas Sensors: Metallic Pd Enhances Sensing Response and Intermetallic In x Pd y Compound Blocks It

The sensing response of metal oxides activated with noble metal nanoparticles is significantly influenced by changes to the chemical state of corresponding elements under operating conditions. Here, a PdO/rh-In 2 O3 consisting of PdO nanoparticles loaded onto rhombohedral In 2 O 3 was studied as a gas sensor for H 2 gas (100–40000 ppm in an oxygen-free atmosphere) in the temperature range of 25–450 °C. The phase composition and chemical state of elements were examined by resistance measurements combined with synchrotron-based in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy. As found, PdO/rh-In 2 O 3 undergoes a series of structural and chemical transformations during operation: from PdO to Pd/PdH x and finally to the intermetallic In x Pd y phase. The maximal sensing response (R N2 /R H2 ) of ~5 · 10 7 towards 40000 ppm (4 vol %) H 2 at 70 °C is correlated with the formation of PdH 0.706 /Pd. The In x Pd y intermetallic compounds formed around 250 °C significantly decrease the sensing response.

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

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li 7‐3 x Ga x La 3 Zr 2 O 12 Garnet‐Type Electrolytes

Abstract One of the most promising electrolytes for all‐solid‐state lithium batteries is Li 7 La 3 Zr 2 O 12 . Previously, their thermodynamic stability, Li‐ion conductivity, and structural features induced by Ga‐doping have not been empirically determined or correlated. Here, their interplay was examined for Li 7−3 x Ga x La 3 Zr 2 O 12 with target x Ga=0, 0.25, 0.50, 0.75, and 1.00 atoms per formula unit (apfu). Formation enthalpies, obtained with calorimetry and found to be exothermic at all compositions, linearly decreased in stability with increased x Ga. At dilute x Ga substitution, the formation enthalpy curve shifted stepwise endothermically, and the conductivity increased to a maximum, coinciding with 0.529 Ga apfu. This correlated with percolation threshold analysis (0.558 Ga apfu). Further substitution (0.787 Ga apfu) produced a large decrease in the stability and conductivity due to a large increase in point defects and blocked Li‐migration pathways. At x Ga=1.140 apfu, a small exothermic shift was related to defect cluster organization extending the Li hopping distance and decreased Li‐ion conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗