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At least 379 records · Page 21

All sources NASA NTRS DOE OSTI

DOE OSTI2021

The role of defects and solid/liquid interfacial interactions on controlling anisotropic growth of novel two-dimensional materials

Atomic-scale understanding about how interfacial properties are modified in the presence of defects and how they are correlated to the properties of nucleation and growth is critical for controlled materials growth on solid/liquid interfaces. The goal of this proposal is to establish preliminary data on the critical role of surface defects and chemical compositions of solvent on the structure, dynamics, reactivity, and free energetics at graphene/ionic liquid (IL) interfaces and their impact on two-dimensional (2D) growth of transition metal oxides on the surface. This study aims to develop generalized physical/chemical principles for directional growth at solid/liquid interfaces to achieve atomic-level control of two-dimensional materials synthesis. The proposed study of the effects of surface defects on the interfacial structure and reactivity will improve our understanding of the critical roles of heterogeneity, disorder, and solvents on 2D materials synthesis and lead to better control of directional growth of materials at solid/liquid interfaces.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Understanding High-Voltage Behavior of Sodium-Ion Battery Cathode Materials Using Synchrotron X-ray and Neutron Techniques: A Review

Despite substantial research efforts in developing high-voltage sodium-ion batteries (SIBs) as high-energy-density alternatives to complement lithium-ion-based energy storage technologies, the lifetime of high-voltage SIBs is still associated with many fundamental scientific questions. In particular, the structure phase transition, oxygen loss, and cathode–electrolyte interphase (CEI) decay are intensely discussed in the field. Synchrotron X-ray and neutron scattering characterization techniques offer unique capabilities for investigating the complex structure and dynamics of high-voltage cathode behavior. In this review, to accelerate the development of stable high-voltage SIBs, we provide a comprehensive and thorough overview of the use of synchrotron X-ray and neutron scattering in studying SIB cathode materials with an emphasis on high-voltage layered transition metal oxide cathodes. We then discuss these characterizations in relation to polyanion-type cathodes, Prussian blue analogues, and organic cathode materials. Finally, future directions of these techniques in high-voltage SIB research are proposed, including CEI studies for polyanion-type cathodes and the extension of neutron scattering techniques, as well as the integration of morphology and phase characterizations.

25 ENERGY STORAGE↗

DOE OSTI2020

Exploring the Charge Compensation Mechanism of P2-Type Na 0.6 Mg 0.3 Mn 0.7 O 2 Cathode Materials for Advanced Sodium-Ion Batteries

P2-type sodium layered transition metal oxides have been intensively investigated as promising cathode materials for sodium-ion batteries (SIBs) by virtue of their high specific capacity and high operating voltage. However, they suffer from problems of voltage decay, capacity fading, and structural deterioration, which hinder their practical application. Therefore, a mechanistic understanding of the cationic/anionic redox activity and capacity fading is indispensable for the further improvement of electrochemical performance. Here, a prototype cathode material of P2-type Na 0.6 Mg 0.3 Mn 0.7 O 2 is comprehensively investigated, which presents both cationic and anionic redox behaviors during the cycling process. By a combination of soft X-ray absorption spectroscopy and electroanalytical methods, we unambiguously reveal that only oxygen redox reaction is involved in the initial charge process, then both oxygen and manganese participate in the charge compensation in the following discharge process. In addition, a gradient distribution of Mn valence state from surface to bulk is disclosed, which could be mainly related to the irreversible oxygen activity during the charge process. Furthermore, we find that the average oxidation state of Mn is reduced upon extended cycles, leading to the noticeable capacity fading. Our results provide deeper insights into the intrinsic cationic/anionic redox mechanism of P2-type materials, which is vital for the rational design and optimization of advanced cathode materials for SIBs.

25 ENERGY STORAGE↗

DOE OSTI2025

Electrical Behavior of Combinatorial Thin-Film Zr x Ta 1−x O y

Combinatorial magnetron sputtering and electrical characterization were used to systematically study the impact of compositional changes in the resistive switching of transition metal oxides, specifically the Zr x Ta 1−x O y system. Current-voltage behavior across a range of temperatures provided insights into the mechanisms that contribute to differences in the electrical conductivity of the pristine Ta 2 O 5 and ZrO 2 , and mixed Zr x Ta 1−x O y devices. The underlying conductive mechanism was found to be a mixture of charge trapping and ionic motion, where charge trapping/emission dictated the short-term cycling behavior while ion motion contributed to changes in the conduction with increased cycling number. ToF-SIMS was used to identify the origin of the “wake-up” behavior of the devices, revealing an ionic motion contribution. This understanding of how cation concentration affects conduction in mixed valence systems helps provide a foundation for a new approach toward manipulating resistive switching in these active layer materials.

36 MATERIALS SCIENCE↗

NASA NTRS1978

Catalysts for electrochemical generation of oxygen

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

Hagans, P.↗

NASA NTRS1994

Overcharge and overdischarge protection of ambient temperature secondary lithium cells

A cathode additive is provided for protecting an ambient temperature secondary lithium cell from overcharging or overdischarging. The cathode additive is chosen to create an upper voltage plateau which is slightly higher than a characteristic charge cutoff voltage of the cathode of the cell. The cathode additive additionally creates a lower voltage plateau which is slightly lower than the characteristic discharge cutoff voltage of the cell. Preferably, the cathode additive is a transition metal oxide or a sulfide and may, for example, include a mixture of Li2Mn2O4 and Li(0.1)MoO2.

Huang, Chen-Kuo↗

NASA NTRS2005

Performance and Safety Evaluations of Moli Spinel Lithium-Ion Cells

The current spike obtained during the hard external short test is small (8.2 A) compared to those obtained from a LiCoO2 system (60 to 80 A). The simulated internal short did not result in an explosion or fire as it does with the LiCoO2 systems. The temperatures obtained during the heat-to-vent test are not very high compared to the cobaltate cells. The cells do not retain capacity very well, but the capacity can be recovered with cycling. The spinel cells are much safer under abuse conditions than the lithium-ion cells with other transition metal oxides.

Jevarajan, Judith↗

DOE OSTI2021

Catalytic conversion of ethanol to 1-/2-butenes

Simple and economical conversion of aqueous ethanol feed streams into butenes by a single step method using transition metal oxides on a silica supports under preselected processing conditions. By directly producing a C4-rich olefin mixture from an ethanol containing stream various advantages are presented including, but not limited to, significant cost reduction in capital expenses and operational expenses.

Dagle, Vanessa M.↗

DOE OSTI2021

Metal fluoride passivation coatings prepared by atomic layer deposition for Li-ion batteries

The fabrication of robust interfaces between transition metal oxides and non-aqueous electrolytes is one of the great challenges of lithium ion batteries. Atomic layer deposition (ALD) of aluminum tungsten fluoride (AlWxFy) improves the electrochemical stability of LiCoO2. AlWxFy thin films were deposited by combining trimethylaluminum and tungsten hexafluoride. in-situ quartz crystal microbalance and transmission electron microscopy studies show that the films grow in a layer-by-layer fashion and are amorphous nature. Ultrathin AlWxFy coatings (<10 Å) on LiCoO2 significantly enhance stability relative to bare LiCoO2 when cycled to 4.4 V. The coated LiCoO2 exhibited superior rate capability (up to 400 mA/g) and discharge capacities at a current of 400 mA/g were 51% and 92% of the first cycle capacities for the bare and AlWxFy coated materials. These results open new possibilities for designing ultrathin and electrochemically robust coatings of metal fluorides via ALD to enhance the stability of Li-ion electrodes.

Mane, Anil U.↗

DOE OSTI2021

Process for fabrication of enhanced β″-alumina solid electrolytes for energy storage devices and energy applications

A dense β″-alumina/zirconia composite solid electrolyte and process for fabrication are disclosed. The process allows fabrication at temperatures at or below 1600° C. The solid electrolytes include a dense composite matrix of β″-alumina and zirconia, and one or more transition metal oxides that aid the conversion and densification of precursor salts during sintering. The composite solid electrolytes find application in sodium energy storage devices and power-grid systems and devices for energy applications.

Lu, Xiaochuan↗

DOE OSTI2021

Regenerable battery electrode

A binder-free, self-supporting electrode including an electrochemically active material in the absence of a binder and a current collector is claimed. The electrochemically active material is a self-supporting transition metal oxide. A method of regenerating the electrode to restore capacity of the electrode is also claimed.

Takeuchi, Esther Sans↗

DOE OSTI2024

PRODUCTION OF GLASS-TO-METAL SEALS USING ADDITIVE MANUFACTURING TECHNIQUES

Glass-to-metal (GtM) seals are hermetic barriers between glass and metal components, often used in the electronic and vacuum industries. Creating the seals traditionally requires heating all the components to the glass melting temperature, where the glass will flow and bond to the metal. Due to the manufacturing constraints of the individual components and sealing conditions there are geometric and material restrictions. Additive manufacturing techniques were used to make GtM seals to reduce these restrictions. Hermetic, single pin seals were produced using printed metal shells, by selective laser melting (SLM), and digital light processing (DLP) printed glass preforms. Glass preforms were printed with photosensitive resin mixed with a silicate sealing glass powder in a 1:2 weight ratio. Thermal analysis, TGA/DSC, and screening experiments were used to determine an organic removal schedule. Video techniques determined a sintering schedule by producing a densification curve at different isothermal holds which were fit with a viscous sintering model. Single pin seals were also produced use a laser assisted manufacturing (LAM) process as an alternative to the conventional furnace sealing process. A Nd:YAG laser was focused on a solid glass preform, heating the glass to form the glass-metal bond. The sealing glass was doped with a transition metal oxide, Fe2O3 or CuO, to increase absorption of the laser wavelength. The interface of hermetic LAM seals were analyzed using electron microscopy, compared to conventional prepared seals, finding a reduction of interfacial morphologies.

Read, Aaron Reece↗

DOE OSTI2024

Metal fluoride passivation coatings prepared by atomic layer deposition for Li-ion batteries

The fabrication of robust interfaces between transition metal oxides and non-aqueous electrolytes is one of the great challenges of lithium ion batteries. Atomic layer deposition (ALD) of aluminum tungsten fluoride (AlWxFy) improves the electrochemical stability of LiCoO 2 . AlWxFy thin films were deposited by combining trimethylaluminum and tungsten hexafluoride. in-situ quartz crystal microbalance and transmission electron microscopy studies show that the films grow in a layer-by-layer fashion and are amorphous nature. Ultrathin AlWxFy coatings (<10 Å) on LiCoO 2 significantly enhance stability relative to bare LiCoO 2 when cycled to 4.4 V. The coated LiCoO 2 exhibited superior rate capability (up to 400 mA/g) and discharge capacities at a current of 400 mA/g were 51% and 92% of the first cycle capacities for the bare and AlWxFy coated materials. These results open new possibilities for designing ultrathin and electrochemically robust coatings of metal fluorides via ALD to enhance the stability of Li-ion electrodes.

Mane, Anil U.↗

DOE OSTI2024

Electrical connectors including glass seals and methods of fabrication

An electrical connector comprises an outer shell, at least one pin, and an insulating seal. The outer shell includes at least one side wall defining a cavity and having an inner surface. The outer shell is formed from electrically conductive material. The pin is positioned within the cavity and is also formed from electrically conductive material. The insulating seal is configured to provide electrical isolation of the pin and fills the cavity between the inner surface of the side wall and the pin. The insulating seal is formed from glass doped with a transition metal oxide.

Eichorst, Dennis J.↗

DOE OSTI2024

Graphene-transition metal catalyst for hydrogen evolution reaction

Functionalized catalysts for use in a hydrogen evolution reaction (HER) contain nanoparticles containing a transition metal enveloped in layers of graphene, which renders the nanoparticles resistant to passivation while maintaining an optimal ratio of transition metal and transition metal oxide in the nanoparticles. The catalysts can be utilized with anionic exchange polymer membranes for hydrogen production by alkaline water electrolysis.

Mukerjee, Sanjeev↗

DOE OSTI2020

Roles of Carburization and Oxidation on Transition-Metal Catalyzed Surface Reactions

Many industrial chemical transformation processes are based on reactions catalyzed by transition metals. In some cases the nano-size particles used as catalysts are synthesized simultaneously or right before the initiation of the main catalytic reaction. Synthesis treatments involve complex processes such as reductions followed by calcinations in oxygenated environments coupled to the presence of gases used for the main reaction. Synthesis details are crucial because they have important consequences on the catalyst shape, size, and chemical composition, and may also affect the structure and composition of the catalyst support. All these effects may alter the main catalyzed reaction in unexpected ways. This work focuses on the synthesis of the overall catalytic system that includes catalyst and support taking place in parallel with the initial stages of the main catalyzed reaction. Two important processes are characterized: carburization and oxidation of the transition metal catalyst during synthesis or initial stages of the main reaction. The objective is to understand how the coking mechanism coupled to surface oxidation and changes in the substrate influence the dry reforming of methane taken as a model reaction. The approach uses first principles computational methods to investigate the catalyst synthesis and characterization and catalytic reaction mechanisms. These studies are complemented with experimental characterization done by the group of Dr. Renu Sharma at the National Institute of Standards and Technology (unfunded collaborator) using high resolution transmission electron microscopy. Specific goals are to identify the role of the synthesis process on the initial nanocatalyst structure and composition, and to determine how that structure and composition may evolve after being exposed to the reactants atmosphere. These studies facilitate a systematic analysis of conditions where the nanoparticle composition can be optimized regarding activity and stability. Moreover, the fundamental study of catalyst/support interactions yields valuable insights for other catalytic processes and is a first step toward controlled nanocatalyst synthesis.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi 0.5 Mn 1.5 O 4

In our initial study on the high-voltage 5 V cobalt-free spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a large cell format was used. This delamination problem prompted us to investigate further by studying the transition metal (TM) dissolution mechanism of cobalt-free LNMO cathodes, and as a comparison, some cobalt-containing lithium nickel manganese cobalt oxides (NMC) cathodes, as the leachates from the soaking experiment might be the culprit for the delamination. Unlike other previous reports, we are interested in the intrinsic stability of the cathode in the presence of a baseline Gen2 electrolyte consisting of 1.2 M of LiPF 6 in ethylene carbonate/ethyl methyl carbonate (EC/EMC), similar to a storage condition. The electrode laminates (transition metal oxides, transition metal oxides, TMOs, coated on an Al current collector with a loading level of around 2.5 mAh/cm 2 ) or the TMO powders (pure commercial quality spinel LNMO, NMC, etc.) were stored in the baseline solution, and the transition metal dissolution was studied through nuclear magnetic resonance, such as 1 H NMR, 19 F NMR, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). Significant electrolyte decomposition was observed and could be the cause that leads to the TM dissolution of LNMO. To address this TM dissolution, additives were introduced into the baseline electrolyte, effectively alleviating the issue of TM dissolution. The results suggest that the observed delamination is caused by electrolyte decompositions that lead to etching, and additives such as lithium difluorooxalato borate and p-toluenesulfonyl isocyanate can alleviate this issue by forming a firm cathode electrolyte interface. This study provides a new perspective on cell degradation induced by electrode/electrolyte interactions under storage conditions.

25 ENERGY STORAGE↗

DOE OSTI2021

Determine Oxidation State of Transition Metals in Molten Salt Corrosion using Electron Energy Loss Spectroscopy

This work utilizes electron energy loss spectroscopy (EELS) to identify oxidation state of alloying elements in Ni-based alloys after exposure to molten chloride salt systems. Pure Ni and Ni 20Cr model alloy were corroded in molten ZnCl2 and KCl-MgCl2 under argon atmosphere at various temperatures. Oxidation states of Cr (Cr3+) and Ni (Ni2+) in the molten salt after corrosion were determined by monitoring changes in the L2,3 edges of corresponding EELS spectra. Oxidation state mapping technique using principal component analysis and multiple linear least squares fitting in HyperSpy Python package was developed.

36 MATERIALS SCIENCE↗