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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 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Revealing the Conversion Mechanism of Transition Metal Oxide Electrodes during Lithiation from First-Principles

Transition metal oxides such as Co3O4 and NiO are of significant interest as conversion anode materials for lithium-ion batteries (LIBs), due to their remarkably high theoretical capacities and low cost. While many previous experiments have found that the charge/discharge reactions of Co3O4 and NiO can be highly reversible, detailed information about the mechanisms of these reactions, such as the origin of the voltage hysteresis (>1.0 V) between the charge/discharge cycles, is still poorly understood. In this work, we develop and utilize a new computational mechanistic approach that helps elucidate the hysteresis and nonequilibrium reaction pathways associated with these conversion materials. We apply this methodology to investigate a variety of lithiation reaction pathways of Co3O4 and NiO by systematically exploring the energetics of a large number of equilibrium and nonequilibrium LixCo3O4 (0 ≤ x ≤ 8) and LixNiO (0 ≤ x ≤ 2) structural configurations using first-principles calculations. The overall value of the voltages from our nonequilibrium pathway is in much better agreement with experimental lithiation than the calculated equilibrium voltage while the overall value of the latter reasonably agrees with experimental delithiation. Hence, we propose the charge and discharge processes proceed through equilibrium and nonequilibrium reaction paths, respectively, which contribute significantly to the experimentally observed voltage hysteresis in Co3O4 and NiO. Additionally, we find a low-energy, lithiated intermediate phase (Li3Co3O4) with an oxygen framework equal to that of the initial Co3O4 spinel phase. This intermediate phase represents the capacity threshold below which limited volume expansion and better reversibility can be realized and above which reactions lead to structural degradation and huge expansion.

Yao, Zhenpeng↗
DOE OSTI2017

Aqueous Synthesis of Technetium-Doped Titanium Dioxide by Direct Oxidation of Titanium Powder, a Precursor for Ceramic Nuclear Waste Forms

Technetium-99 (Tc) is a problematic fission product that complicates the long-term disposal of nuclear waste due to its long half-life, high fission yield, and the environmental mobility of pertechnetate, its stable form in aerobic environments. One approach to preventing Tc contamination is through incorporation into durable waste forms based on weathering-resistant minerals such as rutile (titanium dioxide). Here, the incorporation of technetium into titanium dioxide by means of simple, aqueous chemistry - direct oxidation of titanium powder in the presence of ammonium fluoride - is achieved. X-ray absorption fine structure spectroscopy and diffuse reflectance spectroscopy indicate that Tc(IV) replaces Ti(IV) within the structure. Rather than being incorporated as isolated Tc(IV) ions, Tc is present as pairs of edge-sharing Tc(IV) octahedra similar to molecular Tc(IV) complexes such as [(H 2 EDTA)TcIV](μ-O) 2 . Technetium-doped TiO 2 was suspended in deionized water under aerobic conditions, and the Tc leached under these conditions was followed for 8 months. The normalized release rate of Tc (LR Tc ) from the TiO 2 particles is low (3 × 10 -6 g m -2 d -1 ), which illustrates the potential utility of TiO 2 as waste form. However, the small size of the as-prepared TiO 2 nanoparticles results in an estimated retention of Tc of 10 4 years, which is only a fraction of the half-life of Tc (2.1 × 10 5 years).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

A Mg-Doped High-Nickel Layered Oxide Cathode Enabling Safer, High-Energy-Density Li-Ion Batteries

High-nickel layered oxide cathodes with a Ni content of > 90% show substantial potential for next-generation lithium-ion batteries (LIBs) due to their high capacity and lower cost. However, they are plagued by rapid capacity decay and poor thermal stability, which hamper their practical viability. Here we present Li 0.98 Mg 0.02 Ni 0.94 Co 0.06 O 2 (NC-Mg) with 2% Mg doping, aiming to provide a strategic guideline for solving the issues. The Mg 2+ ions occupy the lithium layer and are pro-posed to act as pillar ions, which substantially enhances the structural reversibility and reduces the anisotropic lattice distortion upon cycling, thereby greatly improving the electrochemical and thermal stability of NC-Mg compared to the undoped LiNi 0.94 Co 0.06 O 2 (NC). Specifically, NC-Mg delivers 214 mA h g -1 with a capacity retention of 80.1% after 500 cycles in pouch-type full cells, much higher than the retention of NC (56.3%). A discharge capacity of 158 mA h g -1 at 10C rate demonstrates its remarkable rate capability. Additionally, the Mg doping significantly elevates the exothermic peak tem-perature of NC-Mg to 211 °C, in sharp contrast to 177 °C for NC, highlighting the improved thermal stability of NC-Mg. Collectively, the superior performance of NC-Mg demonstrates a feasible alternative strategy for developing safer, high-energy-density LIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Enhanced Oxide Reduction by Hydrogen at Cuprous Oxide–Copper Interfaces near Ascending Step Edges

We report that understanding the dynamic processes involved in the interaction of hydrogen with oxides is of fundamental importance in catalysis. This paper probes the reduction of Cu 2 O-‘29’ surfaces by hydrogen at room temperature combining in situ ambient pressure scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. Reduction of the atomic layer thin Cu 2 O film is observed to be preferentially initiated2 at step edges and terrace defects, where perfect Cu 2 O(111) terraces are found to be stable towards hydrogenation under the same conditions. After a long induction period, regions of partially reduced Cu 2 O-‘29’ and metallic Cu co-exist before the surface is fully reduced to Cu(111). The reduction rate strongly depends on the nature of nearby Cu step edges. We propose a mechanism for the reduction of Cu 2 O-‘29’ by hydrogen where free copper atoms from ascending metallic step edges facilitate the formation of active ensembles for H 2 dissociation and transfer H to the edges of Cu2O regions

08 HYDROGEN↗
DOE OSTI2018

Wide Band Gap CuGa(S,Se) 2 Thin Films on Transparent Conductive Fluorinated Tin Oxide Substrates as Photocathode Candidates for Tandem Water Splitting Devices

Theaim of this report was to explore the potential of CuGa(S,Se)2 thin films as wide-E G top cell absorbers for photoelectrochemical (PEC) water splitting. A synthesis was developed on fluorinated tin oxide (FTO) photocathodes by converting copper-rich co-evaporated CuGaSe2 into CuGa(S,Se)2 via a post-deposition annealing. We found it necessary to first anneal CuGaSe2 at low-temperature in sulfur then at high-temperature in nitrogen to preserve the transparency and conductivity of the FTO. Using this two-step synthesis, we fabricated a 1.72eV CuGa(S,Se) 2 photocathode with a saturation current density and photocurrent onset potential of 10mA/cm 2 and -0.20V vs. RHE, respectively. Yet we found that the PEC performance and sub-E G transmittance, worsened with increasing copper content. Using flatband potential measurements and the Gerischer model, we show that divergences in PEC performance of CuGa(S,Se) 2 photocathodes can be explained by differences in conduction band minimums and Fermi levels. We also explain that sub-E G transmittance is likely hampered by a defect band 100-400 meV below E C . Additional external quantum efficiency measurements of a high-efficiency 1.1 eV Cu(In,Ga)Se 2 photovoltaic driver, while shaded by the CuGa(S,Se) 2 photocathode, yielded a short-circuit current density of 4.14 mA/cm 2 revealing that CuGa(S,Se) 2 reflects promise as a top cell for PEC water splitting.

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

Spin-Selective Oxygen Evolution Reaction in Chiral Iron Oxide Nanoparticles: Synergistic Impact of Inherent Magnetic Moment and Chirality

Electron spin polarization is identified as a promising avenue for enhancing the oxygen evolution reaction (OER), which is the bottleneck that limits the energy efficiency of water-splitting. Here, in this work, we report that both ferrimagnetic (f-Fe 3 O 4 ) and superparamagnetic iron oxide (s-Fe 3 O 4 ) catalysts can exhibit external magnetic field (Hext)-induced OER enhancement, and the activity is proportional to their intrinsic magnetic moment. Additionally, the chirality-induced spin selectivity (CISS) effect was utilized in synergy with Hext to get a maximum enhancement of up to 89% improvement in current density (at 1.8 V vs RHE) with a low onset potential of 270 mV in s-Fe 3 O 4 catalysts. Spin polarization and the resultant spin selectivity suppress the production of H 2 O 2 and promote the formation of ground state triplet O 2 during the OER. Furthermore, the design of chiral s-Fe 3 O 4 with synergistic spin potential effect demonstrates a high spin polarization of ∼42%, as measured using conductive atomic force microscopy (c-AFM).

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

Synthesis of [60]- and [70]Fullerene-Fused Tetrahydroquinoxaline Derivatives by Oxidative [4 + 2] Cycloaddition with Unusual Reactivity and Regioselectivity

The oxidative [4 + 2] reaction of o-phenylenediamine-derived disulfonamides with fullerene C 60 and C 70 is reported, in which electron-deficient reactants showed high reactivity. The reaction of C 70 exhibited unusual regioselectivity, yielding a [5,6]-adduct as the major product, which was characterized by 1 H, 13 C NMR and single-crystal X-ray diffraction. Here, DFT calculations revealed the reaction is an inverse-electron-demand Diels–Alder (IEDDA) reaction, and the [5,6]-adduct of C 70 is a kinetic product.

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

Glassy Carbon Substrate Oxidation Effects on Electrode Stability for Oxygen Evolution Reaction Catalysis Stability Benchmarking

Employing benchmarking metrics to capture the activity and stability of electrocatalysts for the oxygen evolution reaction (OER) in acid is a critical practice that enables meaningful comparison of catalyst material candidates reported throughout the literature. In this work, we find that ubiquitously used glassy carbon electrode substrates oxidize under typical OER operating conditions, forming a pacified, electrically insulating, and oxygen-rich surface layer that causes drastic loss of current density over the course of extended chronoamperometric stability tests at an anodic potential of 1.7 VRHE. We show that the experimentally observed stability of glassy carbon-based electrodes is approximately two orders of magnitude lower than that expected solely from dissolution-based catalyst intrinsic stability of Ir-based catalysts. We additionally find that glassy carbon-based electrode stability measured by chronoamperometric holds is greatly impacted by catalyst loading, with high catalyst loadings improving the stability of the overall electrode via a protective effect on the glassy carbon substrate. Altogether, our investigation highlights that glassy carbon is not electrochemically inert under OER conditions on the timescale of common stability tests, which can cause electrodes to exhibit performance losses that do not reflect the intrinsic stability of the actual catalyst material being investigated. In light of our findings, we underscore the usefulness of metrics, such as the S-number, to reflect intrinsic catalyst material stability.

25 ENERGY STORAGE↗
DOE OSTI2020

Solid Electrolytes for Li–S Batteries: Solid Solutions of Poly(ethylene oxide) with Li x PON- and Li x SiPON-Based Polymers

We report here efforts to synthesize free-standing, dry polymer electrolytes that exhibit superior ionic conductivities at ambient for Li–S batteries. Co-dissolution of poly(ethylene oxide) (PEO) (M n 900k) with Li x PON and Li x SiPON polymer systems at a ratio of approximately 3:2 followed by casting provides transparent, solid-solution films 25–50 μm thick, lowering PEO crystallinity, and providing measured impedance values of 0.1–2.8 × 10 –3 S/cm at ambient. These values are much higher than simple PEO/Li + salt systems. These solid-solution polymer electrolytes (PEs) are (1) thermally stable to 100 °C; (2) offer activation energies of 0.2–0.5 eV; (3) suppress dendrite formation; and (4) enable the use of lithium anodes at current densities as high as 3.5 mAh/cm 2 . Here, galvanostatic cycling of SPAN/PEs/Li cell (SPAN = sulfurized, carbonized polyacrylonitrile) shows discharge capacities of 1000 mAh/g sulfur at 0.25C and 800 mAh/g sulfur at 1C with high coulumbic efficiency over 100 cycles.

25 ENERGY STORAGE↗
DOE OSTI2021

Laponite-Incorporated UiO-66-NH2-Polyethylene Oxide Composite Membranes for Protection against Chemical Warfare Agent Simulants

A strategy is developed to enhance the barrier protection of polyethylene oxide (PEO)-metal–organic framework (MOF) composite films against chemical warfare agent simulants. To achieve enhanced protection, an impermeable high-aspect-ratio filler in the form of Laponite RD (LRD) clay platelets was incorporated into a composite PEO film containing MOF UiO-66-NH 2 . The inclusion of the platelets aids in mitigating permeation of inert hydrocarbons (octane) and toxic chemicals (2-chloroethyl ethyl sulfide, 2-CEES) of dimensions/chemistry similar to prominent vesicant threats while still maintaining high water vapor transport rates (WVTR). By utilizing small-angle neutron scattering, small-angle X-ray scattering, and wide-angle X-ray scattering, the LRD platelet alignment of the films was determined, and the structure of the films was correlated with performance as a barrier material. Performance of the membranes against toxic chemical threats was assessed using permeation testing of octane and 2-CEES, a common simulant for the vesicant mustard gas, and breathability of the membranes was assessed using WVTR measurements. To assess their robustness, chemical exposure (in situ diffuse reflectance infrared Fourier transform spectroscopy) and mechanical (tensile strength) measurements were also performed. It was demonstrated that the barrier performance of the film upon inclusion of the LRD platelets exceeds that of other MOF-polymer composites found in the literature and that this approach establishes a new path for improving permselective materials for chemical protection applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

General Kinetic Model for pH Dependence of Proton-Coupled Electron Transfer: Application to an Electrochemical Water Oxidation System

The pH dependence of proton-coupled electron transfer (PCET) reactions, which are critical to many chemical and biological processes, is a powerful probe for elucidating their fundamental mechanisms. Herein, a general, multichannel kinetic model is introduced to describe the pH dependence of both homogeneous and electrochemical PCET reactions. According to this model, a weak pH dependence can arise from the competition among multiple sequential and concerted PCET channels involving different forms of the redox species, such as protonated and deprotonated forms, as well as different proton donors and acceptors. The contribution of each channel is influenced by the relative populations of the reactant species, which often depend strongly on pH, leading to complex pH dependence of PCET apparent rate constants. This model is used to explain the origins of the experimentally observed weak pH dependence of the electrochemical PCET apparent rate constant for a ruthenium-based water oxidation catalyst attached to a tin-doped In2O3 (ITO) surface. The weak pH dependence is found to arise from the intrinsic differences in the rate constants of participating channels and the dependence of their relative contributions on pH. This model predicts that the apparent maximum rate constant will become pH-independent at higher pH, which is confirmed by experimental measurements. Our analysis also suggests that the dominant channels are electron transfer at lower pH and sequential PCET via electron transfer followed by fast proton transfer at higher pH. Furthermore, this work highlights the importance of considering multiple competing channels simultaneously for PCET processes.

Catalysts↗