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Liu, Yi-Sheng

Publications and source records attributed to Liu, Yi-Sheng.

16 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Time-Resolved X-ray Emission Spectroscopy and Resonant Inelastic X-ray Scattering Spectroscopy of Laser Irradiated Carbon

The existence of liquid carbon as an intermediate phase preceding the formation of novel carbon materials has been a point of contention for several decades. Experimental observation of such a liquid state requires nonthermal melting of solid carbon materials at various laser fluences and pulse properties. Reflectivity experiments performed in the mid-1980s reached opposing conclusions regarding the metallic or insulating properties of the purported liquid state. Time-resolved X-ray absorption studies showed shortening of C–C bonds and increasing diffraction densities, thought to evidence a liquid or glassy carbon state, respectively. Nevertheless, none of these experiments provided information on the electronic structure of the proposed liquid state. Herein, we report the results of time-resolved resonant inelastic X-ray scattering (RIXS) and time-resolved X-ray emission spectroscopy (XES) studies on amorphous carbon (a-C) and ultrananocrystalline diamond (UNCD) as a function of delay time between the irradiating pulse and X-ray probe. For both a-C and UNCD, we attribute decreases in RIXS or XES signals to transition blocking, relaxation, and finally, ablation. Increased signal at 20 ps following the irradiation of the UNCD is attributed to the probable formation of nanoscale structures in the ablation plume. Further, differences in the amount of signal observed between a-C and UNCD are explained by the difference in sample thickness and, specifically, incomplete melting of the UNCD film. Comparisons to spectral simulations based on MD trajectories at extreme conditions indicate that the carbon state in our experiments is crystalline. Normal mode analysis confirmed that symmetrical bending or stretching of the C–C bonds in the diamond lattice results in XES spectra with small intensity differences. Overall, we observed no evidence of melting to a liquid state, as determined by the lack of changes in the spectral properties for up to 100 ps delays following the melting pulses.

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

Coordination-Dependent Chemical Reactivity of TFSI Anions at a Mg Metal Interface

Charge transfer across the electrode–electrolyte interface is a highly complex and convoluted process involving diverse solvated species with varying structures and compositions. Despite recent advances in in situ and operando interfacial analysis, molecular specific reactivity of solvated species is inaccessible due to a lack of precise control over the interfacial constituents and/or an unclear understanding of their spectroscopic fingerprints. However, such molecular-specific understanding is critical to the rational design of energy-efficient solid–electrolyte interphase layers. We have employed ion soft landing, a versatile and highly controlled method, to prepare well-defined interfaces assembled with selected ions, either as solvated species or as bare ions, with distinguishing molecular precision. Equipped with precise control over interfacial composition, we employed in situ multimodal spectroscopic characterization to unravel the molecular specific reactivity of Mg solvated species comprising (i.e., bis(trifluoromethanesulfonyl)imide, TFSI – ) anions and solvent molecules (i.e., dimethoxyethane, DME/G1) on a Mg metal surface relevant to multivalent Mg batteries. In situ multimodal spectroscopic characterization revealed higher reactivity of the undercoordinated solvated species [Mg-TFSI-G1] + compared to the fully coordinated [Mg-TFSI-(G1) 2 ] + species or even the bare TFSI – . These results were corroborated by the computed reaction pathways and energy barriers for decomposition of the TFSI – within Mg solvated species relative to bare TFSI – . Finally, we evaluated the TFSI reactivity under electrochemical conditions using Mg(TFSI) 2 –DME-based phase-separated electrolytes representing different solvated constituents. Based on our multimodal study, we report a detailed understanding of TFSI – decomposition processes as part of coordinated solvated species at a Mg-metal anode that will aid the rational design of improved sustainable electrochemical energy technologies.

25 ENERGY STORAGE↗
DOE OSTI2021

Additive Destabilization of Porous Magnesium Borohydride Framework with Core--Shell Structure

Design of interfaces with thermodynamic and kinetic specificity is of great importance for hydrogen storage from both an applied and fundamental perspective. Here, in order to destabilize the metal hydride and protect the dehydrogenated products from oxidizing, a unique core-shell structure of porous Mg(BH4)2-based framework with a thin layer (no more than 5 nm) of MgCl2 additives on the surface, has been proposed and synthesized via a wet-chemical method. The local structure and electronic state of the present complex system are systematically investigated to understand the correlation between the distribution of additives and dehydrogenation property of Mg(BH4)2. A significant improvement is achieved for hydrogen desorption with chlorides: initial hydrogen release from MgCl2 decorated ..gamma..-phase Mg(BH4)2 particles commences at 100 °C and reaches a maximum of 9.4 wt% at 385 °C. Besides the decreased decomposition temperature, an activation barrier of about 76.4 kJ mol-1 lower than that of Mg(BH4)2 without MgCl2 is obtained. Moreover, MgCl2 decoration can also prevent the whole decomposed system (both Mg- and B- elements) from oxidizing, which is a necessary condition to reversibility.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

In situ/operando soft x-ray spectroscopy of chemical interfaces in gas and liquid environments

Many energy storage and energy conversion systems are based on the complexity of material architecture, chemistry, and interfacial interactions. To understand and thus ultimately control the energy applications calls for in situ/operando characterization tools. Over the years, in situ/operando soft x-ray spectroscopy has been developed for the studies of gas molecules, molecular liquids, catalytic, and electrochemical reactions. Soft x-ray spectroscopy offers electronic structure characterization of materials in energy conversion, energy storage, and catalysis regarding functionality, complexity of material architecture, and chemical interactions. It has been shown how to use the powerful in situ/operando soft x-ray spectroscopy characterization techniques of interfacial phenomena and how to reveal the mechanism of charge transfer and chemical transformation of solid/gas and solid/liquid interfaces of energy storage and catalytic materials in a realistic environment. It has been demonstrated how to overcome the challenge that soft x-rays cannot easily peek into the high-pressure catalytic or liquid electrochemical reactions. Finally, the unique design of in situ/operando soft x-ray spectroscopy instrumentation and fabrication principle and examples of experiments are presented.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Utilizing the unique charge extraction properties of antimony tin oxide nanoparticles for efficient and stable organic photovoltaics

Simultaneously enhancing device performance and longevity, as well as balancing the requirements on cost, scalability, and simplification of processing, is the goal of interface engineering of organic solar cells (OSCs). In our work, we strategically introduce antimony (Sb 3+ ) cations into an efficient and generic n-type SnO 2 nanoparticles (NPs) host during the scalable flame spray pyrolysis synthesis. Accordingly, a significant switch of conduction property from an n-type character to a p-type character is observed, with a corresponding shift in the work function (WF) from 4.01 ± 0.02 eV for pristine SnO 2 NPs to 5.28 ± 0.02 eV for SnO 2 NPs with 20 mol. % Sb content (ATO). Both pristine SnO 2 and ATO NPs with fine-tuned optoelectronic properties exhibit remarkable charge carrier extraction properties, excellent UV resistance and photo-stability being compatible with various state-of-the-art OSCs systems. The reliable and scalable pristine SnO 2 and ATO NPs processed by doctor-blading in air demand no complex post-treatment. Our work offers a simple but unique approach to accelerate the development of advanced interfacial materials, which could circumvent the major existing interfacial problems in solution-processed OSCs.

14 SOLAR ENERGY↗
DOE OSTI2020

Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO 2 nanorod surface

Efficient electrocatalysts for the oxygen evolution reaction (OER) are paramount to the development of electrochemical devices for clean energy and fuel conversion. However, the structural complexity of heterogeneous electrocatalysts makes it a great challenge to elucidate the surface catalytic sites and OER mechanisms. Here, we report that catalytic single-site Co in a well-defined brookite TiO 2 nanorod (210) surface (Co-TiO 2 ) presents turnover frequencies that are among the highest for Co-based heterogeneous catalysts reported to date, reaching 6.6 ± 1.2 and 181.4 ± 28 s -1 at 300 and 400 mV overpotentials, respectively. Based on grand canonical quantum mechanics calculations and the single-site Co atomic structure validated by in situ and ex situ spectroscopic probes, we have established a full description of the catalytic reaction kinetics for Co-TiO 2 as a function of applied potential, revealing an adsorbate evolution mechanism for the OER. The computationally predicted Tafel slope and turnover frequencies exhibit exceedingly good agreement with experiment.

25 ENERGY STORAGE↗
DOE OSTI2020

Tailoring a Three-Phase Microenvironment for High-Performance Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

Despite tremendous progress in catalyst development for rate-limiting cathodic oxygen reduction reaction (ORR), reducing Pt usage while meeting performance requirements in practical proton exchange membrane fuel cells (PEMFCs) remains a challenge. The ORR in PEMFCs occurs at a catalyst–electrolyte–gas three-phase interface. A desirable interface should exhibit highly active and available catalytic sites, as well as allow efficient oxygen and proton feeding to the catalytic sites and timely removal of water to avoid interface flooding. In this work, we report the design of a three-phase microenvironment in PEFMCs, showing that carbon surface chemistry can be tuned to modulate its interaction with the ionomers and create favorable transport paths for rapid delivery of both reactants and products. With such an elaborate interfacial design, for the first time we have demonstrated PEMFCs with all key ORR catalyst performance metrics, including mass activity, rated power, and durability, surpassing the US Department of Energy targets.

25 ENERGY STORAGE↗
DOE OSTI2020

Phonon Dispersion Relation of Bulk Boron-Doped Graphitic Carbon

In this work, bulk turbostratic graphitic carbon of varying levels of disorder and chemical compositions has been synthesized by a direct synthesis method in the temperature range of 750–1100 °C, with a focus on boron incorporation within the graphitic lattice. The atomistic and electronic/vibrational structures were characterized by X-ray diffraction, energy-dispersive X-ray spectroscopy, Auger electron spectroscopy, X-ray absorption spectroscopy, and Raman spectroscopy. The phonon dispersion relation of graphitic carbon was found to be uniquely sensitive to substitutional boron doping, which perturbs the phonon structure while leaving the lattice structure unchanged. The dispersion relation of the D peak measured by Raman spectroscopy can be used to uniquely identify bulk graphitic materials containing a large content of ordered trigonal planar g-BC 3 units, which are of high interest in applications ranging from hydrogen storage to lithium-ion batteries.

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

A lithium-sulfur battery with a solution-mediated pathway operating under lean electrolyte conditions

Lithium-sulfur (Li-S) battery is one of the most promising candidates for the next generation energy storage systems. However, several barriers, including polysulfide shuttle effect, the slow solid-solid surface reaction pathway in the lower discharge plateau, and corrosion of Li anode still limit its practical applications, especially under the lean electrolyte condition required for high energy density applications. Here, we propose a solution-mediated sulfur reduction pathway to improve the capacity and reversibility of the sulfur cathode and suppress dendrite growth on the Li metal anode simultaneously. With this method, a high coulombic efficiency (99%) and stable cycle life over 100 cycles were achieved under application-relevant conditions (S loading: 6.2 mg cm-2; electrolyte to sulfur ratio: 3 mLE gs-1; sulfur weigh ratio: 72 wt%). This result is enabled by a specially designed Li2S4-rich electrolyte, in which Li2S is formed through a chemical disproportionation reaction instead of electrochemical routes. A diglyme solvent was used to obtain electrolytes with the optimum range of Li2S4 concentration. Operando X-ray absorption spectroscopy confirms the solution pathway in a practical Li-S cell. This solution pathway not only introduces a new electrolyte regime for practical Li-S batteries, but also provides a new perspective for bypassing the inefficient surface pathway for other electrochemical processes.

Wang, Hui↗
DOE OSTI2020

Rapid assessment of structural and compositional changes during early stages of zirconium alloy oxidation

A multimodal chemical imaging approach has been developed and applied to detail the dynamic, atomic-scale changes associated with oxidation of a zirconium alloy (Zircaloy-4). Scanning transmission electron microscopy, a gas-phase reactor chamber attached to an atom probe tomography instrument, and synchrotron-based X-ray absorption near-edge spectroscopy were employed to reveal morphology, composition, crystal, and electronic structure changes that occur during initial stages of oxidation at 300 °C. Oxidation was carried out in 10 mbar O 2 gas for short exposure times of 1 and 5 min. A multilayered oxide film with a cubic ZrO adjacent to the oxide/metal interface, a nanoscopic transition region with a graded composition of ZrO 2-x (where 0 < x < 1), and tetragonal ZrO 2 in the outermost oxide were formed. Partitioning of the major alloying element (tin) to the oxide/metal interface and heterogeneously within the oxide accompanied the development of the layered oxide. Our work provides a rapid, high-throughput approach for detailed characterisation of initial stages of zirconium alloy oxidation at an accelerated time scale, with implications for several other alloy systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Disparate Exciton-Phonon Couplings for Zone-Center and Boundary Phonons in Solid-State Graphite

The exciton-phonon coupling in highly oriented pyrolytic graphite is studied using resonant inelastic x-ray scattering (RIXS) spectroscopy. With ~70 meV energy resolution, multiple low energy excitations associated with coupling to phonons can be clearly resolved in the RIXS spectra. Here, using resonance dependence and the closed form for RIXS cross section without considering the intermediate state mixing of phonon modes, the dimensionless coupling constant g is determined to be 5 and 0.35, corresponding to the coupling strength of 0.42 eV+/-20 meV and 0.20 eV+/-20 meV, for zone center and boundary phonons, respectively. The reduced g value for the zone-boundary phonon may be related to its double resonance nature.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Factors Defining the Intercalation Electrochemistry of CaFe 2 O 4 -Type Manganese Oxides

Oxides with the CaFe 2 O 4 -type structure have been predicted as being suitable hosts for reactions of intercalation of light cations such as Li and Mg because of their favorable cationic diffusion. Although Li has been shown to intercalate into the Mn 2 O 4 variant, the key structure property correlations determining function are not fully ascertained. This basic information is needed before attempting the intercalation of divalent cations, which face comparably higher migration barriers. For this purpose, here the electrode function of CaFe 2 O 4 -type Li 0.8 Mn 2 O 4 was compared for materials made by a direct high-pressure route or through cation exchange from NaMn 2 O 4 . X-ray diffraction and absorption spectroscopy revealed that, despite having largely the same bulk structure, the presence of surface defects blocked Li + transfer in Li 0.8 Mn 2 O 4 made at high pressure. These defects were not present in the cation-exchanged material, which resulted in highly reversible Li intercalation with very fast kinetics in micrometric crystals. Delithiated electrodes from the cation-exchange synthesis were subsequently reduced in an ionic liquid electrolyte containing Mg 2+ . The process induced topotactic changes in the bulk, strongly suggesting the existence of intercalation, but it is accompanied by severe reactivity with the electrolyte that impedes reversibility. This study uncovers that defects affect the fundamentals of cation intercalation in this novel class of materials. The ability of the cation-exchanged material to conduct fast reactions with Li is consistent with calculated activation energy barriers and creates promise for their use as Mg hosts, provided that novel electrolytes enhanced stability at high potential can be realized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗