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Liu, Yuzi

Publications and source records attributed to Liu, Yuzi.

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Direct observation of the formation and stabilization of metallic nanoparticles on carbon supports

Direct formation of ultra-small nanoparticles on carbon supports by rapid high temperature synthesis method offers new opportunities for scalable nanomanufacturing and the synthesis of stable multi-elemental nanoparticles. However, the underlying mechanisms affecting the dispersion and stability of nanoparticles on the supports during high temperature processing remain enigmatic. In this work, we report the observation of metallic nanoparticles formation and stabilization on carbon supports through in situ Joule heating method. We find that the formation of metallic nanoparticles is associated with the simultaneous phase transition of amorphous carbon to a highly defective turbostratic graphite (T-graphite). Molecular dynamic (MD) simulations suggest that the defective T-graphite provide numerous nucleation sites for the nanoparticles to form. Furthermore, the nanoparticles partially intercalate and take root on edge planes, leading to high binding energy on support. This interaction between nanoparticles and T-graphite substrate strengthens the anchoring and provides excellent thermal stability to the nanoparticles. These findings provide mechanistic understanding of rapid high temperature synthesis of metal nanoparticles on carbon supports and the origin of their stability.

36 MATERIALS SCIENCE↗
DOE OSTI2020

In-Situ Characterization of Dynamic Morphological and Phase Changes of Selenium-doped Germanium Using a Single Particle Cell and Synchrotron Transmission X-ray Microscopy

The dynamic information of lithium-ion battery active materials obtained from coin cell-based in-situ characterizations might not represent the properties of the active material itself because many other factors in the cell could have impacts on the cell performance. To address this problem, a single particle cell was developed to perform the in-situ characterization without the interference of inactive materials in the battery electrode as well as the X-ray-induced damage. In this study, the dynamic morphological and phase changes of selenium-doped germanium (Ge 0.9 Se 0.1 ) at the single particle level were investigated via synchrotron-based in-situ transmission X-ray microscopy. The results demonstrate the good reversibility of Ge 0.9 Se 0.1 at high cycling rate that helps understand its good cycling performance and rate capability. This in-situ and operando technique based on a single particle battery cell provides an approach to understanding the dynamic electrochemical processes of battery materials during charging and discharging at the particle level.

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

In-situ synchrotron diffraction study of the localized phase transformation and deformation behavior in NiTi SMA

The accumulation of dislocation defect was generally recognized as the origin of residual strain and the pseudoelastic instability in NiTi shape memory alloys (SMAs). In the present work, the pseudoelastic instability was studied by comparing the characteristics of Luders-type and uniform transformation mechanism via in-situ synchrotron-based high-energy X-ray diffraction (XRD) characterization. The experimental results showed that the Liiders-type mechanism could result in an intense and sharp increase of stress-induced martensite at the expense of austenite. The residual austenite with high lattice strain within the Luders band might be fully martensitic beyond the stress plateau of the E-a curve. With the accumulation of dislocation defect, the uniform martensitic transformation took place by the progressively homogeneous nucleation and growth of martensite in a local region. While the residual martensite and dislocation density was stabilized during mechanical cycling, the deformation of NiTi SMA turned into a mixture of (i) a balanced forward and reverse phase transformation between austenite and martensite, as well as (ii) the elastic deformation of the aggregate. As a result, there was no apparent increase in dislocation density detected during further cycling.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The effect of annealing on optical transmittance and structure of ZLANI fluorozirconate glass thin films

In this work, we report the effect of thermal annealing on structure, composition, optical transmittance and thickness of a novel fluorozirconate glass (ZLANI) containing Zr, La, Al, Na and In fluorides. In this work, pulsed laser depo- sition was used to grow thin films of ZLANI, and thermal annealing at different temperatures was performed on the films. Annealing did not change the composition, but a clear structural evolution of the ZLANI glass was observed by transmission electron microscopy (TEM), showing that we can control microstructure independent of composition. An increase in transmittance after the film was subject to a 100 °C thermal anneal was ascribed to the removal of defects and structural relaxation in the amorphous state. Following an anneal of 200 °C, the transmittance decreases due to heterogeneous formation of crystalline nuclei and changes in the local bonding. After the final annealing at 300 °C, a wider-scale crystallization occurred, with some major crystal phases formed as Zr 2 F 8 (H 2 O) 6 and ZrO 2 , which alters the shape of the transmittance curve. The crystalline content of the crystal phases that form in the annealed films was quantified using hollow cone dark field TEM imaging. The 100 °C or 200 °C annealing decreases the film thickness by inducing structural relaxation and densification of the amorphous films, while the thickness increase of the 300 °C annealed film resulted from the formed large crystals. These results provide insights for the design of multilayer nanocomposites with a ZLANI glass matrix, which have potential applications as up-/down-conversion luminescent materials and X-ray storage phosphors.

36 MATERIALS SCIENCE↗
DOE OSTI2020

In Situ Oxidation Studies of High-Entropy Alloy Nanoparticles

Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe 0.28 Co 0.21 Ni 0.20 Cu 0.08 Pt 0.23 HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner's theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe 2 O 3 , CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Blade-Type Reaction Front in Micrometer-Sized Germanium Particles during Lithiation

To investigate the lithium transport mechanism in micrometer-sized germanium (Ge) particles, in situ focused ion beam-scanning electron microscopy was used to monitor the structural evolution of individual Ge particles during lithiation. Our results show that there are two types of reaction fronts during lithiation, representing the differences of reactions on the surface and in bulk. Further, the cross-sectional SEM images and transmission electron microscopy characterizations show that the interface between amorphous Li x Ge and Ge has a wedge shape because of the higher Li transport rate on the surface of the particle. The blade-type reaction front is formed at the interface of the amorphous Li x Ge and crystalline Ge and is attributed to the large strain at the interface.

25 ENERGY STORAGE↗
DOE OSTI2020

Long interior carrier lifetime in selective-area InAs nanowires on silicon

Catalyst-free, position-controlled indium arsenide (InAs) nanowires (NWs) of variable diameters were grown on Si (111) by selective-area epitaxy (SAE). Ultrafast pump-probe spectroscopy was conducted, from which carrier recombination mechanisms on the NW surface and interior were resolved and characterized. NWs grown using SAE demonstrated high optical quality, showing minority carrier lifetimes more than two-fold longer than that of the randomly-positioned (RP) NWs. The extracted SAE-InAs NW interior recombination lifetime was found to be as long as 7.2 ns , 13X longer than previous measurements on RP-NWs; and the surface recombination velocity 4154 cm · s - 1 . Transmission electron microscopy revealed a high density of stacking defects within the NWs, suggesting that interior recombination lifetime can be further increased by improving NW interior crystalline quality.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Microfluidic, One-Batch Synthesis of Pd Nanocrystals on N-Doped Carbon in Surfactant-Free Deep Eutectic Solvents for Formic Acid Electrochemical Oxidation

One of the grand challenges that impedes practical applications of nanomaterials is the lack of robust manufacturing methods that are scalable, cheap, and environmentally friendly. In this work, we address this challenge by developing a microfluidic approach that produces surfactant-free Pd nanocrystals (NCs) uniformly loaded on N-doped porous carbon in a one-batch process. The deep eutectic solvent (DES) prepared from choline chloride and ethylene glycol was employed as a novel synthesis solvent, and its extended hydrogen networks and abundant ionic species effectively stabilize Pd facets and confine nanocrystal sizes without using surfactants. The microreactors provide faster heat exchange and more uniform mass transport, which in combination with DES produced Pd NCs with better-defined shape and predominately exposed Pd (100) facet. Furthermore, we describe that the N-doped functional groups in porous carbon direct dense and uniform heterogeneous growth of Pd NCs in a one-batch process, thereby eliminating a separate catalyst deposition step that is often involved in conventional synthesis. The Pd NCs in the one-batch-produced Pd/C catalysts exhibited a size distribution of similar to ~13 ± 3.5 nm and a high ESCA of 46.0 m 2 /g and delivered 362 mA/mg for formic acid electrochemical oxidation with improved stability, demonstrating the unique potentials of microfluidic reactors and DES for the controllable and scalable synthesis of electrocatalyst materials for practical applications.

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

In Situ and Operando Morphology Study of Germanium-Selenium Alloy Anode for Li-ion Batteries

Selenium-doped germanium (GeSe) micrometersized particles have been reported with good cycling performance and rate capability due to a Li-Se-Ge network formed during the first lithiation that provides a Li-ion fast pathway. To understand the effect of the Li-Se-Ge network at a high cycling rate, we monitored the morphology change of both pure Ge and GeSe particles during cycling with an in situ/operando focused-ion beam-scanning electron microscope method. Our results showed that the proposed inactive Li-Se-Ge network can provide fast Li-ion transport and also buffer volume variation, resulting in homogeneous volume change and uniform microstructural evolution.

germanium↗
DOE OSTI2020

Highly selective electrocatalytic CO 2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper

Direct electrochemical conversion of CO 2 to ethanol offers a promising strategy of lowering CO 2 emission while storing energy from renewable electricity. However, current electrocatalysts offer only limited selectivity toward ethanol. Here we report a copper catalyst synthesized by a unique Cu-Li amalgm method over a commercial carbon support that achieved Faradaic efficiency (FE) higher than 91% at -0.7 V (RHE) and the active potential as low as -0.4 V (RHE) during direct electrocatalytic CO 2 -to-ethanol conversion. The catalyst also demonstrated stability over an extended period of operation. A strong correlation between the catalytic selectivity and the initial Cu atoms dispersion was found and Operando X-ray absorption spectroscopy identified a dynamic and reversible transformation from atomically dispersed copper atoms to Cu n (n = 3 and 4) under the electrochemical reaction. Frist-principles calculations further elucidate the possible catalytic mechanism of CO 2 reduction over Cu n .

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

LixNiO/Ni Heterostructure with Strong Basic Lattice Oxygen Enables Electrocatalytic Hydrogen Evolution with Pt-like Activity

The low-cost hydrogen production from water electrolysis is crucial for practical deployment of sustainable hydrogen economy, but is often constrained by the lack of active and robust electrocatalysts from Earth-abundant materials. We describe here an unconventional heterostructure composed of strongly coupled Ni-deficient LixNiO nanoclusters and polycrystalline Ni nanocrystals, and its exceptional activities toward hydrogen evolution reaction (HER) in aqueous electrolytes. The presence of unique lattice oxygen species with strong Brønsted basicity is a significant feature, which spontaneously split water molecules and effectively accelerate the sluggish Volmer H-OH dissociation step in neutral and alkaline HER. In combination with the unpreceded level of intimate LixNiO and Ni interfacial junctions that produces abundant “hotspots” for promoted hydride coupling, the catalyst exhibited kinetic activities almost identical as Pt/C and decent long term stability in universal pH.

Lu, Ke↗
DOE OSTI2020

A macromolecular assembly directed ceramic aerogel monolith material

Ceramic aerogels exhibit remarkable thermal insulation for energy efficient building applications, while it is indispensable to understand their nanoporous structure evolution to control their thermal regulation performance. In this study, we design and synthesize a lightweight porous silica aerogel monolithic material, and demonstrate its thermal insulation performance regulated by the morphology of porous nanostructures controlled by surfactant induced self-assembly. The micelle networks and in situ gas bubble formation guide the formation of uniform pores in the as-synthesized monolith, which shows superior thermal and acoustic insulation and robust mechanical stability with a thermal conductivity of 0.032 W m –1 K –1 , a soundproof performance improvement by 17% at a frequency of 800 Hz, and a 1.3 MPa compressive strength with a Young's modulus of 15 MPa. Lastly, these findings provide a new route to manufacture low-cost aerogel monolithic insulation materials for energy efficient building applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Lead-Free Cs 4 CuSb 2 Cl 12 Layered Double Perovskite Nanocrystals

Concerns about the toxicity of lead-based perovskites have aroused great interest for the development of alternative lead-free perovskite-type materials. Recently, theoretical calculations predict that Pb 2+ cations can be substituted by a combination of Cu 2+ and Sb 3+ cations to form a vacancy-ordered layered double perovskite structure with superior optoelectronic properties. However, accessibilities to this class of perovskite-type materials remain inadequate, hindering their practical implementations in various applications. Here, we report the first colloidal synthesis of Cs 4 CuSb 2 Cl 12 perovskite-type nanocrystals (NCs). The resulting NCs exhibit a layered double perovskite structure with ordered vacancies and a direct bandgap of 1.79 eV. A composition-structure-property relationship has been established by investigating a series of Cs 4 Cu x Ag 2-2x Sb 2 Cl 12 perovskite-type NCs (0 ≤ x ≤ 1). The composition-induced crystal structure transformation, thus the electronic bandgap evolution has been explored by experimental observations and further confirmed by theoretical calculations. Taking advantages of both the unique electronic structure and solution processability, we demonstrate that the Cs 4 CuSb 2 Cl 12 NCs can be solution-processed as high-speed photodetectors with ultrafast photo-response and narrow bandwidth. We anticipate that our study will prompt future research to design and fabricate novel and high-performance lead-free perovskite-type NCs for a range of applications.

25 ENERGY STORAGE↗
DOE OSTI2020

Stabilized Electrode/Electrolyte Interphase by a Saturated Ionic Liquid Electrolyte for High-Voltage NMC532/Si-Graphite Cells

Nonaqueous electrolyte has become one of the technical barriers in enabling Li-ion battery comprising of a high voltage cathode and high capacity anode. Here, we demonstrate a saturated piperidinum bis(fluorosulfonyl)imide ionic liquid (IL) with a LiFSI salt not only supports the redox reaction on the cathode at high voltages, but also shows exceptional kinetic stability on the lithiated anode as evidenced by its improved cycling performance in a NMC532/Si-graphite full cells cycled between 4.6 and 3.0 V. On the basis of the spectroscopic/microscopic analysis and molecular dynamics (MD) simulations, the superior performance of the cells is attributed to the formation of solid-electrolyte-interphase on both electrode as well as unique solvation structure where a deadlocked coordination network is established at the saturated state, which prevents transition metal dissolution into the electrolyte via a solvation process.

25 ENERGY STORAGE↗
DOE OSTI2020

A practical phosphorus-based anode material for high-energy lithium-ion batteries

State-of-the-art lithium-ion batteries cannot satisfy the increasing energy demand worldwide because of the low specific capacity of the graphite anode. Silicon and phosphorus both show much higher specific capacity; however, their practical use is significantly hindered by their large volume changes during charge/discharge. Although significant efforts have been made to improve their cycle life, the initial coulombic efficiencies of the reported Si-based and P-based anodes are still unsatisfactory (<90%). In this study, by using a scalable high-energy ball milling approach, we report a practical hierarchical micro/nanostructured P-based anode material for high-energy lithium-ion batteries, which possesses a high initial coulombic efficiency of 91% and high specific capacity of ~2500 mAh g –1 together with long cycle life and fast charging capability. In situ high-energy X-ray diffraction and in situ single-particle charging/discharging were used to understand its superior lithium storage performance. Moreover, proof-of-concept full-cell lithium-ion batteries using such an anode and a LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode were assembled to show their practical use. The findings presented here can serve as a good guideline for the future design of high-performance anode materials for lithium-ion batteries.

25 ENERGY STORAGE↗