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Chen, Hao

Publications and source records attributed to Chen, Hao.

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Capturing the swelling of solid-electrolyte interphase in lithium metal batteries

Although liquid-solid interfaces are foundational in broad areas of science, characterizing this delicate interface remains inherently difficult because of shortcomings in existing tools to access liquid and solid phases simultaneously at the nanoscale. This leads to substantial gaps in our understanding of the structure and chemistry of key interfaces in battery systems. We adopt and modify a thin film vitrification method to preserve the sensitive yet critical interfaces in batteries at native liquid electrolyte environments to enable cryo–electron microscopy and spectroscopy. We report substantial swelling of the solid-electrolyte interphase (SEI) on lithium metal anode in various electrolytes. Here, the swelling behavior is dependent on electrolyte chemistry and is highly correlated to battery performance. Higher degrees of SEI swelling tend to exhibit poor electrochemical cycling.

25 ENERGY STORAGE↗
DOE OSTI2021

Dynamic spatial progression of isolated lithium during battery operations

The increasing demand for next-generation energy storage systems necessitates the development of high-performance lithium batteries. Unfortunately, current Li anodes exhibit rapid capacity decay and a short cycle life, owing to the continuous generation of solid electrolyte interface and isolated Li (i-Li). The formation of i-Li during the nonuniform dissolution of Li dendrites leads to a substantial capacity loss in lithium batteries under most testing conditions. Because i-Li loses electrical connection with the current collector, it has been considered electrochemically inactive or ‘dead’ in batteries. In this work, contradicting this commonly accepted presumption, we show that i-Li is highly responsive to battery operations, owing to its dynamic polarization to the electric field in the electrolyte. Simultaneous Li deposition and dissolution occurs on two ends of the i-Li, leading to its spatial progression toward the cathode (anode) during charge (discharge). Revealed by our simulation results, the progression rate of i-Li is mainly affected by its length, orientation and the applied current density. Moreover, we successfully demonstrate the recovery of i-Li in Cu–Li cells with >100% Coulombic efficiency and realize LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC)–Li full cells with extended cycle life.

25 ENERGY STORAGE↗
DOE OSTI2021

The influence of dietary intake of omega-3 polyunsaturated fatty acids on the association between short-term exposure to ambient nitrogen dioxide and respiratory and cardiovascular outcomes among healthy adults

Background: Short-term exposure to ambient nitrogen dioxide (NO 2 ) is associated with adverse respiratory and cardiovascular outcomes. Supplementation of omega-3 polyunsaturated fatty acids (PUFA) has shown protection against exposure to fine particulate matter. This study aims to investigate whether habitual omega-3 PUFA intake differentially modify the associations between respiratory and cardiovascular responses and short-term exposure to ambient NO 2 . Methods: Sixty-two healthy participants were enrolled into low or high omega-3 groups based on their habitual omega-3 PUFA intake. Each participant was repeatedly assessed for lung function, blood lipids, markers of coagulation and fibrinolysis, vascular function, and heart rate variability (HRV) in up to five sessions, each separated by at least 7 days. This study was carried out in the Research Triangle area of North Carolina, USA between October 2016 and September 2019. Daily ambient NO 2 concentrations were obtained from an area air quality monitoring station on the day of outcome assessment (Lag0), 4 days prior (Lag1-4), as well as 5-day moving average (5dMA). The associations between short-term exposure to NO 2 and the measured indices were evaluated using linear mixed-effects models stratified by omega-3 levels and adjusted by covariates including relative humidity and temperature. Results: The average concentration of ambient NO 2 during the study periods was 5.3±3.8 ppb which was below the National Ambient Air Quality Standards (NAAQS). In the high omega-3 group, an interquartile range (IQR) increase in short-term NO 2 concentrations was significantly associated with increased lung function [e.g. 1.2% (95%CI: 0.2%, 2.2%) in FVC at lag1, 2.6% (95%CI: 0.4%, 4.8%) in FEV1 at 5dMA], decreased blood lipids [e.g. -2.6% (95%CI: -4.4%, -0.9%) in total cholesterol at lag2, -3.1% (95%CI: -6.1%, 0.0%) in HDL at 5dMA, and -3.1% (95%CI: -5.5%, -0.7%) in LDL at lag2], improved vascular function [e.g. 8.9% (95%CI: 0.6%, 17.2%) increase in FMD and 43.1% (95%CI: -79.8%, -6.3%) decrease in endothelin-1 at 5dMA], and changed HRV parameters [e.g. -7.2% (95%CI: -13.6%, -0.8%) in HFn and 13.4% (95%CI: 0.2%, 28.3%) in LF/HF ratio at lag3]. In the low omega-3 group, an IQR increase in ambient NO 2 was associated with elevations in coagulation markers (von Willebrand Factor, D-dimer) and a decrease in HRV (very-low frequency); however, null associations were observed between short-term NO 2 exposure and changes in lung function, blood lipids, and vascular function. Conclusions: The results in this study imply that dietary omega-3 PUFA consumption may offer respiratory and vascular benefits in response to short-term exposure of healthy adults to NO 2 levels below the NAAQS.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Catalytic materials for lithium-sulfur batteries: mechanisms, design strategies and future perspective

Lithium-sulfur batteries (LSBs) are attractive candidates for post-lithium-ion battery technologies because of their ultrahigh theoretical energy density and low cost of active cathode materials. However, the commercialization of LSBs remains extremely challenging primarily due to poor cycling performance and safety concerns, which are inherently caused by low conductivity of S 8 and Li 2 S, severe polysulfide shuttling, and high polarization by solid Li 2 S 2 /Li 2 S deposition. Catalytic materials could facilitate the large-scale practical application of LSBs by overcoming all these challenges. In this review, we investigate the sulfur species evolution in LSBs and explore the roles of catalytic materials in charge/discharge processes, highlighting the catalysis of solid S 8 to liquid polysulfides and solid Li 2 S 2 to Li 2 S. Furthermore, we offer systematic strategies from atomic to macro levels, including defect engineering, morphology engineering and catalyst compositing, to enhance catalysis efficiency in terms of sulfur supercooling, fast charge transfer, thiosulfate generation, disulfide bond cleavage, tuneable Li 2 S growth and Li 2 S decomposition enhancement. Finally, the design and availability of the proposed catalytic materials will further advance LSB technology from coin cells and pouch cells to the subsequent commercialization scale.

25 ENERGY STORAGE↗
DOE OSTI2021

Tunnel magnetoresistance detection of skyrmions (Final Scientific/Technical Report for Magnon Current Transmission Through Insulators)

Micromagnetic simulations are used to investigate different strategies for tunnel magnetoresistance detection of the Néel skyrmion core direction and Bloch skyrmion chirality. When a Néel skyrmion passes beneath a perpendicularly magnetized dot separated by a tunnel barrier, a peak or dip in the tunnel magnetoresistance as a function of time shows a peak followed by a dip, or vice versa, depending on the chirality. The results are compared with existing detection methods based on the Hall resistance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Graphitic Aza-Fused π-Conjugated Networks: Construction, Engineering, and Task-Specific Applications

2D π-conjugated networks linked by aza-fused units represent a pivotal category of graphitic materials with stacked nanosheet architectures. Extensive efforts have been directed at their fabrication and application since the discovery of covalent triazine frameworks (CTFs). Besides the triazine cores, tricycloquinazoline and hexaazatriphenylene linkages are further introduced to tailor the structures and properties. Diverse related materials have been developed rapidly, and a thorough outlook is necessitated to unveil the structure–property–application relationships across multiple subcategories, which is pivotal to guide the design and fabrication toward enhanced task-specific performance. Herein, the structure types and development of related materials including CTFs, covalent quinazoline networks, and hexaazatriphenylene networks, are introduced. Advanced synthetic strategies coupled with characterization techniques provide powerful tools to engineer the properties and tune the associated behaviors in corresponding applications. Case studies in the areas of gas adsorption, membrane-based separation, thermo-/electro-/photocatalysis, and energy storage are then addressed, focusing on the correlation between structure/property engineering and optimization of the corresponding performance, particularly the preferred features and strategies in each specific field. In the last section, the underlying challenges and opportunities in construction and application of this emerging and promising material category are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A Morphologically Stable Li/Electrolyte Interface for All-Solid-State Batteries Enabled by 3D-Micropatterned Garnet

Morphological degradation at the Li/solid-state electrolyte (SSE) interface is a prevalent issue causing performance fading of all-solid-state batteries (ASSBs). To maintain the interfacial integrity, most ASSBs are operated under low current density with considerable stack pressure, which significantly limits their widespread usage. In this work, a novel 3D-micropatterned SSE (3D-SSE) that can stabilize the morphology of the Li/SSE interface even under relatively high current density and limited stack pressure is reported. Under the pressure of 1.0 MPa, the Li symmetric cell using a garnet-type 3D-SSE fabricated by laser machining shows a high critical current density of 0.7 mA cm –2 and stable cycling over 500 h under 0.5 mA cm –2 . This excellent performance is attributed to the reduced local current density and amplified mechanical stress at the Li/3D-SSE interface. These two effects can benefit the flux balance between Li stripping and creep at the interface, thereby pre-venting interfacial degradation such as void formation and dendrite growth.

3D-micropatterned garnet↗
DOE OSTI2021

Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO 2 Electroreduction

Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-art F-CTFs synthesized via the ZnCl 2 -promoted procedure have quite low fluorine contents due to C-F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400-700 °C). Fabricating F-CTFs with high fluorine contents (> 30 wt%) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf 2 ) 2 ] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt%), surface area up to 367 m 2 g -1 , and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO 2 to CO, with faradaic efficiency of 95.7% at –0.8 V and high current density (–141 mA cm -2 ) surpassing most of the metal-free electrocatalysts.

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

A bifunctional zeolitic porous liquid with incompatible Lewis pairs for antagonistic cascade catalysis

The emergence of porous liquids (PLs) opened opportunities to form unique antagonistic systems capable of fulfilling cascade reactions promoted by incompatible active sites in one pot, which is a long-term challenging subject in catalysis. Herein, unique bifunctional type III PL-based systems were facilely fabricated via assembly of zeolite nanosheets with ionic liquids. Rational structural design afforded PLs that feature high zeolite concentration, stable dispersion after 2 years, abundant cavity distribution, and involvement of antagonistic groups (acid and base sites) in separated and active form via steric hindrance control and electronic repulsion regulation. These unique properties worked cooperatively to fulfill the cascade deacetalization-Knoevenagel/Aldol condensation in one pot with superior catalytic efficiency outperforming the traditional systems. The key to success lies in the formation of bifunctional composites, transformation of zeolite from heterogeneous to homogeneous via surface modification, as well as rapid mass transfer ensured by the rigid porous architecture.

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

Nonlinear Multiple Models Adaptive Secondary Voltage Control of Microgrids

This article proposes a model-free secondary voltage control (SVC) for microgrids (MG) using nonlinear multiple models adaptive control. Firstly, a linear robust adaptive controller is designed to guarantee the voltage stability in the bounded-input- bounded-output (BIBO) manner so as to meet the operation requirements of MGs. Secondly, a nonlinear adaptive controller is developed to improve the voltage tracking performance with the help of artificial neural networks (ANNs). A switching mechanism for coordinating such two controllers is designed to guarantee the closed-loop stability while achieving accurate voltage tracking. Here, by an online identification based on the input and output data of MGs, the proposed method does not resort to any apriori information of system model and primary control, thus exhibiting good robustness, ease of deployment and disturbance rejection.

17 WIND ENERGY↗
DOE OSTI2021

Genomic insights into the origin, domestication and diversification of Brassica juncea

Despite early domestication around 3000 BC, the evolutionary history of the ancient allotetraploid species Brassica juncea (L.) Czern & Coss remains uncertain. Here, we report a chromosome-scale de novo assembly of a yellow-seeded B. juncea genome by integrating long-read and short-read sequencing, optical mapping and Hi-C technologies. Nuclear and organelle phylogenies of 480 accessions worldwide supported that B. juncea is most likely a single origin in West Asia, 8,000–14,000 years ago, via natural interspecific hybridization. Subsequently, new crop types evolved through spontaneous gene mutations and introgressions along three independent routes of eastward expansion. Selective sweeps, genome-wide trait associations and tissue-specific RNA-sequencing analysis shed light on the domestication history of flowering time and seed weight, and on human selection for morphological diversification in this versatile species. Our data provide a comprehensive insight into the origin and domestication and a foundation for genomics-based breeding of B. juncea.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Synthesis of Poly(ionic Liquid)s-block-poly(methyl Methacrylate) Copolymer-Grafted Silica Particle Brushes with Enhanced CO 2 Permeability and Mechanical Performance

Poly(ionic liquid) (PIL)-based block copolymers are of particular interest as they combine the specific properties of PILs with the self-assembling behaviors of block copolymers, broadening the range of potential applications for PIL-based materials. In this work, three particle brushes: SiO 2 -g-poly(methyl methacrylate) (PMMA), SiO 2 -g-PIL, and SiO 2 -g-PMMA-b-PIL were prepared through surface-initiated atom transfer radical polymerization. Unlike the homogeneous homopolymer particle brushes, the block copolymer particle brush SiO 2 -g-PMMA-b-PIL exhibited a bimodal chain architecture and unique phase-separated morphology, which were confirmed by size-exclusion chromatography and transmission electron microscopy. In addition, the influence of the introduction of the PMMA segment on the gas separation and mechanical performance of the PIL-containing block copolymer particle brushes were investigated. A significant improvement of Young’s modulus was observed in the SiO 2 -g-PMMA-b-PIL compared to the SiO 2 -g-PIL bulk films; meanwhile, their gas separation performances (CO 2 permeability and CO 2 /N 2 selectivity) were the same, which demonstrates the possibility of improving the mechanical properties of PIL-based particle brushes without compromising their gas separation performance.

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

Ultrasound-driven fabrication of high-entropy alloy nanocatalysts promoted by alcoholic ionic liquids

High-entropy alloy nanoparticles (HEA-NPs) are highly underutilized in heterogeneous catalysis due to the absence of a reliable, sustainable, and facile synthetic method. Herein, we report a facile synthesis of HEA nanocatalysts realized via an ultrasound-driven wet chemistry method promoted by alcoholic ionic liquids (AILs). Owing to the intrinsic reducing ability of the hydroxyl group, AILs were synthesized and utilized as environmentally friendly alternatives to conventional reducing agents and volatile organic solvents in the synthetic process. Under high-intensity ultrasound irradiation, Au 3+ , Pd 2+ , Pt 2+ , Rh 3+ , and Ru 3+ ions were co-reduced and transformed into single-phase HEA (AuPdPtRhRu) nanocrystals without calcination. Characterization results reveal that the as-synthesized nanocrystals are composed of elements of Au, Pd, Pt, Rh, and Ru as expected. Compared to the monometallic counterparts such as Pd-NPs, the carbon-supported HEA nanocatalysts show superior catalytic performance for selective hydrogenation of phenol to cyclohexanone in terms of yield and selectivity. Our synthetic strategy provides an improved and facile methodology for the sustainable synthesis of multicomponent alloys for catalysis and other applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Benchmark CO 2 separation achieved by highly fluorinated nanoporous molecular sieve membranes from nonporous precursor via in situ cross-linking

Molecular sieve membranes with rigid micropores and CO 2 -philic functionalities within the architectures are promising candidates in CO 2 separation. However, the development of ctieve approaches for their fabrication still remains a significant challenge. In this study, an in situ cross-linking strategy is developed for the preparation of nanoporous fluorinated moleffecular sieve membranes using commercially available dense and non-porous polystyrene (M PS ) as a precursor template. Based on the dehydrative Friedel-Crafts reactions with highly fluorinated benzylic alcohols, M PS membranes are cross-linked in situ upon exposure to Brønsted acid (CF 3 SO 3 H), affording fluorinated microporous polymeric membranes with surface areas up to 523 m 2 g –1 and the presence of micropores centered at 1.1–1.3 nm as well as ultra-micropores (~0.6 nm). The obtained modified membranes exhibit good ideal CO 2 permeability of 797 barrer and CO 2 /N 2 selectivity of 28.5. In addition, high fluorine content (up to 28.5 wt%) and good thermal stability made the cross-linked membranes promising candidates to produce fluorinated carbon molecular sieve membranes with improved textural properties, exhibiting surface areas up to 1020 m 2 g –1 and ultra-micropores of ~0.4 nm. These membranes achieve superior CO 2 /N 2 separation performances exceeding the Robeson upper bound limit (2008).

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

Asymmetric ferroelectricity by design in atomic-layer superlattices with broken inversion symmetry

In atomic-layer superlattices constructed using three constituent phases, CaTiO 3 , SrTiO 3 , and BaTiO 3 , the stacking sequence of the atomic layers is found to control the symmetry of the high-temperature dielectric response. In such a superlattice when a nanostructured asymmetric strain is programmed into the lattice via the stacking order, the natural symmetry at high temperatures is removed and a polarized sample is obtained in which the polarization increases as the temperature is lowered. Here, in contrast to a ferroelectric characterized by a bistable ground state with two equal and opposite electronic polarizations, our experiments show evidence of asymmetric ferroelectric correlations that set in when such a sample becomes hysteretic below a temperature T x , with two unequal polarization states. We further show that both the magnitude and direction of this ferroelectric asymmetry can be controlled by the engineered atomic-layer stacking order and periodicity of the superlattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗