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At least 487 records · Page 27

Cold startup and low temperature performance of the Brayton cycle electrical subsystem

Cold performance tests and startup tests were conducted on the Brayton-cycle inverter, motor-driven pump, dc supply, speed control with parasitic load resistor and the Brayton control system. These tests were performed with the components in a vacuum and mounted on coldplates. A temperature range of ?25 to -50 C was used for the tests. No failures occurred, and component performance gave no indication that there would be any problem with the safe operation of the Brayton power generating system.

Vrancik, J. E.↗

Enhanced Photoreversible Color Switching of Redox Dyes Catalyzed by Barium-Doped TiO 2 Nanocrystals

We developed colloidal barium-doped TiO 2 nanocrystals that enable the highly reversible light-responsive color switching of redox dyes with excellent cycling performance and high switching rates. Oxygen vacancies resulting from the Ba doping serve as effective sacrificial electron donors (SEDs) to scavenge the holes photogenerated in TiO 2 nanocrystals under UV irradiation and subsequently promote the reduction of methylene blue to its colorless leuco form. Effective color switching can therefore be realized without relying on external SEDs, thus greatly increasing the number of switching cycles. Moreover, Ba doping can also accelerate the recoloration under visible-light irradiation by shifting the absorption edge of TiO 2 nanocrystals to a shorter wavelength. Such a system can be further casted into a solid film to produce a rewritable paper on which letters and patters can be repeatedly printed using UV light and then erased by heating; this process can be repeated for many cycles and does not require additional inks.

36 MATERIALS SCIENCE↗

Performance improvement of Li-rich layer-structured Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 by integration with spinel LiNi 0.5 Mn 1.5 O 4

Li-rich layered Li 1+x MnyM 1-x-y O 2 (or denoted xLi 2 MnO 3 center dot 1-x LiMO 2 , M = Ni, Co, Mn, etc.) are promising cathode materials for high energy-density Li-ion batteries. However, their commercial applications suffer from problems such as a drop in the capacity and discharge voltage during cycling. In this work, the cycling performance of a layered oxide Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 is improved by integration with spinel LiNi 0.5 Mn 1.5 O 4 to obtain a layered-spinel composite. Characterization by powder X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) as well as cyclic voltammetry (CV) indicates that delayed degradation of layered Li 2 MnO 3 and the suppressed growth of LiMn 2 O 4 -like spinel are responsible for the performance improvement.

36 MATERIALS SCIENCE↗

Tailoring P2/P3‐Intergrowth in Manganese‐Based Layered Transition Metal Oxide Positive Electrodes via Sodium Content for Na‐Ion Batteries

High-manganese content sodium-ion positive electrodes have received heightened interest as an alternative to contemporary Li-ion chemistries due to their high abundance, low toxicity, and even geographical distribution. However, these materials typically suffer from poor capacity, unstable cycling performance, and sluggish Na + kinetics. Herein, we explore a manganese-based layered transition metal oxide (Na x N 0.25 Mn 0.75 O 2 ) and show by X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) that careful variation of the sodium content can instigate the formation of a biphasic intergrowth. This intergrown P2/P3 material offered a higher capacity than its monophasic P2 counterpart due to the P3 structure having greater low-voltage Mn 3+/4+ redox. Further, the intergrowth material offers greatly enhanced kinetics and cycling stability when compared to single-phase P3 material, due to the stabilizing nature of the P2 structure, elucidated by galvanostatic intermittent titration technique (GITT) and operando synchrotron X-ray diffraction. These results highlight the beneficial effect that the intergrowth structure has on the electrochemical performance of high-manganese content positive electrode for future sodium-ion batteries.

25 ENERGY STORAGE↗

Improved Low Temperature Performance of Graphite/Li Cells Using Isoxazole as a Novel Cosolvent in Electrolytes

An investigation of novel electrolyte formulations to improve low temperature performance of Li/graphite half cells has been conducted. A novel electrolyte co-solvent, isoxazole (IZ), has been investigated in electrolyte systems composed of lithium difluoro(oxalato)borate (LiDFOB) in fluoroethylene carbonate (FEC) and LiDFOB in ethylene carbonate (EC). Cells containing 1 M LiDFOB FEC: IZ electrolyte have a significant improvement in capacity retention and reversible capacity at −10 °C. Ex-situ surface analysis of the cycled electrodes suggests that reduction of LiDFOB results in an oxalate rich solid electrolyte interphase (SEI). Addition of FEC, results in improved stability of the anode SEI preventing further decomposition of isoxazole solvent and improving cycling performance.

25 ENERGY STORAGE↗

Tracing U.S. fuel life-cycle greenhouse gas emissions in a multi-sector dynamics model using LC-GCAM

Model-based analysis of fuel pathways is essential for informing energy and environmental policy. Two major model types are typically used: multi-sector dynamics models, which capture the broader energy-economy, such as GCAM (Global Change Analysis Model), and life cycle assessment models, such as GREET (Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation). Each has distinct strengths and limitations, and recent studies increasingly adopt hybrid approaches to harness the advantages of both. However, such integration is often time-consuming and complicated by inconsistencies in system boundaries and technology definitions. We present LC-GCAM, a new tool that enables estimation of life-cycle greenhouse gas emissions and primary energy use for any fuel pathway represented in GCAM. We apply LC-GCAM to 300 scenarios designed to explore key uncertainties affecting the life-cycle performance of future fuel options in the U.S. freight sector. To evaluate LC-GCAM, we compare its results with those from GREET for nine fuel types in a 2030 reference scenario. When input assumptions are modestly aligned, LC-GCAM and GREET estimates typically agree within 10% (absolute sum-based mean absolute percentage error). LC-GCAM offers a flexible and efficient approach to generating life-cycle metrics within an integrated modeling framework, supporting robust policy analysis across a wide range of interacting energy system uncertainties.

Wolfram, Paul↗

Role of Solution Structure in Solid Electrolyte Interphase Formation on Graphite with LiPF 6 in Propylene Carbonate

An investigation of the interrelationship of cycling performance, solution structure, and electrode surface film structure has been conducted for electrolytes composed of different concentrations of LiPF6 in propylene carbonate (PC) with a binderfree (BF) graphite electrode. Varying the concentration of LiPF6 changes the solution structure, altering the predominant mechanism of electrolyte reduction at the electrode interface. The change in mechanism results in a change in the structure of the solid electrolyte interface (SEI) and the reversible cycling of the cell. At low concentrations of LiPF6 in PC (1.2 M), electrochemical cycling and cyclic voltammetry (CV) of BF graphite electrodes reveal continuous electrolyte reduction and no lithiation/delithiation of the graphite. The solution structure is dominated by solvent-separated ion pairs (Li+(PC)4// PF6 -), and the primary reduction product of the electrolyte is lithium propylene dicarbonate (LPDC). At high concentrations of LiPF6 in PC (3.0-3.5 M), electrochemical cycling and CV reveal reversible lithiation/delithiation of the graphite electrode. The solution structure is dominated by contact ion pairs (Li+(PC)3PF6 -), and the primary reduction product of the electrolyte is LiF.

36 MATERIALS SCIENCE↗

Realization of an Asymmetric Non‐Aqueous Redox Flow Battery through Molecular Design to Minimize Active Species Crossover and Decomposition

Abstract This communication presents a mechanism‐based approach to identify organic electrolytes for non‐aqueous redox flow batteries (RFBs). Symmetrical flow cell cycling of a pyridinium anolyte and a cyclopropenium catholyte resulted in extensive capacity fade due to competing decomposition of the pyridinium species. Characterization of this decomposition pathway enabled the rational design of next‐generation anolyte/catholyte pairs with dramatically enhanced cycling performance. Three factors were identified as critical for slowing capacity fade: (1) separating the anolyte–catholyte in an asymmetric flow cell using an anion exchange membrane (AEM); (2) moving from monomeric to oligomeric electrolytes to limit crossover through the AEM; and (3) removing the basic carbonyl moiety from the anolyte to slow the protonation‐induced decomposition pathway. Ultimately, these modifications led to a novel anolyte–catholyte pair that can be cycled in an AEM‐separated asymmetric RFB for 96 h with >95 % capacity retention at an open circuit voltage of 1.57 V.

Shrestha, Anuska↗

Fabrication of MoS2@SnO2-SnS2 composites and their applications as anodes for lithium ion batteries

Highlights: • The MoS{sub 2}@SnO{sub 2}-SnS{sub 2} composites were successfully fabricated. • The composites show long-term cycling performance used as anode for LIBs. • The superior performance ascribes to the synergistic effect between MoS{sub 2} and SnO{sub 2}. - Abstract: Sn-based anode for lithium-ion batteries (LIBs) has been received extensive concern, due to its high theoretical specific capacity. However, its poor stability induced by serious volume changes during charge/discharge process limits its application. MoS{sub 2} possesses a 2-dimisional (2D) graphene-like layered structure facilitates lithium ions insertion and extraction and can be served as the buffer to alleviate the volume variation. Unfortunately, 2D MoS{sub 2} nanosheets are highly susceptible to stacking/restacking during cycles, which is fatal to their capacity retention. Herein, a novel MoS{sub 2}@SnO{sub 2}-SnS{sub 2} composite has been designed and fabricated via a two-step simple hydrothermal route. Due to the synergistic effect between the ultrathin MoS{sub 2} nanosheets and the SnO{sub 2}-SnS{sub 2} nanosheets, the MoS{sub 2}@SnO{sub 2}-SnS{sub 2} composite exhibits excellent electrochemical performance as anode for LIBs.

36 MATERIALS SCIENCE↗

Quantification of Electrochemical Nanoscale Processes in Lithium Batteries By OperandoEC-(S)TEM

Lithium (Li)-ion batteries are currently used for a wide variety of portable electronic devices, electric vehicles and renewable energy applications. In addition, extensive worldwide research efforts are now being devoted to more advanced “beyond Li-ion” battery chemistries - such as lithium-sulfur (Li-S) and lithium-air (Li-O2) - in which the carbon anode is replaced with Li metal. However, the practical application of Li metal anode systems has been highly problematic. The main challenges involve controlling the formation of a solid-electrolyte interphase (SEI) layer and the suppression of Li dendrite growth during the charge/discharge process (achieving “dendrite-free” cycling). The SEI layer formation continuously consumes the electrolyte components creating highly resistive layer, which leads to the rapid decrease of cycling performance and degradation of the Li anode. The growth of Li metal dendrites at the anode contributes to rapid capacity fading (the presence of “dead Li” created during the discharge leads to an increased overpotential) and, in the case of continuous growth, leads to internal short circuits and extreme safety issues. Here we demonstrate the application of an operando electrochemical scanning transmission electron microscopy (ec-(S)TEM) cell to study the SEI layer formation and the initial stages of Li dendrite growth - the goal is to develop a mechanism for mitigating the degradation processes and increasing safety. Bright field (BF) STEM images in Figure 1 A-C show Li metal deposition and dissolution processes at the interface between the Pt working electrode and the lithium hexafluorophosphate (LiPF6) in propylene carbonate (PC) electrolyte during three charge/discharge cycles. A contrast reversal caused by Li metal being lighter/less dense than surrounding electrolyte (Li appears brighter than the background in BF STEM images) allows Li to be uniquely identified from the other components in the system - the only solid material that is less dense than the electrolyte is Li metal. Using these images, we can precisely quantify the total volume of Li deposition, the thickness of the SEI layer (observed as a ring of positive contrast around the electrode) and alloy formation due to Li+ ion insertion during each cycle. Furthermore, at the end of each discharge cycle we can quantify the presence of “dead Li” detached from the Pt electrode, thereby demonstrating the degree of irreversibility (and degradation of Pt electrode) associated with insertion/removal of Li+during this process with direct correlation to electrochemical performance. Such analyses provide significant insights into Li metal dendrite growth, which is critical to understand the complex interfacial reactions needed to be controlled for future Li-based and next generation energy storage systems.

batteries↗

Synthesis and electrochemical capacitive properties of nitrogen-doped porous carbon micropolyhedra by direct carbonization of zeolitic imidazolate framework-11

Highlights: • Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were prepared from ZIF-11. • The activated N-PCMPs with fused KOH (N-PCMPs-A) have high specific surface area. • N-PCMPs-A exhibits high specific capacitance. • N-PCMPs-A reveals good cycling performance even at a high current density. - Abstract: Nitrogen-doped porous carbon micropolyhedra (N-PCMPs) were successfully prepared by direct carbonization of ZIF-11 polyhedra and further activated with fused KOH to obtain N-PCMPs-A. The morphology and microstructure of samples were examined by scanning electron microscopy, X-ray diffraction, and micropore and chemisorption analyzer. Electrochemical properties were characterized by cyclic voltammetry and galvanostatic charge/discharge method in 1.0 M H{sub 2}SO{sub 4} aqueous solution on a standard three-electrode system. Results show that, compared with N-PCMPs, N-PCMPs-A has higher specific surface area (2188 m{sup 2} g{sup −1}) and exhibits improved electrochemical capacitive properties (307 F g{sup −1} at 1.0 A g{sup −1}). The mass specific capacitance of N-PCMPs-A is also higher than that of most MOF-derived carbons, some carbide-derived carbons and carbon aerogel-derived carbons. In addition, the capacitance of the N-PCMPs-A retains 90% after 4000 cycles even at a high current density of 10 A g{sup −1}. These imply that N-PCMPs-A is the promising materials for the construction of a high-performance supercapacitor.

36 MATERIALS SCIENCE↗

Functional Organosulfide Electrolyte Promotes an Alternate Reaction Pathway to Achieve High Performance in Lithium–Sulfur Batteries

Abstract Lithium–sulfur (Li‐S) batteries have recently received great attention because they promise to provide energy density far beyond current lithium ion batteries. Typically, Li‐S batteries operate by conversion of sulfur to reversibly form different soluble lithium polysulfide intermediates and insoluble lithium sulfides through multistep redox reactions. Herein, we report a functional electrolyte system incorporating dimethyl disulfide as a co‐solvent that enables a new electrochemical reduction pathway for sulfur cathodes. This pathway uses soluble dimethyl polysulfides and lithium organosulfides as intermediates and products, which can boost cell capacity and lead to improved discharge–charge reversibility and cycling performance of sulfur cathodes. This electrolyte system can potentially enable Li‐S batteries to achieve high energy density.

Chen, Shuru↗

Functional Organosulfide Electrolyte Promotes an Alternate Reaction Pathway to Achieve High Performance in Lithium–Sulfur Batteries

Abstract Lithium–sulfur (Li‐S) batteries have recently received great attention because they promise to provide energy density far beyond current lithium ion batteries. Typically, Li‐S batteries operate by conversion of sulfur to reversibly form different soluble lithium polysulfide intermediates and insoluble lithium sulfides through multistep redox reactions. Herein, we report a functional electrolyte system incorporating dimethyl disulfide as a co‐solvent that enables a new electrochemical reduction pathway for sulfur cathodes. This pathway uses soluble dimethyl polysulfides and lithium organosulfides as intermediates and products, which can boost cell capacity and lead to improved discharge–charge reversibility and cycling performance of sulfur cathodes. This electrolyte system can potentially enable Li‐S batteries to achieve high energy density.

Chen, Shuru↗

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries

We report P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries to replace Li-ion technology in certain applications. Still, the structure instability originates from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2- Na 0.72 Mn 0.75 Li 0.24 X 0.01 O 2 (X= Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in Na half-cells. Our finding shows Ti locates on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as protective layer that alleviate side reactions in carbonate-based electrolyte. Meanwhile, Si can regulate the local electronic structure and suppress oxygen redox activities. Notably, full-cells with hard carbon (≈300-335 Whkg -1 based on the cathode mass) deliver the capacity retention of 83% for P2- Na 0.72 Mn 0.75 Li 0.24 Si 0.01 O 2 and 66% for P2-Na 0.72 Mn 0.75 Li 0.24 Ti 0.01 O 2 after 500 cycles; this electrochemical stability is the best compared to other reported cathodes based on oxygen redox at present. The superior cycle performance also stems from the ability to inhibit microcracking and planar gliding within the particles. Altogether, this finding offers new composition towards developing high performance low-cost cathodes for Na-ion batteries and highlights the unique role of Ti/Si ions.

25 ENERGY STORAGE↗

Validity of a heart rate monitor during work in the laboratory and on the Space Shuttle

Accurate heart rate measurement during work is required for many industrial hygiene and ergonomics situations. The purpose of this investigation was to determine the validity of heart rate measurements obtained by a simple, lightweight, commercially available wrist-worn heart rate monitor (HRM) during work (cycle exercise) sessions conducted in the laboratory and also during the particularly challenging work environment of space flight. Three different comparisons were made. The first compared HRM data to simultaneous electrocardiogram (ECG) recordings of varying heart rates that were generated by an ECG simulator. The second compared HRM data to ECG recordings collected during work sessions of 14 subjects in the laboratory. Finally, ECG downlink and HRM data were compared in four astronauts who performed cycle exercise during space flight. The data were analyzed using regression techniques. The results were that the HRM recorded virtually identical heart rates compared with ECG recordings for the data set generated by an ECG simulator. The regression equation for the relationship between ECG versus HRM heart rate data during work in the laboratory was: ECG HR = 0.99 x (HRM) + 0.82 (r2 = 0.99). Finally, the agreement between ECG downlink data and HRM data during space flight was also very high, with the regression equation being: Downlink ECG HR = 1.05 x (HRM) -5.71 (r2 = 0.99). The results of this study indicate that the HRM provides accurate data and may be used to reliably obtain valid data regarding heart rate responses during work.

STS Shuttle Project↗

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↗

A core–shell structured nanocomposite of NiO with carbon nanotubes as positive electrode material of high capacitance for supercapacitors

Highlights: • A core–shell structured NiO@CNTs nanocomposite is synthesized by a simple hydrothermal method. • The CNTs core effectively improves the capacitance, rate and cycling performance of NiO. • A supercapacitor is assembled when activated carbon is used as the negative electrode. • The supercapacitor presents an energy density up to 52.6 Wh kg{sup −1}. - Abstract: A nanocomposite of carbon nanotubes coated with nickel oxide was prepared by a simple hydrothermal method. The structure, morphology and electrochemical performance of the nanocomposite were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy, electrochemical tests including cyclic voltammogram, galvanostatic charge–discharge and electrochemical impedance spectroscopy, respectively. It presents the highest specific capacitance of 1844 F g{sup −1} at 1 A g{sup −1} and 1145 F g{sup −1} at current density of 10 A g{sup −1} with 88.9% (at 1 A g{sup −1}) capacitance retention after 1000 cycles. The specific capacitance of the nanocomposite is almost double of that of the virginal NiO (972 F g{sup −1} at 1 A g{sup −1}). Its cycling behavior is also very good. When combined with activated carbon as the negative electrode, the energy density can be up to 52.6 Wh kg{sup −1}. Such good electrochemical behavior indicates that the nanocomposite is a promising electrode material for supercapacitors.

36 MATERIALS SCIENCE↗