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At least 649 records · Page 36

Hollow-core optical fibre sensors for operando Raman spectroscopy investigation of Li-ion battery liquid electrolytes

Improved analytical tools are urgently required to identify degradation and failure mechanisms in Li-ion batteries. However, understanding and ultimately avoiding these detrimental mechanisms requires continuous tracking of complex electrochemical processes in different battery components. Here, we report an operando spectroscopy method that enables monitoring the chemistry of a carbonate-based liquid electrolyte during electrochemical cycling in Li-ion batteries with a graphite anode and a LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode. By embedding a hollow-core optical fibre probe inside a lab-scale pouch cell, we demonstrate the effective evolution of the liquid electrolyte species by background-free Raman spectroscopy. The analysis of the spectroscopy measurements reveals changes in the ratio of carbonate solvents and electrolyte additives as a function of the cell voltage and show the potential to track the lithium-ion solvation dynamics. The proposed operando methodology contributes to understanding better the current Li-ion battery limitations and paves the way for studies of the degradation mechanisms in different electrochemical energy storage systems.

47 OTHER INSTRUMENTATION↗

Facile Synthesis of Fe/N/S‐Doped Carbon Tubes as High‐Performance Cathode and Anode for Microbial Fuel Cells

Abstract As a renewable energy technology, microbial fuel cell (MFC) has been attracting increasing attention in recent decades. However, practical applications of MFCs has been hampered by the unsatisfactory electrode performance, in particular, at the cathode. Herein, Fe/N/S‐doped carbon hollow tubes were prepared by a facile two‐stage procedure involving hydrothermal treatment and pyrolysis at controlled temperatures. Electrochemical studies showed that the obtained samples exhibited an apparent electrocatalytic activity towards oxygen reduction reaction in both alkaline and acidic media, a performance comparable to that of commercial Pt/C, and the sample prepared at 800 °C stood out as the best among the series with a half‐wave potential of +0.81 V vs. RHE and an electron transfer number of 3.98 at +0.6 V vs. RHE. The Fe/N/S‐doped carbon tubes also exhibited a remarkable performance as an MFC anode by facilitating bacterial growth and electron transfer between the biofilm and electrode. In fact, an MFC based on the carbon tubes as both cathode and anode showed a markedly higher performance (maximum power density 479 W m −3 ) than the control MFC based on a graphene aerogel anode and Pt/C cathode (359 W m −3 ). These results suggest that Fe/N/S‐doped carbon composites can be used for the fabrication of high‐efficiency MFC electrodes.

Yang, Wei↗

Development of sputtered techniques for thrust chambers

Procedures for closing out coolant passages in regeneratively cooled thrust chambers by triode sputtering, using post and hollow Cu-0.15 percent Zr cathodes are described. The effects of aluminum composite filler materials, substrate preparation, sputter cleaning, substrate bias current density and system geometry on closeout layer bond strength and structure are evaluated. High strength closeout layers were sputtered over aluminum fillers. The tensile strength and microstructure of continuously sputtered Cu-0.15 percent Zr deposits were determined. These continuous sputtered deposits were as thick as 0.75 cm. Tensile strengths were consistently twice as great as the strength of the material in wrought form.

Mullaly, J. R.↗

Fuel cell components and systems having carbon-containing electrically-conductive hollow fibers

According to one embodiment, a system includes a structure having an ionically-conductive, electrically-resistive electrolyte/separator layer covering an inner or outer surface of a carbon-containing electrically-conductive hollow fiber and a catalyst coupled to the hollow fiber, an anode extending along at least part of a length of the structure, and a cathode extending along at least part of the length of the structure, the cathode being on an opposite side of the hollow fiber as the anode. In another embodiment, a method includes acquiring a structure having an ionically-conductive, electrically-resistive electrolyte/separator layer covering an inner or outer surface of a carbon-containing electrically-conductive hollow fiber and a catalyst along one side thereof, adding an anode that extends along at least part of a length of the structure, and adding a cathode that extends along at least part of the length of the structure on an opposite side as the anode.

25 ENERGY STORAGE↗

Transition characteristics and electron kinetics in microhollow cathode discharges

We demonstrate the transition characteristics and electron kinetics of microdischarges in a microgap with a cathode having microstructures using two-dimensional particle-in-cell/Monte Carlo collision (2d3v) simulations. It is found that the microdischarge is inside the hollow cavity at lower pressures, forming microhollow cathode discharges (MHCDs), while the dominant discharge moves outside the cavity at higher pressures, locating above the cathode rectangular protrusion tip. The spatial distributions of the microdischarge parameters (e.g., electric potential and electron density) are presented by capturing the transition characteristics. The electron kinetics of the microdischarges are examined based on the moment analysis of the electron Boltzmann equation. The collisional and non-collisional components of the electron power absorption are decomposed, which were seldomly investigated for microdischarges previously. The results provide fundamental insights into MHCD formation with a structured electrode at varying pressure conditions, which could be beneficial for the design and fabrication of microplasma devices in practical applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Fuel cell components and systems having carbon-containing electrically-conductive hollow fibers

A method, according to one embodiment, includes acquiring a structure having an ionically-conductive, electrically-resistive electrolyte/separator layer covering an inner or outer surface of a carbon-containing electrically-conductive hollow fiber and a catalyst along one side thereof, adding an anode that extends along at least part of a length of the structure, and adding a cathode that extends along at least part of the length of the structure, the cathode being on an opposite side of the hollow fiber as the anode.

25 ENERGY STORAGE↗

Multiple electron beam generation with different energies and comparable currents from a single cathode potential for high power traveling wave tubes (TWTs)

We present a technique for generating multiple electron beams with different energies and comparable currents from a single cathode stalk at a single potential using nested magnetically insulated coaxial diodes (MICDs). The application is for a multi-stream traveling wave tube. Particle-in-cell simulations are performed for an experimental parameter-based geometry where two thin-walled intense relativistic electron beams immersed in a strong uniform magnetic field propagate through a cylindrical vacuum channel. The analytically derived results are obtained by extending Fedosov’s solution for generating a hollow electron beam from an MICD on a cathode stalk in an infinite magnetic field. Two electron beams are generated and accelerated downstream assuming zero initial kinetic energy of the electrons from the cathodes. Results show both electron beam currents ranging from 66 to 2.8 kA with an energy difference ranging from 6% to 27% depending on voltages applied from 100 to 600 kV and the geometry of the two MICDs. An optimal geometry is a crucial factor in achieving the maximum energy difference between the electron beams for comparable currents. The analytical and numerical simulation results show good agreement. We are currently in the process of planning experiments using the electron beam accelerator (SINUS-6 at UNM) to validate the analytical and simulation results.

Islam, K. N. (ORCID:0000000214397710)↗

One-step atmospheric microplasma synthesis of an NMC-type lithium-ion battery cathode

The manufacture of battery cathode materials is the most energy-intensive step in the production of commercial lithium-ion batteries; specifically, the synthesis of the widely used transition metal oxide cathodes can require tens of hours at temperatures exceeding 700 °C. Attempts to limit the reaction time and energy required to form crystalline cathode materials often still include a heating or calcination step. This communication aims to highlight a nascent yet novel synthesis route: a one-step atmospheric microplasma process for synthesizing cathode particles in less than one second. The hollow-tube reactor employed produces crystalline particles measuring 0.1–3 μm in diameter, displays narrow XRD peaks corresponding to the 003, 104, and 101 planes, and exhibits anodic redox behavior at 3.75 V vs. lithium—characteristic of transition-metal oxide cathode materials—all without requiring an additional calcination step.

25 ENERGY STORAGE↗

Development of potassium ion conducting hollow glass fibers

Potassium ion conducting glasses, chemically resistant to potassium, potassium sulfide and sulfur, were made and their possible utility as the membrane material for a potassium/sulfur battery was evaluated. At least one satisfactory candidate was found. It possesses an electrical resistance which makes it usable as a membrane in the form of a fine hollow fiber. It's chemical and electrochemical resistances are excellent. The other aspects of the possible potassium sulfur battery utilizing such fine hollow fibers, including the header (or tube sheet) and a cathode current collector were studied. Several cathode materials were found to be satisfactory. None of the tube sheet materials studied possessed all the desired properties. Multi-fiber cells had very limited life-time due to physical failure of fibers at the fiber/tube sheet junctions.

Tsang, F. Y.↗

Lithium-Sulfur Batteries with a Block Copolymer Electrolyte Analyzed by X-ray Microtomography

Most of the work on Lithium-sulfur (LiS) batteries use liquid electrolytes that have limited stability when coupled with Li metal anodes. We have studied LiS batteries with a solid block copolymer electrolyte which exhibits improved stability against Li anodes. Additionally, the electrolyte comprises a polystyrene-b-poly(ethylene oxide) (SEO) copolymer doped with a Li salt. Hollow carbon nanospheres impregnated with sulfur were used to build a composite cathode. Two types of sulfur-impregnated functionalized carbon nanospheres were used: One with carboxylic acid groups and the other with short lithium poly(4-styrenesulfonyl(trifluoromethylsulfonyl)imide) (PSTFSI-Li) chains. Cells with Li S dissolved in the SEO based electrolyte served as the baseline. After cycling, the reason for capacity fade was determined by imaging the batteries using synchrotron hard X-ray microtomography. It is generally assumed that LiS cells fail due to dissolution of polysulfide into the liquid electrolyte, i.e., the main problems related to the cathode. In our all-solid cells, failure was primarily due to delamination of the Li foil from the polymer electrolyte layer. Delamination is also observed at the sulfur cathode. It is likely that the large changes in volume of the active materials during cycling induce delamination in all-solid LiS cells. 2 8

25 ENERGY STORAGE↗

Porous Hollow Carbon@Sulfur Composites for High-Power Lithium-Sulfur Batteries

Slowing down the shuttle: C@S nanocomposites (see TEM images) based on mesoporous, hollow carbon capsules were generated by a template-based approach. As the cathode material in a Li–S secondary battery, they display outstanding electrochemical features attributed to sequestration of elemental sulfur in the carbon capsules and to its favorable effect in limiting polysulfide shuttling as well as to enhanced electron transport from the sulfur.

catalysis (heterogeneous)↗

Palladium nanocrystals-imbedded mesoporous hollow carbon spheres with enhanced electrochemical kinetics for high performance lithium sulfur batteries

Lithium sulfur (Li-S) battery is one promising candidate for high energy density electrochemical energy storage system. Accelerating the sluggish reaction kinetics of sulfur cathode and suppressing the lithium polysulfide (LiPS) shuttle are crucial for the high-performance Li-S batteries. Herein, we prepared the catalytic palladium nano-particles (Pd NPs) imbedded in hollow carbon spheres (Pd@HCS) as sulfur host by a sacrificial template method. Benefitting from the hollow nanostructure and strong chemisorption ability of Pd NPs, Pd@HCS can effectively mitigate the LiPS shuttling via physical and chemical pathways. Furthermore, the Pd NPs as one electrocatalyst can accelerate the redox reaction kinetics of LiPS. The theoretical calculation and X-ray absorption spectroscopy elucidate that the moderate Pd-S bonding between Pd NPs and sulfur species are beneficial to LiPS conversion. The Pd@HCS/S electrode delivers a high initial capacity of 1306 mAh g –1 and 885 mAh g –1 after 100 cycles at 0.2 C, as well as the good cycling stability (a slight capacity decay of 0.068% per cycle over 400 cycles at 1 C). In conclusion, the Pd@HCS/S cathode with the high sulfur loading of 5.88 mg cm –2 delivers an initial capacity of 873 mAh g –1 at 0.2 C and good capacity retention of 85% after 100 cycles.

25 ENERGY STORAGE↗

Impact of Silicon Impurity on the Hydrometallurgical Recovery of NCM622 Cathode

Hydrometallurgy is one of the best approaches to date for recycling LIBs due to its high efficiency, low energy usage, and industrial scalability. However, impurities have always been a thorny issue because they could have unintended impacts on the recovered cathode materials. This research marks the first systematic investigation into the influence of silicon impurity on the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode obtained from hydrometallurgical recycling. Here we find that silicon nanoparticles will be nucleated at the center of the precursor particles during co-precipitation synthesis, and the silicon core will slowly dissolve in the surrounding ammonia, creating a special hollow structure in the particle. More importantly, the dissolution of silicon impurity will eventually lead to the deposition of silicates in the cathode material, which is an unfavorable result. Test data indicate that NCM622 cathode with 5 at% silicon has a capacity of 148.8 mAh g −1 after 100 cycles at 1/3 C, approximately 10 mAh g −1 lower than the virgin. Despite being relatively mild, the adverse influence of silicon impurity in hydrometallurgical recycling still requires attention.

25 ENERGY STORAGE↗

Operating High-Energy Lithium-Metal Pouch Cells with Reduced Stack Pressure Through a Rational Lithium-Host Design

Transitioning from a liquid electrolyte to an inorganic solid electrolyte offers a potential pathway to enable highly reversible lithium-metal anodes. However, the solid-electrolyte-protected lithium-metal anode suffers from poor interfacial ionic contacts and requires an impractically high stack pressure (>1.0 MPa) to maintain the interfacial contacts. It is demonstrated here that combining a hollow silver/carbon fiber scaffold and an inorganic/organic composite electrolyte enables a highly reversible lithium-metal anode. Since the high surface area of the electrode provides intimate contact and the hollow structure of the electrode relieves the lithium plating-induced stress, the electrode/electrolyte interface remains stable during cycling even under mild stack pressure. This unconventional structural design is validated in practical pouch cells assembled with the 3D lithium host containing a onefold excess of lithium and a high-nickel cathode. At a mild stack pressure of 320 kPa, the pouch cell displays 83% capacity retention for 200 cycles. This work illustrates that combining a hollow electrode architecture and a robust solid electrolyte offers a practical pathway toward rechargeable lithium-metal anodes.

36 MATERIALS SCIENCE↗

Carbon nanotube-linked hollow carbon nanospheres doped with iron and nitrogen as single-atom catalysts for the oxygen reduction reaction in acidic solutions

Non-noble metal electrocatalysts toward the oxygen reduction reaction (ORR) are highly required to substitute expensive Pt/C as the cathode of proton exchange membrane fuel cells. However, the relatively low ORR activity of Pt-free catalysts under acidic conditions is the major issue. Herein, we engineered a three-dimensional structure consisting of atomically dispersed Fe, N-doped hollow carbon nanospheres linked by carbon nanotubes as an electrocatalyst for the ORR. Benefiting from the unique structure and high-density atomic Fe–N x sites, this new type of electrocatalyst showed an impressive ORR half-wave potential of 0.84 V and kinetic current density of 13.1 mA cm -2 at a potential of 0.8 V in acidic media, which was even better those of commercial Pt/C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient sulfur host based on NiCo{sub 2}O{sub 4} hollow microtubes for advanced Li-S batteries

High energy density and cost effectiveness make lithium-sulfur battery a promising candidate for next-generation electrochemical energy storage technology. Here, we have synthesized a highly efficient sulfur host namely NiCo{sub 2}O{sub 4} hollow microtubes/sulfur composite (NiCo{sub 2}O{sub 4}/S). The hollow interior cavity providing structural integrity while sufficient self-functionalized surfaces of NiCo{sub 2}O{sub 4} chemically bind polysulfides to prevent their dissolution in the organic electrolyte. When used in lithium-sulfur batteries, the synthesized NiCo{sub 2}O{sub 4}/S cathode delivers high specific capacity (1274 mAh g{sup −1} at 0.2 C), long cycling performance at 0.5 C, and good rate capability at high current rates. - Highlights: • Hollow NiCo{sub 2}O{sub 4}/S microtubes were evaluated as an efficient sulfur host. • The designed 1D hollow architecture resulted in better cycling performance. • NiCo{sub 2}O{sub 4}/S delivered high capacity, long cycle life and good rate capability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical system and method for electropolishing hollow metal bodies

A method and system for electrochemically machining a hollow body of a metal or a metal alloy. An electrode is positioned within a hollow body including a metal or metal alloy, where the hollow body has a variable internal diameter. The hollow body is oriented vertically, with the electrode oriented vertically therein. The hollow body is at least partially filled with an aqueous, acidic electrolyte solution, the electrolyte solution being devoid of hydrofluoric acid and having a viscosity less than 15 cP. An electric current is passed between the hollow body and the electrode, where the electric current includes a plurality of anodic pulses and a plurality of cathodic pulses, and where the cathodic pulses are interposed between at least some of the anodic pulses.

36 MATERIALS SCIENCE↗

Trak Investigation of Focusing Electrode Geometries for the DARHT Axis-I Diode

An investigation was carried out on the effects of different cathode shroud geometries of the DARHT Axis-1 diode using the Trak ray tracing software. Pierce angles of 20, 30, 45, 60, and 67.5 degrees were investigated. For each geometry the current density with respect to radial position will be presented as it evolves in the longitudinal direction. In addition the emittances for each geometry are compared and this information is used to determine the optimal geometry from the selected angles. These results are compared to the baseline geometry currently employed at DARHT of a simple 2.5mm recessed velvet cathode. Of the selected angles it was found that 45 degrees produced the lowest normalized emittance value, whereas 60 degrees produced the most uniform current density profile at 1cm away from the emission surface. For the purpose of this investigation the effects of the bucking coil and solenoid around the hollow anode of the DARHT Axis I injector are neglected.

47 OTHER INSTRUMENTATION↗