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At least 199 records · Page 11

Defect Chemistry in High‐Voltage Cathode Materials for Lithium‐Ion Batteries

High-voltage cathodes (HVCs) have emerged as a paramount role for the next-generation high-energy-density lithium-ion batteries (LIBs). However, the pursuit of HVCs comes with inherent challenges related to defective structures, which significantly impact the electrochemical performance of LIBs. The current obstacle lies in the lack of a comprehensive understanding of defects and their precise effects. This perspective aims to provide insights into defect chemistry for governing HVCs. The classifications, formation mechanisms, and evolution of defects are outlined to explore the intricate relationship between defects and electrochemical behavior. The pressing need for cutting-edge characterization techniques that comprehensively investigate defects across various temporal and spatial scales is emphasized. Building on these fundamental understandings, engineering strategies such as composition tailoring, morphology design, interface modification, and structural control to mitigate or utilize defects are thoroughly discussed for enhanced HVCs performance. Furthermore, these insights are expected to provide vital guidelines for developing high-performance HVCs for next-generation high-energy lithium-ion batteries.

cross-scale characterization↗

Deciphering Chemical/Electrochemical Compatibility of Li 3 InCl 6 in 5.2 V High-Voltage LiCoO 2 All-Solid-State Batteries

Large interfacial resistance is a widely recognized impediment to the advancement of high-voltage, all-solid-state batteries. However, a comprehensive understanding of the fundamental cause behind the interfacial resistance between solid electrolytes and typical layered oxide cathodes has not yet been achieved. Here, we investigated the high-voltage stability of Li 3 InCl 6 and elucidated the underlying interfacial electrochemical reactions between LiCoO 2 and Li 3 InCl 6 . Further, the pairing of Li 3 InCl 6 with LiCoO 2 exhibited a superior capacity retention of 73.6% even at 5.2 V, much higher than 28.2% charged at 4.6 V in lithium-ion batteries after 70 cycles. The enhanced high-voltage stability of ASSBs is attributed to the stable interface formed between LiCoO 2 and Li 3 InCl 6 and the reinforced surface and bulk structure stability. On the other hand, the ultrahigh voltage still causes the partial decomposition of Li 3 InCl 6 and generates interfacial compounds such as InClO and cobalt and indium chlorides/oxides.

25 ENERGY STORAGE↗

HERACLES: A high-voltage DC test beamline for high average current photocathodes

Here, we present commissioning results of the High ElectRon Average Current for Lifetime ExperimentS (HERACLES) beamline at Cornell University. 10 mA average beam current at 200 keV was achieved with a Cs3Sb photocathode operated with an Argon laser at 488 nm. HERACLES is intended to be a test facility to improve the robustness of photocathodes developed for high average current beam operation in conjunction with the Cornell photocathode laboratory.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Spherical electrode eliminates high-voltage breakdown

Spherical electrodes surrounding electrode-dielectric junctions eliminate high-voltage breakdown. The gap between the spherical electrode and the dielectric must be of an optimum size for proper operation. Modified, this electrode should be suitable as a high-voltage feedthrough between various liquid and gaseous media.

Finke, R. C.↗

Evaluation of Niobium as Candidate Electrode Material for DC High Voltage Photoelectron Guns

The field emission characteristics of niobium electrodes were compared to those of stainless steel electrodes using a DC high voltage field emission test apparatus. A total of eight electrodes were evaluated: two 304 stainless steel electrodes polished to mirror-like finish with diamond grit and six niobium electrodes (two single-crystal, two large-grain, and two fine-grain) that were chemically polished using a buffered-chemical acid solution. Upon the first application of high voltage, the best large-grain and single-crystal niobium electrodes performed better than the best stainless steel electrodes, exhibiting less field emission at comparable voltage and field strength. In all cases, field emission from electrodes (stainless steel and/or niobium) could be significantly reduced and sometimes completely eliminated, by introducing krypton gas into the vacuum chamber while the electrode was biased at high voltage. Of all the electrodes tested, a large-grain niobium electrode performed the best, exhibiting no measurable field emission (< 10 pA) at 225 kV with 20 mm cathode/anode gap, corresponding to a field strength of 18:7 MV/m.

BastaniNejad, M.↗

Steric Effect Tuned Ion Solvation Enabling Stable Cycling of High-Voltage Lithium Metal Battery

1,2-Dimethoxyethane (DME) is a common electrolyte solvent for lithium metal batteries. Various DME-based electrolyte designs have improved long-term cyclability of high-voltage full cells. However, insufficient Coulombic efficiency at the Li anode and poor high-voltage stability remain a challenge for DME electrolytes. Here, we report a molecular design principle that utilizes a steric hindrance effect to tune the solvation structures of Li + ions. In this work, we hypothesized that by substituting the methoxy groups on DME with larger-sized ethoxy groups, the resulting 1,2-diethoxyethane (DEE) should have a weaker solvation ability and consequently more anion-rich inner solvation shells, both of which enhance interfacial stability at the cathode and anode. Experimental and computational evidence indicates such steric-effect-based design leads to an appreciable improvement in electrochemical stability of lithium bis(fluorosulfonyl)imide (LiFSI)/DEE electrolytes. Under stringent full-cell conditions of 4.8 mAh cm –2 NMC811, 50 μm thin Li, and high cutoff voltage at 4.4 V, 4 M LiFSI/DEE enabled 182 cycles until 80% capacity retention while 4 M LiFSI/DME only achieved 94 cycles. This work points out a promising path toward the molecular design of non-fluorinated ether-based electrolyte solvents for practical high-voltage Li metal batteries.

25 ENERGY STORAGE↗

Electrical safety for high voltage arrays

A number of key electrical safety requirements for the high voltage arrays of central station photovoltaic power systems are explored. The suitability of representative industrial DC power switchgear for control and fault protection was evaluated. Included were AC/DC circuit breakers, electromechanical contactors and relays, load interruptors, cold disconnect devices, sectionalizing switches, and high voltage DC fuses. As appropriate, steady state and transient characteristics were analyzed. Failure modes impacting upon operation and maintenance safety were also identified, as were the voltage withstand and current interruption levels.

Marshall, N. A.↗

Convergent Aeronautics Solutions (CAS) High Voltage Hybrid Electric Propulsion (HVHEP) Activity

Overview of Convergent Aeronautics Solutions (CAS) High Voltage Hybrid Electric Propulsion (HVHEP) activity. CAS HVHEP activity demonstrated feasibility of variable frequency, variable high voltage power system using doubly fed electric machines (DFM), and provided 90% reduction in power electronic weight for 35 megawatt system. DFM enables multi-phase (9) ac operation, with enhanced control and integrated protection methods for improved safety through minimization of fault energy.

CAS↗

Garnet solid electrolyte blended LiNi 0.6 Mn 0.2 Co 0.2 O 2 as high-voltage stable cathodes for advanced lithium-ion batteries

Ni-rich LiNi 1-x Co x/2 Mn x/2 O 2 layered materials have been widely adopted as cathodes for current electric vehicles (EVs) due to their high gravimetric and volumetric energy densities. However, their high-voltage instability (e.g., > 4.3 V vsLi ) limited their usable capacities corresponding to about 60 – 70 % of theoretical capacities. The major problems of high-voltage operation stem from instability of Ni 3+/4+ at cathode-electrolyte interphase (CEI) in contact with electrolytes. Here we propose garnet-type Li 6.7 La 3 Zr 1.7 Ta 0.3 O 12 (LLZT) solid-electrolyte-blended LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC) as high-voltage stable cathodes. The LLZT not only passivates the CEI but scavenges protons and moisture in electrolytes. From well-balanced ionic and electronic transport properties, 5 wt% LLZT blended NMC cathodes delivered enhanced electrochemical performances in full-cells. Unlike other complicated coating processes, our proposed solid-electrolyte blending approach can be readily implementable in commercial Li-ion batteries due to its manufacturing friendliness, energy saving, and cost effectiveness.

33 ADVANCED PROPULSION SYSTEMS↗

High Voltage Surge Protection by a Varistor-Filled Air Gap

The electric discharge across a varistor granule filled air gap under a fast-rising voltage pulse was investigated for surge protection applications. The effects of temperature and pressure on the arc and the electrical conduction were analyzed by the characteristic changes in voltage waveforms triggered by a fast-rising high voltage pulse. In addition to the gap size, experimental results show that competing mechanisms among arc conduction, conduction through the varistor granule network, thermionic emission from Joule heating at granule-to-granule contact points, and the magnitude of the switching voltage dictate the maximum surge protection voltage for the filled air gap. Experimental evidence indicated that accumulated degradation was created at small contact points between varistor granules by repetitive assaults from longer duration, high voltage pulses. The uniqueness of using varistor over other dielectric granules in an air gap for surge protection is identified and discussed.

36 MATERIALS SCIENCE↗

Feasibility of Micro-Multilayer Multifunctional Electrical Insulation (MMEI) System for High Voltage Applications

The newly patented micro-multilayer multifunctional electrical insulation (MMEI) system was developed for future electric aircraft applications which critically require lightweight but high voltage (HV), high temperature, and corona or partial discharge (PD) resistant insulation. During the initial development stages, the concept and practicability of the MMEI system were successfully validated with its exceptionally high dielectric breakdown voltages. The multilayer structures were optimized in terms of material type, individual layer thickness, and overall layer configuration along with potential mechanisms identified for its superior performance. Subsequently, scalability, manufacturability, and commercial applicability of the MMEI system were demonstrated with the 1 meter long, 3-phase HV, high power (HP) bus bar prototypes. Two prototypes, one with the conventional SOA insulation system including Mica sheet and the other with an optimized MMEI, were designed, fabricated, and tested successfully. Both prototypes passed both HiPot and PD tests up to the highest test voltage available, 15 kVAC, although the latter showed a slight increase in PD activities at 12.5 kV. However, the prototype with MMEI was 15% lighter or 12% thinner than the other one. Current efforts to significantly enhance the PD resistance of the MMEI system by employing semiconductive shielding layers, which can be also multifunctional, e.g., electromagnetic interference shielding, moisture blocking, heat dissipation, for various HV applications are also discussed in this paper.

Novel Electrical Insulation↗

Feasibility of Micro-Multilayer Multifunctional Electrical Insulation (MMEI) System for High Voltage Applications

The newly patented micro-multilayer multifunctional electrical insulation (MMEI) system was developed for future electric aircraft applications which critically require lightweight but high voltage (HV), high temperature, and corona or partial discharge (PD) resistant insulation. During the initial development stages, the concept and practicability of the MMEI system were successfully validated with its exceptionally high dielectric breakdown voltages. The multilayer structures were optimized in terms of material type, individual layer thickness, and overall layer configuration along with potential mechanisms identified for its superior performance. Subsequently, scalability, manufacturability, and commercial applicability of the MMEI system were demonstrated with the 1 meter long, 3-phase HV, high power (HP) bus bar prototypes. Two prototypes, one with the conventional SOA insulation system including Mica sheet and the other with an optimized MMEI, were designed, fabricated, and tested successfully. Both prototypes passed both HiPot and PD tests up to the highest test voltage available, 15 kVAC, although the latter showed a slight increase in PD activities at 12.5 kV. However, the prototype with MMEI was 15% lighter or 12% thinner than the other one. Current efforts to significantly enhance the PD resistance of the MMEI system by employing semiconductive shielding layers, which can be also multifunctional, e.g., electromagnetic interference shielding, moisture blocking, heat dissipation, for various HV applications are also discussed in this paper.

Novel Electrical Insulation↗

Oxygen redox activities governing high-voltage charging reversibility of Ni-rich layered cathodes

A schematic illustration indicative of the improved structural reversibility through stabilizing oxidized oxygen by Al doping. The chemical reactions and phase transitions at high voltages are generally considered to determine the electrochemical properties of high-voltage layered cathodes such as Ni-rich rhombohedral oxides. Even if significantly higher SOCs (states-of-charge) are utilized above the capability of transition metal redox (primarily Ni and Co), the effect of oxygen redox on Ni-rich rhombohedral oxides still looks mysterious thereby necessitating research that can clarify the relationship between redox reactions and phase transitions. Here, we performed a comprehensive and comparative study of the cationic and anionic redox reactions, as well as the structural evolution of a series of commercial Ni-rich layered oxides with and without Al doping. We combined the results from X-ray spectroscopy, operando electrochemical mass spectrometry, and neutron diffraction with electrochemical properties and thereby revealed the different oxygen redox activities associated with structural and electrochemical degradations. We reveal that Al doping suppresses the irreversible oxygen release but enhances the lattice oxygen oxidization. With this modulated oxygen redox activity, the Ni-rich layered oxides’ notorious H2–H3 structural phase transition becomes highly reversible. Our findings disentangle the different oxygen redox activities during high-voltage cycling and clarify the role of dopants in the Ni-rich layered oxides in terms of structural and electrochemical stability, shedding light on the future direction of optimizing layered cathode materials for safer high energy-density secondary batteries.

Lee, Gi-Hyeok↗

Boeing's High Voltage Solar Tile Test Results

Real concerns of spacecraft charging and experience with solar array augmented electrostatic discharge arcs on spacecraft have minimized the use of high voltages on large solar arrays despite numerous vehicle system mass and efficiency advantages. Boeing's solar tile (patent pending) allows high voltage to be generated at the array without the mass and efficiency losses of electronic conversion. Direct drive electric propulsion and higher power payloads (lower spacecraft weight) will benefit from this design. As future power demand grows, spacecraft designers must use higher voltage to minimize transmission loss and power cable mass for very large area arrays. This paper will describe the design and discuss the successful test of Boeing's 500-Volt Solar Tile in NASA Glenn's Tenney chamber in the Space Plasma Interaction Facility. The work was sponsored by NASA's Space Solar Power Exploratory Research and Technology (SERT) Program and will result in updated high voltage solar array design guidelines being published.

Reed, Brian J.↗

High-Voltage, Low-Power BNC Feedthrough Terminator

This innovation is a high-voltage, lowpower BNC (Bayonet Neill-Concelman) feedthrough that enables the user to terminate an instrumentation cable properly while connected to a high voltage, without the use of a voltage divider. This feedthrough is low power, which will not load the source, and will properly terminate the instrumentation cable to the instrumentation, even if the cable impedance is not constant. The Space Shuttle Program had a requirement to measure voltage transients on the orbiter bus through the Ground Lightning Measurement System (GLMS). This measurement has a bandwidth requirement of 1 MHz. The GLMS voltage measurement is connected to the orbiter through a DC panel. The DC panel is connected to the bus through a nonuniform cable that is approximately 75 ft (approximately equal to 23 m) long. A 15-ft (approximately equal to 5-m), 50-ohm triaxial cable is connected between the DC panel and the digitizer. Based on calculations and simulations, cable resonances and reflections due to mismatched impedances of the cable connecting the orbiter bus and the digitizer causes the output not to reflect accurately what is on the bus. A voltage divider at the DC panel, and terminating the 50-ohm cable properly, would eliminate this issue. Due to implementation issues, an alternative design was needed to terminate the cable properly without the use of a voltage divider. Analysis shows how the cable resonances and reflections due to the mismatched impedances of the cable connecting the orbiter bus and the digitizer causes the output not to reflect accurately what is on the bus. After simulating a dampening circuit located at the digitizer, simulations were performed to show how the cable resonances were dampened and the accuracy was improved significantly. Test cables built to verify simulations were accurate. Since the dampening circuit is low power, it can be packaged in a BNC feedthrough.

Bearden, Douglas↗

Lithium-Ion Electrolytes with Improved Safety Tolerance to High Voltage Systems

The invention discloses various embodiments of electrolytes for use in lithium-ion batteries, the electrolytes having improved safety and the ability to operate with high capacity anodes and high voltage cathodes. In one embodiment there is provided an electrolyte for use in a lithium-ion battery comprising an anode and a high voltage cathode. The electrolyte has a mixture of a cyclic carbonate of ethylene carbonate (EC) or mono-fluoroethylene carbonate (FEC) co-solvent, ethyl methyl carbonate (EMC), a flame retardant additive, a lithium salt, and an electrolyte additive that improves compatibility and performance of the lithium-ion battery with a high voltage cathode. The lithium-ion battery is charged to a voltage in a range of from about 2.0 V (Volts) to about 5.0 V (Volts).

Smart, Marshall C.↗

Interaction of high voltage surfaces with the space plasma

High voltage solar arrays provide spacecraft power while optimizing mass and power efficiency. Operating such arrays in the space plasma environment can result in anomalously large currents being collected through insulation defects. Two thicknesses of the insulating material were tested, with no effect found due to insulator thickness. In these tests the polyimide thickness was always much less than the pinhole diameter. The pinhole area was varied over an area range of more than 30:1. It was found that the current collected was independent of the pinhole area for hole diameters from 0.35 to 2.0 mm. Two types of adhesives were tried in two different configurations. The adhesives were chosen for their extreme difference in vacuum qualifications. Neither adhesive types nor configuration made a significant difference in current collection. The temperature of the insulating material was also varied. It was found that current collection decreased with increasing temperature. Tests were conducted to see if pinhole current collection decreased with time, as was indicated by the effects of several short tests. Current was collected for over four hours while the conductor potential was held constant at 1000 volts. A smooth decrease with time was not observed, but rather a roughly constant current collection with brief surges to high values. Tests were also conducted with the simulated solar cell biased negative. The current was found to be proportional to pinhole area.

Kaufman, H. R.↗