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At least 1,405 records · Page 78

Emerging investigator series: local pH effects on carbon oxidation in capacitive deionization architectures

In this work, the effect of pH and potential is examined for the oxidation of carbon cloth electrodes used in capacitive deionization (CDI) processes. The degree of oxidation of the electrode surface, examined using the electrode's potential of zero charge (E pzc ) and measured using chronoamperometry and cyclic voltammetry, is found to be strongly correlated to the pH of the solution at the interface. Local pH measurements are examined at anodes and cathodes in full CDI and membrane-assisted capacitive deionization (MCDI) cells at cell voltages ranging from 0.3–1.2 V. The cathode is shown to be basic under charging potentials while the anode is found to be acidic. This local pH is found to be highly transient during charging and discharging in CDI cells while the pH is found to be relatively static in the MCDI cells, maintaining a basic pH at the cathode and an acidic pH at the anode even when the cell is discharged. Ion exchange membranes (IEM) are found to have two functions: (1) limiting co-ion expulsion that results from specific ion adsorption and (2) limiting the effects of parasitic Faradaic reactions on the separation process by stabilizing the local pH thereby mitigating dissolved oxygen reduction at the cathode and lessening carbon oxidation at the anode. Performance comparisons including the salt adsorption capacity and charge efficiency are also compared for these systems.

54 ENVIRONMENTAL SCIENCES↗

Dual functionality of over-lithiated NMC for high energy silicon-based lithium-ion batteries

Owing to their high specific capacity and suitably low operating potential, silicon-based anodes are an attractive alternative to graphite in next-generation lithium-ion batteries. However, silicon anodes suffer from low initial coulombic efficiency and fast capacity decay, limiting their widespread application. Pre-lithiation strategies are highly appealing to compensate for irreversible active lithium loss and to boost the cell energy density. In this work, we maximize the cell energy density by direct pre-lithiation of the NMC (LiNi 0.5 Mn 0.3 Co 0.2 O 2 ) cathode to Li 1+x NMCO 2 without introducing inactive deadweight to either electrode. First, we demonstrate that Li 1+x NMCO 2 can be synthesized chemically, via reaction between NMC and lithium napthalide, and electrochemically. The NMC cathode is tolerant of a one-time over-lithiation up to 60 mA h g NMC -1 , giving capacity retention on par with untreated NMC in half cell electrochemical cycling. Using synchrotron X-ray absorption spectroscopy (ex situ) and diffraction (in situ), we demonstrate that higher amounts of over-lithiation lead to local structure distortion – driven by transition metal reduction to Jahn–Teller active Mn 3+ and Co 2+ – as well as bulk structural hysteresis during over-lithiation and layer “buckling” that increases the amount of lithium extracted from the structure in the charged state. The Li 1+x NMCO 2 with low-to-moderate over-lithiation capacity (23, 46, and 70 mA h g NMC -1 ) is proven to be a highly effective dual-purpose lithium source and cathode material in full cell tests with a commercially relevant Si–graphite anode. These cells show higher capacity, superior cycle life, and improved coulombic efficiencies when compared to those with stoichiometric NMC cathodes. Finally, this study introduces a new and simple method to pre-lithiate layered transition metal oxide cathodes, opening up new possibilities for the development of high energy density lithium-ion batteries with next-generation anodes.

25 ENERGY STORAGE↗

In situ formed catalysts for active, durable, and thermally stable ammonia protonic ceramic fuel cells at 550 °C

Ammonia protonic ceramic fuel cells (NH 3 -PCFCs) are promising and attractive energy-conversion devices owing to their high energy density, zero-carbon emission, and safety. The development of NH 3 -PCFCs, however, depends largely on the insufficient activity and poor durability of typical Ni-based anodes for ammonia decomposition, especially at low temperatures such as 550 °C. Herein, we report a self-assembled heterostructured Ru 0.95 Cu 0.05 Ni x (RCN) catalyst obtained through an in situ reaction between the surface-decorated Ru 0.95 Cu 0.05 nanoparticles and the Ni grain in the anode under typical processing conditions. At 550 °C, Ni–BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3 anode-supported PCFCs with RCN catalysts exhibit a high peak power density of 0.732 W cm -2 and a significantly enhanced durability of 100 h in NH 3 . Moreover, the cells demonstrate improved thermal stability compared with the bare cell during a 31-cycle thermal cycling test in NH 3 between 550 and 700 °C. In conclusion, the enhanced performance is likely attributed to the synergistic effects of Ru and Cu in RCN for NH 3 decomposition, resulting in a more vital interaction of NH 3 than that of the bare anode surfaces, as confirmed by NH 3 thermal conversion, electrochemical performance, and theoretical simulations.

30 DIRECT ENERGY CONVERSION↗

Single-event burnout in homojunction GaN vertical PiN diodes with hybrid edge termination design

GaN devices play a major role in modern electronics, providing high-power handling, efficient high-frequency operation, and resilience in harsh environments. However, electric field crowding at the edge of the anode often limits its full potential, leading to single-event effects (SEEs) at lower bias voltages under heavy ion radiation. Here, in this work, we report on the performance of homojunction GaN vertical PiN diodes with a hybrid edge termination design under heavy ion irradiation, specifically, oxygen ions, chlorine ions, Cf-252 fission fragments, and alpha particles from an Am-241 source. The unique hybrid edge termination (HET) design provides better electric field management, preventing breakdown from occurring at the edge of the anode at lower voltages. The results of this study reveal that these devices exhibit excellent tolerance to 12-MeV oxygen and 16-MeV chlorine ions, owing to their low linear energy transfer (LET) and range in GaN. However, single-event burnout (SEB) is observed during the Cf-252 exposure at about 50% of the diodes' electrical breakdown voltage due to the presence of higher LET and longer-range ions. Optical and scanning electron microscopy (SEM) reveal that the damage that caused by SEB lies close to the center of these devices rather than the anode edge. Devices with junction termination extension (JTE) instead of HET edge termination also show similar SEB when irradiated with Cf-252 fission fragments. Physical damage due to SEB occurs at the edge of the anode for these devices. These comparative results show the benefits of HET for enhancing the resistance of GaN-based PiN diodes to heavy ion irradiation.

42 ENGINEERING↗

The DUNE Far Detector Vertical Drift Technology. Technical Design Report

DUNE is an international experiment dedicated to addressing some of the questions at the forefront of particle physics and astrophysics, including the mystifying preponderance of matter over antimatter in the early universe. The dual-site experiment will employ an intense neutrino beam focused on a near and a far detector as it aims to determine the neutrino mass hierarchy and to make high-precision measurements of the PMNS matrix parameters, including the CP-violating phase. It will also stand ready to observe supernova neutrino bursts, and seeks to observe nucleon decay as a signature of a grand unified theory underlying the standard model. The DUNE far detector implements liquid argon time-projection chamber (LArTPC) technology, and combines the many tens-of-kiloton fiducial mass necessary for rare event searches with the sub-centimeter spatial resolution required to image those events with high precision. The addition of a photon detection system enhances physics capabilities for all DUNE physics drivers and opens prospects for further physics explorations. Given its size, the far detector will be implemented as a set of modules, with LArTPC designs that differ from one another as newer technologies arise. In the vertical drift LArTPC design, a horizontal cathode bisects the detector, creating two stacked drift volumes in which ionization charges drift towards anodes at either the top or bottom. The anodes are composed of perforated PCB layers with conductive strips, enabling reconstruction in 3D. Light-trap-style photon detection modules are placed both on the cryostat's side walls and on the central cathode where they are optically powered. This Technical Design Report describes in detail the technical implementations of each subsystem of this LArTPC that, together with the other far detector modules and the near detector, will enable DUNE to achieve its physics goals.

47 OTHER INSTRUMENTATION↗

High-rate heavy-ion tracking using MWPCs and PPACs with an Anti-Discharge Unit

This work reports on the development of two robust, heavy-ion beam tracking concepts operating at low pressure (< 15 Torr) for high rate applications (> 200 kHz). The first concept consists of a Multi-Wire Proportional Counter (MWPC) with a central anode consisting of 12 μm Au-plated Tungsten wires spaced 1 mm from each other. The anode grid is sandwiched between two segmented cathodes aligned orthogonally in the two dimensions for (x,y) particle localization. The second detector is a Parallel-Plate Avalanche Counter (PPAC) that uses the same readout geometry as the MWPC, but replaces the wire anode with a 150 nm silver layer deposited on both sides of a thin (< 1 mg/cm 2 ) polypropylene foil. Additionally, the bias circuitry for the PPAC anode central foil is equipped with an Anti-Discharge Unit (ADU) to prevent transitions from proportional operation to streamer formation, thereby avoiding damaging discharges. The localization capability of both detectors was tested with a low-rate alpha-particle source (241-Am). A position resolution of < 1 mm (FWHM) was achieved under stable, high-gas-gain (> 1000) operating conditions. Their performance in terms of detection efficiency as a function of the isotope charge (Z) was determined by irradiating the detectors with a cocktail beam (Z ≤ 15) with energy of ∼ 100 MeV/u. Full detection efficiency is maintained for all available fragments under optimal operational conditions (i.e., voltage bias). Full detection efficiency was achieved at rates above 200 kHz by irradiating the detectors with a 1 cm diameter 238 U beam at an energy of 143 MeV/u.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

In Situ Reliability Investigation of All-Vanadium Redox Flow Batteries by a Stable Reference Electrode

Redox flow batteries (RFBs) have been studied over the past several decades as a promising candidate for stationary energy storage applications. It is therefore important to understand the reliability of RFBs and the mechanisms that cause degradation with time. Contributions from individual electrodes (cathode or anode) are difficult to separate especially for long-term cycle testing, due to the lack of a stable reference electrode. In our work, the reliability and degradation mechanisms of an all-vanadium RFB were investigated by a stable reference electrode based on the dynamic hydrogen electrode (DHE). With factor exploration and design optimization, the newly developed DHE reference electrode demonstrated high accuracy and long-term stability that enables in-situ monitoring of individual electrode signals (potentials and impedances) over hundreds of cycles in a vanadium RFB. This approach enables the full cell degradation to be separated and the degradation attributed to contributions from the cathode and anode. The cathode and anode were found to play quite different roles in the increase in overpotential of the vanadium RFB during long-term cycling. The anode reaction limited both the charge and discharge capacity over 100 cycles. In addition, the negative side also appeared to be the rate limiting factor throughout cycling as determined by EIS measurement. The cathode contributed to the performance degradation as cycling exceeded 50 cycles.

Huang, Qian↗

Fast Charging of Li-Ion Cells: Part V. Design and Demonstration of Protocols to Avoid Li-Plating

Fast charging of Li-ion batteries would make “fueling” of electric vehicles comparable in time to fueling of gasoline-powered cars, increasing consumer appeal of the new technology. Taking the US Department of Energy goal of safe 6 C charging to 80% capacity as a guide, we describe approaches that can mitigate Li plating on the graphite anode. To make this possible, a variable-rate anode potential charging protocol has been implemented by using a microprobe reference electrode to continuously monitor and adjust the current, in this way avoiding low anode potentials that favor Li deposition. Various implementations of the anode potential control are considered using electrochemical modeling and compared with the experimental data. For charge to 80% capacity at 30 °C, an average C-rate of 4.97 C was obtained for an NCM523/graphite cell with 70 μ m thick graphite electrode and 7.40 C for a cell with 47 μ m thick graphite electrode. Our electrochemical model accounts for these observations and provides a means to extrapolate the approach to other cell designs and operation regimes, drawing the maximum average fast charging rates that can still avoid Li plating.

25 ENERGY STORAGE↗

Promoting CO 2 Release from CO 3 2- -Containing Solvents during Water Electrolysis for Direct Air Capture

The pH swings from water electrolysis are leveraged to condition OH – -based facile CO 2 capture solvents using an electrochemical flow cell for direct air capture (DAC). Besides demonstrating the DAC using a membrane contactor, promoting CO 2 release from a CO 3 2– solution at the anode is specifically studied by adjusting the volumetric flow rate, anode chamber volume, residence time, and K 2 CO 3 concentration. Through case-by-case comparisons coupled with modeled results, increasing current, reducing volumetric flow rate, and/or reducing CO 3 2– concentration are the effective methods to promote CO 2 release from a CO 3 2– -containing solvent, whereas enlarging the anode chamber volume poses a minor effect. Moreover, the discrepancies between the experimental and modeled results may be caused by H + crossover rather than K + transport through the Nafion membrane during water electrolysis based upon the total alkalinity measurements for the K 2 CO 3 solutions gleaned from the anode. Here, it is believed that such results will provide guidance to design and operate an electrochemical flow cell for electrochemistry-assisted DAC and point source CO 2 capture.

20 FOSSIL-FUELED POWER PLANTS↗

Electrolyzer Performance Loss from Accelerated Stress Tests and Corresponding Changes to Catalyst Layers and Interfaces

Stress tests are developed for proton exchange membrane electrolyzers that utilize low catalyst loading, elevated potential, and frequent cycling with square- and triangle-waves to accelerate anode catalyst layer degradation during intermittent operation. Kinetics drive performance losses (ohmic/transport secondary) and are accompanied by decreasing exchange current density, decreasing cyclic voltammetric capacitance, and increasing polarization resistance. Decreased kinetics are likely due to a combination of iridium (Ir) migration into electrochemically inaccessible locations in the anode or membrane, Ir particle growth (supported by X-ray scattering), changes in the extent of the Ir oxidation state (supported by X-ray absorption spectroscopy), and anode catalyst layer reordering. Decreasing catalyst/transport layer contact and catalyst/membrane interfacial tearing may add contact resistances and account for increasing ohmic losses. Performance losses for low and moderate catalyst loading, as well as from accelerated and model wind/solar cycling protocols, were likewise dominated by kinetics but vary in severity. Additionally, accelerated cycling (1 cycle per minute) appears to reasonably accelerate relevant loss mechanisms and can be used to project electrolyzer lifetime from anode deterioration. Ongoing accelerated stress test development and studies into performance loss mechanisms will continue to be critical as electrolysis shifts to intermittent power and low-cost applications.

30 DIRECT ENERGY CONVERSION↗

Understanding and Enhancing Silicon Nanoparticle Distribution during Electrode Processing

Silicon-dominant anodes are of great interest because of their potential to boost the cell-level energy of state-of-the-art Li-ion batteries. While silicon materials have been extensively studied, understanding interactions at the electrode level has recieved little attention, especially the coating process of Si particles, which plays an equally important role in unlocking the full potential of silicon anodes. Herein, the electrode processing of a Si-dominated anode (52.8 wt%, 3.5–4.5 mAh cm −2 ) is being investigated to understand the relationship of processing on the morphology and properties of Si anodes at the electrode level. It has been found that almost-undetectable Si agglomerates easily form during electrode processing, which grow into largeprotrusions after lithiation and trigger potential internal shorting and self-discharge problems. A facile slurry filtration step is proposed to homogenize the particle distribution within Si-dominant electrodes which improves the electrochemical performance and storage stability of Si-based Li ion batteries.

Wu, Bingbin↗

Unlocking Failure Mechanisms and Improvement of Practical Li-S Pouch Cells Through in Operando Pressure Study

For Lithium-sulfur (Li-S) battery commercialization, the study at a pouch cell level is essential, as some problems ignored or deemed minimal at the smaller level could have a greater effect on the performance of the larger pouch cell. Herein, the failure mechanisms of Li-S pouch cells are deeply investigated via in operando pressure analysis. It is found that highly porous structures of cathodes/separators and slow electrolyte diffusion through cathodes/separators can both lead to poor initial wetting. Additionally, Li-metal anode dominates the thickness variation of the whole pouch cell, which is verified by in situ measured pressure variation. Consequently, a real-time approach that combined normalized pressure with dP/dV analysis is proposed and validated to diagnose the morphology evolution of Li-metal anode. Moreover, applied pressure and porosity/tortuosity ratio of the cathode are both identified as independent factors that influence anode performance. In addition to stabilizing anodes, high pressure is proven to improve the cathode connectivity and avoid cathode cracking over cycling, which improves the possibility of developing cathodes with high sulfur mass loading. This work provides insights into Li-S pouch cell design (e.g., cathode and separator) and highlights pathways to improve cell capacity and cycling performance with applied and monitored pressure

25 ENERGY STORAGE↗

A Double Sided LGAD-Based Detector Providing Timing, Position, and Track Angle Information

We describe a detector concept which combines small pixels enabled by 3D sensor-electronics integration with gain produced by a Low Gain Avalanche Diode (LGAD) layer. The detector is double-sided, with electrons collected by the cathode, which provides timing information, and an anode with small pixels to provide position and angle information. The cathode can be coarse grained, providing timing with fewer fast amplifiers to limit power consumption. The anode layer benefits from the gain of the LGAD, with larger signals that also limit the power needed. Position can be reconstructed by measuring the pattern of total charge deposited on the anode. Angle and depth of charge deposit can be measured by the shapes of the anode pulses. We describe a possible assembly technology based on 3D integration.

3D Integration↗

Composite Solid Ion Conductor with Engineered Lithium Interface

Successful widespread commercialization of electric vehicles is contingent upon development of safe high energy density batteries capable of long cycle life. Lithium metal affords the highest theoretical capacity (3,860 mAh/g) and lowest electrochemical potential (-3.04V vs SHE), which offers the highest specific energy density of anode materials today. While Li-ion batteries are capable of delivering energy densities of 400-600 Wh/kg, the development of lithium metal batteries such as Li-S and Li-air may boost this number up to 650 and 950 Wh/kg, respectively. However, significant progress towards the passivation of lithium metal must occur before the energy density benefit can be realized. Issues with lithium dendrite formation, anode volume expansion, and continuous solid electrolyte interphase (SEI) build-up often result in significant safety concerns, high cell resistance, and poor cycle life. The intrinsic high reactivity between lithium metal with conventional lithium ion electrolytes (organic carbonate-based solvents) makes it extremely difficult to overcome these problems. In this project, Wildcat performed focused, fundamental research and development on composite polymer/ceramic electrolytes and protected lithium metal anodes to develop an all solid state lithium metal battery targeting the DOE requirements to enable commercialization. Wildcat successfully leveraged its high throughput battery platform and explored a broad composite electrolyte compositional space. Additionally, Wildcat screened large numbers of inorganic and organic coatings for lithium metal protection using in situ liquid methods and translated the best results to all solid cells. The proposed composite polymer/ceramic electrolyte and a protected lithium metal anode enabled a solid-state lithium metal battery. The ultimate targets from this effort will deliver a safe all solid-state lithium metal pouch cell with over 350 Wh/kg and over 1,000 cycles (C/3) with the cost estimate below $100/kWh. During the course of the project, we demonstrated stable cycling of 10’s of cycles with the composite SSE and our protected lithium. The work has continued after the conclusion of the DOE funding, demonstrating further improvements in catholyte composition and thinner composite solid electrolytes.

25 ENERGY STORAGE↗

Jumpstart Opportunities to Unleash Leadership in Energy Storage (JOULES)

Current-generation Li-ion batteries with cobalt- and nickel-containing cathodes and graphite anodes are approaching performance and cost limits. In this program, 24M Technologies, Inc. (24M) is teaming with the Massachusetts Institute of Technology (MIT) and University of Michigan (UM) to develop low cost and fast charging sodium metal batteries with good low-temperature performance and high energy density, building upon previous work performed under ARPA-E programs. Key achievements include optimization of solid electrolyte and anode current collector, optimized cathode active materials, development of high-performance electrolyte formulations, and integration of these components into full cells. The cell design incorporates (1) an ultra-thick cathode (>9 mAh/cm 2 ) comprising advanced cobalt-free, sodium cathode active material, (2) advanced fast-charging electrolyte (up to 12 mS/cm) developed using machine learning and automated high-throughput screening technology by UM, and (3) ceramic modified separator that enable smooth Na transport and deposition, developed at MIT, enabling a high-energy density anode-free configuration and maximizing the energy density of sodium batteries. The team has successfully combined these approaches to sodium chemistry and paved the way to meeting the fast-charging, high-energy density, and low-cost requirements of next-generation drone, electric vertical take-off and -landing, and electric vehicle batteries. Performance for anode-free sodium cells developed under this program is more powerful than the commercial Li-ion batteries. The final deliverable cell design has achieved over 300 Wh/kg and volumetric energy density above 800 Wh/L (Table 1). Additionally, the team has achieved over (1) a lifetime of 340 cycles, (2) 80% capacity retention at -20 °C (compared 25 °C), and (3) the ability to fast charge to 80% SOC in 20 minutes.

25 ENERGY STORAGE↗

ION PRODUCTION AND MITIGATION IN DC HIGH-VOLTAGE PHOTO-GUNS

One of the biggest obstacles to operating a GaAs polarized electron source with a long charge lifetime is the mitigation of ion back-bombardment. Several techniques exist to either clear ions from the accelerator or to mitigate ion damage of the photocathode. Predicting the effectiveness of these techniques requires sophisticated simulation models of electron impact ionization within the photo-gun. In this work, the effectiveness of applying a positive anode bias voltage to mitigate ion damage and increase the charge lifetime of the GaAs photocath?ode was studied over three run periods at the Continuous Electron Beam Accelerator Facility (CEBAF) at Jefferson Lab (JLab). The charge lifetime with the biased anode configuration was 1.80±0.51 times longer than the lifetime of the usual grounded anode configuration. Sim?ulations of ionization within the CEBAF photo-gun and adjacent beamline were made using General Particle Tracer (GPT) and a new C++ custom element to predict and explain the substantial improvement in charge lifetime. The experimental results and the development of the ionization custom element, with its use in simulations of ion back-bombardment with the biased anode, are described in detail.

Yoskowitz, Joshua↗

Magnetically actuated tuning method for Gunn oscillators

A tunable microwave generator based on the Gunn effect is disclosed. The generator includes a semiconductor material which exhibits the Gunn effect when current flows between anode and cathode end contacts. The material has a plurality of sides each with a scratch at a different distance from the anode contact. A magnetic field is produced by a magnet placed about the semiconductor field. The Lorentz force produced as a function of the current flow and the magnetic field drive the electrons to the surface of one of the sides to cause nucleation to occur at the scratch. A domain formed thereat travels to the anode contact to provide pulses at a frequency which is related to the distance between the scratch and the anode contact.

Sacks, B. H.↗

X-ray emission from high temperature plasmas

The bremsstrahlung X-rays from a plasma focus device were investigated with emphasis on the emission versus position, time, energy, and angle of emission. It is shown that low energy X-rays come from the plasma focus region, but that the higher energy components come from the anode. The emission is anisotropic, the low energy polar diagram resembling a cardioid, while the high energy emission is a lobe into the anode. The plasma parameters were considered indicating that even in the dense focus, the plasma is collisionless near the axis. By considering the radiation patterns of relativistic electrons a qualitative picture is obtained, which explains the measured polar diagrams, assuming the electrons that produce the X-rays have velocity vectors lying roughly in a cone between the point of focus and the anode. The average electron energy is about 3keV at the focus and about 10 keV on the anode surface. Results are consistent with the converging beam model of neutron production.

Harries, W. L.↗