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At least 19 records

Can High Current Density HTS Magnets be Quench Protected Using Methods Used to Protect High Current Density LTS Magnets?

In the 1970s the Lawrence Berkeley Laboratory (LBL) was testing high current density magnets where the EJ 2 limit was up to two orders of magnitude higher than the quench protection methods of the period would permit at the time. LBL was designing a high current density (J) thin solenoid with a large volume and stored energy (E). The accepted EJ 2 limit at the time was ~10 23 J A 2 m -4 . In order to exceed the EJ 2 limit by two orders of magnitude, one had to greatly increase the quench protection voltages (V) and magnet current (I). In 1977, LBL tested four quench protection methods on a 2-meter diameter high current density solenoid with a stored energy of 2 MJ. Three of these quench protection methods worked well, but the fourth didn't appear to work. These methods will be discussed as to whether they can be applied to HTS or MgB 2 high current density magnets.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optical analysis of III-nitride micro-light-emitting diodes with different sidewall treatments at low current density operation

Here, in this work, the optical efficiency of III-nitride blue micro-LEDs (μLEDs) ranged from 5 × 5 to 60 × 60 μm 2 with different sidewall treatments at low current density range was investigated. The results showed dielectric sidewall passivation using atomic layer deposition (ALD) has superior optical enhancement compared to conventional RF sputtering, where most of the enhancement occurred at low current density range. Additionally, the use of ALD sidewall passivation and chemical treatment offered significant efficiency improvement for different sizes of μLEDs at operating less than 1 A cm −2 and the devices without sidewall treatments did not emit light. The effect of sidewall treatments to the effective Shockley–Read–Hall (SRH) nonradiative recombination coefficient, or the effective A coefficient from the ABC model, was estimated. The effective SRH nonradiative recombination coefficient was suppressed by two orders of magnitude for devices with sidewall treatments compared to devices without sidewall passivation.

Wong, Matthew S.↗

Thin Cation-Exchange Layers Enable High-Current-Density Bipolar Membrane Electrolyzers via Improved Water Transport

With suitable water dissociation (WD) catalysts, bipolar membranes (BPMs) can efficiently dissociate water into H + and OH – at the junction between anion- and cation-exchange layers (AEL and CEL, respectively). First, however, water must be transported through the AEL or CEL and thus against the outward flow of hydrated H + and OH – . This is a challenge intrinsic to the BPM architecture and limits operation to current densities typically less than ~0.5 A·cm –2 . Here we explore how water transport affects durability and performance in reference alkaline and acidic membrane electrolyzers, and we use the insight gained to design BPMs with improved water transport. We demonstrate a thin-CEL BPM (2-μm Nafion CEL|~200 nm TiO 2 |~200 nm NiO + ionomer|50 μm Sustainion AEL) which maintains a pH difference of ~14 units between the anode and cathode for current densities of up to 3.4 A·cm –2 with a total water electrolysis voltage of ~4 V and an estimated WD overpotential of ~1.5 V. Finally, such high-current-density operation is crucial for key emerging BPM applications, including in water and carbon-dioxide electrolyzers and in (regenerative) fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Influence of Current Density on Transport of Vanadium Acetylacetonate through a Cation-Exchange Membrane

Fluxes of negatively charged, neutral, and positively charged vanadium acetylacetonates through the cation-exchange membrane Nafion® 211 were measured as functions of current density. Fluxes increase in order V(C 5 H 7 O 2 ) 3 – < V(C 5 H 7 O 2 ) 3 0 < V(C 5 H 7 O 2 ) 3 + as expected for a membrane with fixed negative charges. Furthermore, the dependence of these fluxes on current density is quantitatively consistent with predictions made using independently measured conductivities in Nernst-Planck-Einstein transport equations. However, differences between the three fluxes are smaller than predicted by Donnan equilibrium calculations for Nafion 211 immersed in V(C 5 H 7 O 2 ) 3 solutions. Furthermore, specific interactions between sorbed species appear to be responsible for the relatively rapid transport of V(C 5 H 7 O 2 ) 3 – compared to V(C 5 H 7 O 2 ) 3 + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Current Density Durability of Pt/C and PtCo/C Catalysts at Similar Particle Sizes in PEMFCs

The durability of carbon supported PtCo-alloy based nanoparticle catalysts play a key role in the longevity of proton-exchange membrane fuel cells (PEMFC) in electric vehicle applications. To improve its durability, it is important to understand and mitigate the various factors that cause PtCo-based cathode catalyst layers (CCL) to lose performance over time. These factors include i) electrochemical surface area (ECSA) loss, ii) specific activity loss, iii) H + /O 2 -transport changes and iv) Co 2+ contamination effects. We use a catalyst-specific accelerated stress test (AST) voltage cycling protocol to compare the durability of Pt and PtCo catalysts at similar average nanoparticle size and distribution. Our studies indicate that while Pt and PtCo nanoparticle catalysts suffer from similar magnitudes of electrochemical surface area (ECSA) losses, PtCo catalyst shows a significantly larger cell voltage loss at high current densities upon durability testing. The distinctive factor causing the large cell voltage loss of PtCo catalyst appears to be the secondary effects of the leached Co 2+ cations that contaminate the electrode ionomer. A 1D performance model has been used to quantify the cell voltage losses arising from various factors causing degradation of the membrane electrode assembly (MEA).

08 HYDROGEN↗

Evaluation of current density measurement methods for high-current, low-beta electron beams

Recent current density measurements with a low-beta electron beam (β=0.5-0.75) are strongly affected by electron scatter and Cherenkov limits. These invasive measurements are heavily influenced by the electron energy and the intercepting material properties: density, index of refraction, and atomic number. We evaluate various measurement methods, including x-ray scintillation and Cherenkov emission. To optimize the x-ray scintillation technique for this energy regime, metal foils of differing atomic number (Z) and thickness were placed upstream of a scintillation screen. We have selected Cherenkov emitters, based on a material refractive index, in order to differentiate the contributions from electron scatter and produced fluorescence, Cherenkov emission, and total internal reflection. The observed distributions for both approaches are verified through MCNP6®. Additionally, the simulations provide insight as to what physical processes dominate the measured distribution. We conclude by determining the limits and optimal measurement range for each measurement technique.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Current Density Regulated Atomic to Nanoscale Process on Li Deposition and Solid Electrolyte Interphase Revealed by Cryogenic Transmission Electron Microscopy

Current density has been perceived to play a critical rule for controlling Li deposition morphology and solid electrolyte interphase (SEI). However, the atomic level mechanism of current density on Li deposition and the SEI remains unclear. In this work, based on cryogenic transmission electron microscopy imaging combined with energy dispersive X-ray spectroscopy and electron energy loss spectroscopy electronic structure analyses, we reveal the atomic level correlation of Li deposition morphology and SEI with current density. We discover that increasing current density leads to increased overpotential for Li nucleation and growth, leading to the transition from growth-limited to nucleation-limited mode for Li dendrite. Independence of current density, the electrochemically deposited Li metal (EDLi) exhibits crystalline whisker-like morphology. The SEI formed at low current density (0.1 mA cm -2 ) is monolithic amorphous; while, a current density of above 2 mA cm -2 leads to a mosaic structured SEI, featuring an amorphous matrix with Li 2 O and LiF dispersoids, and the thickness of the SEI increases with the increase of current density. Uniquely, the Li 2 O particles is spatially located at the top surface of the SEI, while LiF is spatially adjacent to the Li-SEI interface. These results highlight the possible tuning of crucial structural and chemical features of EDLi and SEI through altering deposit conditions and consequently direct correlation with electrochemical performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Limiting Current Density in Single-Ion-Conducting and Conventional Block Copolymer Electrolytes

The limiting current density of a conventional polymer electrolyte (PS-PEO/LiTFSI) and a single-ion-conducting polymer electrolyte (PSLiTFSI-PEO) was measured using a new approach based on the fitted slopes of the potential obtained from lithium-polymer-lithium symmetric cells at a constant current density. The results of this method were consistent with those of an alternative framework for identifying the limiting current density taken from the literature. We found the limiting current density of the conventional electrolyte is inversely proportional to electrolyte thickness as expected from theory. The limiting current density of the single-ion-conducting electrolyte was found to be independent of thickness. There are no theories that address the dependence of the limiting current density on thickness for single-ion-conducting electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes

Hybrid organic-inorganic block copolymer electrolytes are of interest to enable batteries containing lithium metal anodes. The conductive block is a standard polymer electrolyte of poly(ethylene oxide) and the mechanically rigid block is an inorganic poly(acryloisobutyl polyhedral oligomeric silsesquioxane) polymer. Here, in this paper, we compare a poly(acryloisobutyl polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS) triblock copolymer and a poly(ethylene oxide)-b- poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide salt. We have experimentally measured the limiting current density in lithium symmetric cells containing hybrid organic-inorganic electrolytes at 90 °C. The cells were polarized at a large range of applied current density. The diblock copolymer electrolyte exhibited a clear plateau in cell potential at all current densities below the limiting current density. At low applied current density, the triblock copolymer electrolyte also exhibited a clear plateau in cell potential. At currents approaching the limiting current density, the triblock copolymer electrolyte exhibited an underdamped potential profile. The cell potential did not reach a plateau at current densities above the limiting current in both systems. The diblock and triblock copolymer electrolytes were fully characterized using electrochemical methods to determine the ionic conductivity, cation current fraction, salt diffusion coefficient, and open circuit voltage as a function of salt concentration. Cell potential and salt concentration as functions of position in the cell at various current densities were calculated using Newman's concentrated solution theory. The theoretical limiting current density was calculated to be the current density at which salt is depleted at the cathode. We see quantitative agreement between experimental measurements and theoretical predictions for the limiting current density in the diblock copolymer electrolyte which has an ordered structure at all salt concentrations, while the experimental limiting current density is lower than the theoretical prediction for the triblock copolymer electrolyte, which exhibits a disordered morphology at high salt concentrations.

25 ENERGY STORAGE↗

Periodic Porous 3D Electrodes Mitigate Gas Bubble Traffic during Alkaline Water Electrolysis at High Current Densities

We report alkaline water electrolysis at high current densities is plagued by gas bubble generation and trapping in stochastic porous electrodes (e.g., Ni foams), which causes a significant reduction in the number of electrolyte accessible catalyst active sites. Here, 3D printed Ni (3DPNi) electrodes with highly controlled, periodic structures are reported that suppress gas bubble coalescence, jamming, and trapping and, hence, result in rapid bubble release. The 3DPNi electrodes decorated with carbon-doped NiO achieve a high current density of 1000 mA cm -2 in 1.0 m KOH electrolyte at hydrogen evolution reaction and oxygen evolution reaction overpotentials of 245 and 425 mV, respectively. This work demonstrates a new approach to the deterministic design of 3D electrodes to facilitate rapid bubble transport and release to enhance the total electrode catalytic activity at commercially relevant current densities.

08 HYDROGEN↗

Morphological Degradation of Oxygen Evolution Reaction-Electrocatalyzing Nickel Selenides at Industrially Relevant Current Densities

We investigated electrodeposited nanoparticulate nickel selenide (pre)catalysts that transform into nickel oxides/ oxyhydroxides under oxygen evolution reaction conditions in alkaline solutions. Previous studies of this transformation were conducted at lower current densities than those of industrial relevance (≥1 A cm −2 ). We used ultramicroelectrodes (UMEs) to achieve such current densities, benefiting from their small size, ensuring low absolute currents and low ohmic drop but high current densities. Morphological degradation of the catalyst material was only observed at current densities exceeding 1 A cm −2 but not for smaller ones. Using X-ray absorption, Xray photoemission spectroscopy, and X-ray diffraction, we confirmed that the degradation was accompanied by the literature-known transformation of nanoparticulate Ni 3 Se 2 (bulk)/NiSe (surface) into nickel oxyhydroxide. The transformation of the precatalyst goes along with a significant improvement in the charge transfer kinetics observed by decreasing Tafel slopes with ongoing experimental time extracted from cyclic voltammetry (CV) experiments and electrochemical impedance spectroscopy (EIS) in the high-frequency range. However, these kinetic improvements are accompanied by limitations in mass transport concluded from decreasing current responses at high overpotentials in CVs and increasing impedance in the low-frequency range of the EIS spectra after extended CV cycling. These mass transport limitations originated from morphological degradations at the UME exceeding 1 A cm −2 which we proved by applying identical location scanning electron microscopy. This has not been reported in studies that have been limited to lower current densities before. Our findings showcase how UMEs can be used to study (pre)catalysts (herein nickel selenides) under current densities of industrial relevance in the absence of ohmic drop-related ambiguities, combined with in-depth materials characterization studies, e.g., identical location microscopy and advanced spectroscopic methods. This approach enables direct evaluation and comparison of catalyst materials and thus demonstrates how to overcome long-standing limitations of electrocatalyst design and testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling the electrochemical behavior and interfacial junction profiles of bipolar membranes at solar flux relevant operating current densities

A 1-dimensional, multi-physics model that accounts for the migration and diffusion of solution species, electrostatics, and chemical reactions, in particular water dissociation (WD), at bipolar membrane (BPM) interfaces was developed to study the electrochemical behavior of bipolar membranes (BPMs) at solar flux relevant operating current densities (tens of mA cm -2 ). Significant partial current densities for WD were observed at BPM voltages much less than the equilibrium voltage, e.g., 59 mV × ΔpH from both experiments and modeling. The co-ion leakage across the BPM at pH differentials accounted for the early presence of the partial current density for WD. Two distinctive electric field dependent WD pathways, the un-catalyzed pathway and the catalyzed pathway, were quantitatively and parametrically studied to improve the turn-on potential of the BPM. The catalyzed pathway accounted for the majority of the partial current density for WD at low voltages, while the un-catalyzed pathway dominated the WD at relatively high voltages. Significant WD was observed only within the interfacial CL (<5 nm), in which a large electric field was present. To improve the electrochemical behavior and the turn-on potential of BPMs, the impacts of the pKa of the immobilized WD catalysts, the electric-field dependent rate constant, the thickness of the catalyst layer and fixed charge density in BPMs on the partial current densities for WD were studied systematically. In addition, the electrochemical behavior and concentration profiles of BPMs in a buffered electrolyte were studied and contrasted with those in an un-buffered electrolyte from both modeling and experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Current Density Cables for Simpler HTS Magnets in Fusion Energy Systems

High current density cables are needed for the engineering design of potentially low cost, simpler geometry high temperature superconducting (HTS) magnets in the promising magnetic configurations as a fusion pilot plant (FPP) option. Significant technology maturation efforts are underway by privately funded startups with the goal to demonstrate mature HTS magnet technology. Test results, however, indicate critical engineering issues remain to be addressed to meet performance goals, and demonstrate HTS coil operation repeatability and reliability. To this end, exploring and enabling multiple viable conductor and cable options is vital. Partnering with a private fusion startup and manufacturers of superconducting strands and cables, Princeton Plasma Physics Laboratory (PPPL) is exploring and seeking to de-risk the aggressive high field approach presently targeted by others. Our main objective is to develop, test and calibrate novel high current density cables for a broad deployment of affordable and reliable coils using Bi-2212 conductors. If successful, such a project will provide technical feasibility for promising FPP configurations including spherical tokamaks (ST) and compact stellarators. Here, we aim at the state-of-the-art Bi-2212 cable technologies toward a current density of 100 A/mm 2 at 16 T and 4.2 K–10 K operation for low cost, simpler geometry toroidal field (TF) coils for compact stellarators developed by fusion startup companies on a timeline consistent with the FPP initiatives and beyond.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Semi-solid alkali metal electrodes enabling high critical current densities in solid electrolyte batteries

The need for higher energy density rechargeable batteries has generated interest in alkali metal electrodes paired with solid electrolytes. However, metal penetration and electrolyte fracture at low current densities have emerged as fundamental barriers. Here, we show that for pure metals in the Li-Na-K system, the critical current densities scale inversely to mechanical deformation resistance. Furthermore, we demonstrate two electrode architectures in which the presence of a liquid phase enables high current densities while preserving the shape retention and packaging advantages of solid electrodes. First, biphasic Na-K alloys show K + critical current densities (with K-β*-Al 2 O 3 electrolyte) that exceed 15 mA∙cm -2 . Second, introducing a wetting interfacial film of Na-K liquid between Li metal and Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO) solid electrolyte doubles the critical current density and permits cycling at areal capacities exceeding 3.5 mAh∙cm -2 . These design approaches hold promise for overcoming electro-chemo-mechanical stability issues that have heretofore limited performance of solid-state metal batteries.

25 ENERGY STORAGE↗

Sub-100 mA/cm 2 CO 2 -to-CO Reduction Current Densities in Hierarchical Porous Gold Electrocatalysts Made by Direct Ink Writing and Dealloying

While most research efforts on CO 2 -to-CO reduction electrocatalysts focus on boosting their selectivity, the reduction rate, directly proportional to the reduction current density, is another critical parameter to be considered in practical applications. This is because mass transport associated with the diffusion of reactant/product species becomes a major concern at a high reduction rate. Nanostructured Au is a promising CO 2 -to-CO reduction electrocatalyst for its very high selectivity. However, the CO 2 -to-CO reduction current density commonly achieved in conventional nanostructured Au electrocatalysts is relatively low (in the range of 1–10 mA/cm 2 ) for practical applications. In this work, we combine direct ink writing-based additive manufacturing and dealloying to design a robust hierarchical porous Au electrocatalyst to improve the mass transport and achieve high CO 2 -to-CO reduction current densities on the order of 64.9 mA/cm 2 with CO partial current density of 33.8 mA/cm 2 at 0.55 V overpotential using an H-cell configuration. Although the current density achieved in our robust hierarchical porous Au electrocatalyst is one order of magnitude higher than the one achieved in conventional nanostructured electrocatalysts, we found that the selectivity of our system is relatively low, namely 52%, which suggests that mass transport remains a critical issue despite the hierarchical porous architecture. We further show that the bulk dimension of our electrocatalyst is a critical parameter governing the interplay between selectivity and reduction rate. In conclusion, the insights gained in this work shed new light on the design of electrocatalysts toward scale-up CO 2 reduction and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid synthesis of phase-engineered tungsten carbide electrocatalysts via flash joule heating for high-current-density hydrogen evolution

Fabricating durable and high-performance electrocatalysts operating at high current densities for industrial acidic hydrogen evolution remains a daunting challenge. Tailoring the phase composition of electrocatalysts is a promising strategy to harness synergistic effects and improve charge transfer, thereby optimizing their performance. Here, this work presents a fast, green method based on flash joule heating (FJH) to synthesize phase-engineered tungsten carbide electrocatalysts for the acidic hydrogen evolution reaction (HER) at high current densities. Tungsten carbide electrodes with varying FJH treatment durations (3, 10, 30, and 60 s) are fabricated to fine-tune the mixture of tungsten monocarbide (WC) and tungsten semicarbide (W 2 C) phases. Results show that samples with a 30-s treatment (TC-3) exhibit an optimal balance between these phases, leading to a low overpotential of 180.97 and 387 mV at current densities of 10 mA/cm 2 and 4 A/cm 2 , respectively. TC-3 exhibits significantly lower charge transfer resistance compared to the other electrocatalysts, which can be attributed to its optimal phase ratio. Notably, the TC-3 electrocatalyst remains stable for over 9 days at 4 A/cm 2 due to their controlled phases and excellent corrosion-resistant properties. This work highlights a new method to fabricate cost-effective, high-performance tungsten carbide electrocatalysts with well-controlled phase compositions.

Acidic hydrogen evolution reaction↗

Investigations on the effect of current density on SiO/Si composite electrodes

An oxide layer on the surface of silicon particles is inevitable and is necessary for their application as anode materials for lithium ion batteries with high capacity and durability. However, a thick surficial oxide layer could significantly reduce the capacity of a Si anode. Here, Si nanoparticles with a thick surficial oxide layer of ~20 nm (Si@SiO x ) were fabricated through thermal oxidation and investigated electrochemically. The results revealed that very low current density is needed to activate Si@SiO x anodes during the first formation cycle. Once activated, the Si@SiO x anode can deliver reversible capacity as high as ~1000 mAh/g with low current density. Then, the Si@SiO x can be cycled at higher current densities of >700 mAh/g. Electrochemical impedance spectroscopy (EIS) shows that the lower current density results in lower charge-transfer resistance of the Si@SiO x anode, suggesting a higher degree of lithiation of the surficial oxide layer during low-current activation. EIS analysis also reveals that the lithiation of the surficial oxide is irreversible. We believe that the surface silicon oxide layer is lithiated and forms lithium silicate during the initial activation process. Lithium silicate has high conductivity and allows the lithiation/delithiation of Si core under the oxide layer during following charge and discharge.

25 ENERGY STORAGE↗