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At least 343 records · Page 19

Extended Bandwidth Spread Spectrum Time Domain Reflectometry Cable Test for Thermal Aging, Low Resistance Fault, and Water Detection

In 2022, researchers at Pacific Northwest National Laboratory (PNNL) used the Accelerated and Real-Time Environmental Nodal Assessment (ARENA) cable and motor test bed to characterize spread spectrum time domain reflectometry (SSTDR) and compare the responses of an SSTDR instrument to those of a frequency domain reflectometry (FDR) instrument. Results showed both techniques could detect and locate cable anomalies such as phase-to-phase low resistance and shorts, thermal insulation damage, mechanical insulation damage, and the presence or absence of water in some conditions. The SSTDR tests used a commercial instrument provided by LiveWire Innovations Inc. This commercial instrument performed tests at 6, 12, 24, and 48 MHz bandwidth. The results of these tests were compared to FDR tests where bandwidths could be extended up to 1.3 GHz, although the best responses for cable tests were from 100 to 500 MHz. Lower bandwidth signals can propagate better along the cable while higher bandwidths have higher resolution for impedance change reflections allowing more precise indication of location and separation of anomalies. The 2022 research found that FDR responses were clearer than SSTDR and speculated that a higher bandwidth SSTDR could more successfully detect and locate cable anomalies. One advantage of the SSTDR system investigated was that it was designed for energized online use up to 1,000 volts, which may be a significant advantage for nuclear power plant use. The LiveWire SSTDR instrument is an established product in the rail and aircraft industry and updating the SSTDR hardware parameters is difficult to justify without more conclusive testing. Therefore, a software adjustable laboratory SSTDR instrument was developed by PNNL and was used to test extended bandwidth SSTDR cable tests. Within the ARENA test bed, 42 cable conditions were tested with the PNNL SSTDR, FDR, and the LiveWire SSTDR—each operating at four different bandwidths. Observations and conclusions regarding the relative performance of the three instruments over different bandwidths are note below. Responses of the PNNL SSTDR (at 50 MHz) and the LiveWire SSTDR (at 48 MHz) were similar. The PNNL SSTDR higher frequency bandwidths behaved as expected showing sharper peaks and higher noise. This validated the PNNL SSTDR as a reasonable implementation of the SSTDR technology. Lower bandwidth SSTDR responses (particularly 6 and 12 MHz) may have increased value for use within longer cables but were not particularly effective at identifying anomalous cable behavior in the 100 ft cables tested here. The higher bandwidths of the PNNL SSTDR (50, 100, 200, and 400 MHz) did not provide substantially clearer cable reflectometry responses, but having the higher frequency responses available did add to the cable test evaluation. Strong responses to shorts and low impedance faults between phases were particularly evident in the higher bandwidth PNNL SSTDR and the FDR data. Measurements were repeatable, with similar responses obtained from a thermally aged cable for tests taken a month apart. Signal noise was affected in the unshielded cable by the local in-tray cable arrangement including proximity to metal edges and rungs of the cable tray. Foam isolation of the cable from the tray metal reduced in both FDR and SSTDR responses. Cable condition monitoring in nuclear power plants will likely benefit from both more informative off-line testing methods and from the development of on-line methods for continuous monitoring of cables in use. The LWRS-funded ARENA test bed was a valuable resource for this development and direct comparison of nuclear electrical cable condition monitoring technologies. Test results are targeted to guide industry advancement of testing and monitoring tools for cable aging management.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Anion Effects on the Interfacial Structure and Bulk Physical Properties in Choline-Based Hydrogen-Bonded Electrolytes

Electrolytes consisting of choline (Ch) salts with acetate (Ac) and oxalate (Ox) anions were studied in mixtures with ethylene glycol (EG), in comparison to chloride (Cl)- and bis(trifluorosulfonyl)imide (TFSI)-containing systems to understand the impact of anion size and charge density on the bulk electrolyte and interfacial properties. These represent hydrogen-bonded concentrated electrolytes where the Ch salts are the H-bond acceptors (HBAs) and EG is the H-bond donor (HBD) in 1:2 and 1:4 HBA:HBD ratios. Increased H-bonding in Ch 2 Ox with EG compacts the liquid compared to ChAc, consistent with the increased dissociation energies of the HBA:HBD clusters with Ox –2 calculated by density functional theory (DFT), thus leading to denser and more viscous liquids. Electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS) were used to investigate interfacial charge density and the electrode surface species. Differential capacitance curves demonstrate weak dependence on potential except for ChAc:EG, where Ac – is found to adsorb on the Au surface, in particular at +0.055 V vs Ag quasi-reference while no specific adsorption was observed on glassy carbon (GC). In situ SERS measurement confirms the formation of a surface layer in the ChAc:EG systems resulting from a Au–acetate interaction. Despite the structural similarities, Ox –2 did not show specific binding or any dependence of capacitance on potential as a result of strongly solvating EG molecules via H-bonds. Furthermore, this study shows that the charge density of the HBAs impacts both bulk properties and the electrical double-layer formation in concentrated H-bonded electrolytes that is relevant to electrochemical kinetics and morphology in electrodeposition processes and energy storage applications.

25 ENERGY STORAGE↗

A Compact, Single Stage, >1 kV Medium-Voltage Line Impedance Stabilization Network

This paper presents the design of a single-phase, single-stage line impedance stabilization network (LISN) for medium-voltage (MV) applications. More than 1 kV rated widebandgap (WBG) power semiconductor switches are increasingly utilized in new, emerging power electronics energy systems to improve power density and efficiency. However, due to inherently fast-switching speeds, WBG switch modules emit considerable electromagnetic interference (EMI) (e.g., common mode (CM) or differential mode (DM)). State-of-the-art offers standardized LISN solutions to validate and certify the new energy system for electromagnetic compatibility (EMC). However, most are for low voltage applications (i.e., < 1 kV). MV LISNs (i.e., > 1 kV) are rare until recently and literature does not provide sufficient guidelines for designing and characterizing such devices. It has been a critical challenge for many scientists and engineers to reliably certify the emerging MV energy systems (e.g., electric ships and aircraft). This paper addresses such a technology gap. Specifically, a CISPR 16-1-2 compliant 50Ω/50μH LISN with 1.5kV, 75A and 30MHz measurement capability has been proposed. Detailed performance study versus non-linear parasitic parameters variations in MV inductors and capacitors have been done. Based on new understandings, novel techniques to intuitively mitigate unwanted parasitic have been proposed to develop the proposed LISN successfully. Thorough characterization of important LISN parameters are presented and factors influencing them are analyzed. A rigorous analysis, experimental tests, and in-depth comparisons over state-of-the-art have been made to validate the effectiveness. This is done through the state-of-the-art 300kVA MV EMI testbed.

42 ENGINEERING↗

Ionic Diffusion in Slurry Electrolytes for Redox Flow Batteries

Slurry electrodes have been proposed as a method to decouple the storage and power capacities of hybrid redox flow batteries by allowing the reduced metal to adhere to a flowing dispersion of electrically conductive particles rather than accumulate in the flow cell. In this work, the ionic mass transport through these slurry electrolytes is investigated via voltammetry at a rotating disc electrode and in a parallel channel flow cell. A modified Levich equation, i l = 0.6 2 nFC ω 1 / 2 ν − 1 / 6 ( D + r 2 Φ ω m ) 2 / 3 , is developed to describe limiting currents to a rotating disc electrode when using a particle filled electrolyte. Mass transfer is demonstrated to be enhanced by greater particle loading so long as there are sufficient particles such that their respective flow velocity boundary layers interact. In the flow cell, faradaic current in a carbon black slurry electrolyte was observed to decrease over time. This suggests that the carbon particles adhere and accumulate on the stationary electrode, impeding mass transport by imposing diffusion path tortuosity. This accumulation is undesirable in hybrid redox flow batteries as it encourages metal deposition in the cell, limiting the scalability of the technology.

Electrochemistry↗

A Comprehensive Experimental Study on Microstructure‐Graded Graphite Anodes for Enhancing Fast‐Charging Capability of Lithium‐Ion Batteries

Lithium‐ion batteries with high gravimetric capacity density and improved cycle life performance under fast‐charging conditions are crucial for widespread electric vehicle (EV) adoption. This study investigates how designing graphite anode microstructure, specifically porosity, and particle‐size gradients, improves lithium‐ion (Li + ) transport during fast‐charging conditions. Three‐layered graphite anodes with varying porosity (24%, 36%, 46%) and particle size gradients (3, 5, 10 μm) were compared to a conventional single‐layered electrode in half‐cell configurations. At room temperature and high discharge rate (2C), both gradient structures showed significantly enhanced capacity retention (80% and 67% vs. 50%) compared to the conventional electrode, highlighting the effectiveness of microstructure engineering for fast charging. The study also investigated the temperature's impact on cycle life. After 200 cycles at 2°C and 45°C, all gradient structures demonstrated superior capacity retention (≈80%) compared to the conventional electrode (35%), suggesting the gradients mitigate degradation rate at high temperatures. Electrochemical impedance spectroscopy confirmed superior Li+ diffusion and lower resistivity in gradient electrodes. Simulations explored the influence of gradient profiles on reaction kinetics across the electrode thickness. Overall, this research demonstrates that the fast‐charging capability of graphite electrodes can be greatly enhanced by engineering the electrode microstructure, thereby making EV technology more accessible and appealing.

Ahmadi, Soma↗

Pitting behavior of friction stir repair-welded 304L stainless steel in 3.5% NaCl solution at room temperature: role of grain and defect structures

Stainless steel (SS) canisters used for storing spent nuclear waste are prone to chloride-induced stress corrosion cracking. Friction stir welding (FSW), being a low heat input process, can be used for repair welding of these canisters. In this study, an artificial crack was introduced on the 304L SS coupons by an electric discharge machining process. The artificial crack was repair-welded by FSW by maintaining the tool temperature a constant at two levels (725 and 825 °C). Friction stirring significantly reduced the grain size of the stirred zone (SZ) from about 47 to 2–4 μm. The fraction of low-angle grain boundaries increased in the SZ from 2 to 37–43%. Here, on the other hand, the fraction of special grain boundaries (Σ3 and Σ9) that was ~ 50% in the base metal reduced to < 10% in the SZ. During friction stirring, the oxide layer of artificial crack was broken and aligned to form a spiral defect called lazy-S structure. All these microstructural changes affected the corrosion behavior of the FSW specimens when tested in 3.5% NaCl at room temperature using cyclic polarization, chronoamperometry, and electrochemical impedance spectroscopy. The FSW specimens showed lower polarization resistance and lower transpassive potential than those of the base metal specimens. However, the pitting protection potentials of the FSW specimens were higher than that of the base metal. The pitting behavior of the FSW specimens was influenced more by the preferential attack on the lazy-S region than by passive film breakdown. The flat band potentials of the passive film formed on the FSW specimens were more positive than that of base metal. The charge carrier density of passive film formed on the FSW specimens was higher than that of the base metal. The higher fraction of low-angle grain boundaries present in the FSW specimens could supply more number of misorientation dislocations at the metal/film interface which could form anion vacancies by a climb process leading to formation of oxide at these locations without stressing the substrate. Therefore, low-angle boundaries are considered helpful for formation of stress-free passive films that will be highly stable and enhance both pitting and stress corrosion cracking resistance.

Dry storage canister↗

Multifunction Hydrophobic Ligand Engineered Cd(S, Se)/ZnS Quantum Dots for Stabilizing Highly Efficient Carbon‐Based Perovskite Solar Cells

The long-term operational stability of perovskite solar cells (PSCs) remains a key challenge impeding their commercialization, particularly due to ambient environments (e.g., moisture, oxygen, heat)-induced degradation. Carbon electrode-based PSCs have emerged as cost-effective and relatively stable alternatives to metal electrode-based devices due to carbon materials' hydrophobic behavior, yet they still lag in both long-term durability and power conversion efficiency (PCE). In this work, an ultrathin hydrophobic ligand-modified core–shell Cd(S,Se)/ZnS quantum dots (QDs) capping layer is introduced as a multifunctional interfacial modifier for carbon-electrode-based PSCs. This oleic acid ligand-modified QDs capping layer exhibits inherent hydrophobicity, effectively serving as a moisture barrier to retard perovskite degradation under ambient conditions. Furthermore, the strong interfacial bonding between the QDs and perovskite halide surfaces leads to efficient trap state passivation, reducing trap density and creating a more uniform electrical contact. The modified QDs/perovskite interface also features an elevated conduction band edge, promoting improved charge extraction. As a result, devices incorporating this quantum dot capping layer retain 98% of their initial PCE after 450 h of ambient aging and achieve a champion efficiency of 20.74%. As a result, this strategy highlights the potential of hydrophobic ligand-modified chalcogenide QDs as surface modifiers to enhance both the stability and performance of carbon-based PSCs, offering a promising route toward scalable fabrication of durable perovskite solar modules.

14 SOLAR ENERGY↗

Processing and properties of hafnium-doped tin-modified lead zirconate titanate 95/5 ceramics

Niobium (Nb)-doped lead-tin-zirconate-titanate (PSZT) ceramics near the lead-zirconate-titanate 95/5 orthorhombic AFE-rhombohedral FE morphotropic phase boundary (PSZT 13.5/81/5.5 -1.6Nb) were prepared with up to 10 mol.% of hafnium (Hf) substituted for zirconium. The ceramics were prepared by a traditional solid-state synthesis route and sintered to near full density at 1150°C for 6 h in sealed alumina crucibles with self-same material as the lead vapor source. All compositions were ~98% dense with no detectable secondary phases by X-ray diffraction. The grain size was ~3 μm for all compositions, consisting of equiaxed grains with intergranular porosity. The compositions exhibited remnant polarization values of ~32 μC/cm 2 . Depolarization by the hydrostatic pressure-induced FE-AFE phase transition occurred at 310 MPa for all compositions, resulting in a total depolarization output of 32.4 μC/cm 2 for the PSZT ceramics. Evaluation of the R3c-R3m and R3m-Pm $\bar{3}$ m phase transition temperatures by impedance spectroscopy showed temperatures on heating ranging from 86 to 92°C and 186 to 182°C, respectively, for increasing nominal Hf content. Thermal hysteresis of the phase transitions was also observed in the ceramics, with the transition temperature on cooling being 1–4°C lower. The study demonstrated that the PSZT ceramics are relatively insensitive to variations in Hf content in the range of 0 to 10 mol.%.

36 MATERIALS SCIENCE↗

Exploring Micro-Environmental Conditions of Urban Agrivoltaics: Advancing Sustainable Green Spaces and Agriculture in Temperate Cities

Agrivoltaics, the integrated land use combining renewable energy production and agriculture, can potentially address key challenges faced by urban communities, including limited access to vacant land, fresh produce, and electricity. However, urban agrivoltaics has rarely been considered a viable solution, primarily due to a lack of experimental systems demonstrating the functionality of urban food production or green spaces alongside solar energy production. To evaluate the potential of solar photovoltaics to help mitigate heat stress on urban agriculture and green spaces in a temperate climate, we examined the microclimatic changes introduced by an urban agrivoltaics system (UrAV) when combined with vegetable crops and turfgrass, respectively. Accordingly, we installed an experimental setup instrumented with environmental sensors to compare full-sun conditions with those of an agrivoltaics system designed for urban environments. We found minimal differences for both land cover types between the control and agrivoltaics sites in air and soil temperature. However, during periods of intensified summer heat, temperatures beneath the panels cooled due to reductions in wind speed and relative humidity, which impeded the movement of hot, moist air and reduced reference evapotranspiration. Further, soil moisture in UrAV was highly spatially heterogeneous, influenced by the layout of the photovoltaic panels and their support structure, which redistributed rainfall and controlled where solar radiation could penetrate and drive evapotranspiration. Overall, our results suggest that PV-induced environmental changes in temperate climates are compatible with cultivating turfgrass or appropriate crops. These findings can help planners and designers integrate agrivoltaics into community gardens, farms, and green spaces in temperate cities.

14 SOLAR ENERGY↗

Enhanced Switching Reliability of Hf 0.5 Zr 0.5 O 2 Ferroelectric Films Induced by Interface Engineering

Ferroelectric materials have been widely researched for applications in memory and energy storage. Among these materials and benefiting from their excellent chemical compatibility with complementary metal–oxide–semiconductor (CMOS) devices, hafnia-based ferroelectric thin films hold great promise for highly scaled semiconductor memories, including nonvolatile ferroelectric capacitors and transistors. However, variation in the switched polarization of this material during field cycling and a limited understanding of the responsible mechanisms have impeded their implementation in technology. Here, we show that ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) capacitors that are nearly free of polarization “wake-up”─a gradual increase in switched polarization as a function of the number of switching cycles─can be achieved by introducing ultrathin HfO 2 buffer layers at the HZO/electrodes interface. High-resolution transmission electron microscopy (HRTEM) reveals crystallite sizes substantially greater than the film thickness for the buffer layer capacitors, indicating that the presence of the buffer layers influences the crystallization of the film (e.g., a lower ratio of nucleation rate to growth rate) during postdeposition annealing. This evidently promotes the formation of a polar orthorhombic (O) phase in the as-fabricated buffer layer samples. Synchrotron X-ray diffraction (XRD) reveals the conversion of the nonpolar tetragonal (T) phase to the polar orthorhombic (O) phase during electric field cycling in the control (no buffer) devices, consistent with the polarization wake-up observed for these capacitors. The extent of T–O transformation in the nonbuffer samples is directly dependent on the duration over which the field is applied. Here these results provide insight into the role of the HZO/electrodes interface in the performance of hafnia-based ferroelectrics and the mechanisms driving the polarization wake-up effect.

36 MATERIALS SCIENCE↗

Development, Characterization, and Testing of Solid-State Electrolytes for Batteries

Traditional liquid electrolytes used in lithium (Li) metal batteries (LMBs) have severe safety issues, poor power density, as well as thermal and electrochemical instability that prevents their scaling to newer applications, such as electric vehicles. Using sulfide-based solid-state electrolytes (SSEs) is a viable method to address many of the issues that plague LMBs. However, the key issue preventing the expansion of sulfide-based SSEs is an interplay between poor interfacial stability with the electrodes and massive external stack pressure required to maintain electrode-electrolyte contact. The need for extensive pressure requires large system-level (i.e., battery pack used in an electric vehicle) housing that causes a disconnect between performance at a smaller scale and actual application. Secondary prevention to sulfide-based SSE adoption are difficulties in manufacturing, as toxic deterioration occurs when these materials are exposed to humidity, as well as drastic reduction in SSE performance at low temperature. This work hypothesizes that unique interfacial designs of electrodes and the modification of the sulfide-based SSE will enable reduction of necessary external cell pressure, and therefore support the design of practical LMBs. This will be done through collaboration within Idaho National Laboratory (INL), where manufacturing practices will be parameterized to produce low defect, low porosity SSEs with slight modifications. Next, artificial interfaces will be produced on electrodes to observe the conformality and mass transport properties between the modified SSE and pre-treated anode. External pressure on Li-metal cells will also be parameterized to reduce interfacial impedance while a reduction in the pressure will allot reasonable housing design for larger scale applications. Focus on novelty in this work occurs by modifications to the solid-solid interfaces between electrolyte and electrode, done through doping of the electrolyte and production of artificial interfaces on the Li-metal anode. The modifications at these interfaces, in addition to modified external pressure could identify and address the poor interfacial impedance that hinders high performance SSEs. Fundamental understanding on how to reduce the key hindrances of all-solid-state batteries (ASSBs) will support the advancement for larger scale production and performance, of which will be held in perspective for future works. Beyond battery development, the knowledge gained from process control and defect analysis is applicable to other ceramic systems, such as nuclear fuel coatings and high temperature electrolyzers.

25 ENERGY STORAGE↗

Development, Characterization, and Testing of Solid-State Electrolytes for Batteries

Traditional liquid electrolytes used in lithium (Li) metal batteries (LMBs) have severe safety issues, poor power density, as well as thermal and electrochemical instability that prevents their scaling to newer applications, such as electric vehicles. Using sulfide-based solid-state electrolytes (SSEs) is a viable method to address many of the issues that plague LMBs. However, the key issue preventing the expansion of sulfide-based SSEs is an interplay between poor interfacial stability with the electrodes and massive external stack pressure required to maintain electrode-electrolyte contact. The need for extensive pressure requires large system-level (i.e., battery pack used in an electric vehicle) housing that causes a disconnect between performance at a smaller scale and actual application. Secondary prevention to sulfide-based SSE adoption are difficulties in manufacturing, as toxic deterioration occurs when these materials are exposed to humidity, as well as drastic reduction in SSE performance at low temperature. This work hypothesizes that unique interfacial designs of electrodes and the modification of the sulfide-based SSE will enable reduction of necessary external cell pressure, and therefore support the design of practical LMBs. This will be done through collaboration within Idaho National Laboratory (INL), where manufacturing practices will be parameterized to produce low defect, low porosity SSEs with slight modifications. Next, artificial interfaces will be produced on electrodes to observe the conformality and mass transport properties between the modified SSE and pre-treated anode. External pressure on Li-metal cells will also be parameterized to reduce interfacial impedance while a reduction in the pressure will allot reasonable housing design for larger scale applications. Focus on novelty in this work occurs by modifications to the solid-solid interfaces between electrolyte and electrode, done through doping of the electrolyte and production of artificial interfaces on the Li-metal anode. The modifications at these interfaces, in addition to modified external pressure could identify and address the poor interfacial impedance that hinders high performance SSEs. Fundamental understanding on how to reduce the key hindrances of all-solid-state batteries (ASSBs) will support the advancement for larger scale production and performance, of which will be held in perspective for future works. Beyond battery development, the knowledge gained from process control and defect analysis is applicable to other ceramic systems, such as nuclear fuel coatings and high temperature electrolyzers.

25 ENERGY STORAGE↗

Electrolyte Study for High-Nickel LiNi 0.9 Mn 0.05 Co 0.05 O 2 Cathodes

With an increasing demand for intermittent renewable energy and electric vehicles, it is imperative to develop lithium-ion batteries with Earth-abundant cathode materials. Cobalt (Co) is preferred to be kept at a minimum because of its high cost and limited mining options, yet it has played an essential role in the high-performance transition metal oxides (TMOs). Herein, we report work from Argonne National Laboratory, conducted under the U.S. DoE's Vehicle Technologies Office, Deep Dive consortium on Next-Generation Cathodes, to optimize electrolytes for LiNi 0.9 Mn 0.05 Co 0.05 O 2 . LiNi 0.9 Mn 0.05 Co 0.05 O 2 is a high-Ni TMO benchmark as it outperforms most other TMOs under standard cycling conditions. In this study, we use the figure-of-merit approach to optimize electrolytes for this novel cathode material. Dual-salt carbonate electrolytes containing lithium difluorooxyphosphate and hexafluorophosphates were found to be the best for capacity retention and slowing the impedance rise. Importantly, transition metal dissolution and lithium inventory losses in the solid electrolyte interface were found to be the major causes for capacity fade.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring conductive networks within hollow carbon nanospheres to host phosphorus for advanced sodium ion batteries

The formidable sustainability challenges in advancing energy storage technologies call for game-changing research in battery designs. The previous pursuing of novel cathode materials with high redox potentials impedes the vast applications due to the simultaneous electrolyte decomposition at high potentials, though they are expected to deliver high specific capacities. Eventually, people start thinking in an opposite way, desirable anode materials with low redox potentials can also own high specific capacities. Among all the promising candidates, phosphorus-based anodes in sodium ion batteries (SIBs) have received considerable attention owing to the low cost and relatively high natural abundance of phosphorus. More importantly, phosphorus can store three sodium atoms and enable a high theoretical capacity of 2596 mAh g -1 , which overwhelms any other SIB anode currently available. However, the poor electronic conductivity and large volume change of phosphorus during cycling severely deteriorate battery performance. The most widely used strategy is to confine phosphorus within well-designed carbon hosts. Here, we thereby introduce a new type of porous hollow carbon with conductive-network interior as phosphorus host, which not only improves the electrical conductivity, but also creates enough interior surface for maximizing phosphorus utilization and shortening the ion's diffusion distance, compared to those conventional hollow carbon hosts. Therefore, the as-prepared red phosphorus-carbon spheres composites (RP/CS) exhibit superior rate performance (similar to 1083 mAh g -1 at 4 A g -1 , similar to 837 mAh g -1 even at 8 A g -1 ) and excellent cycle life (1027 mAh g -1 at 4 A g -1 more than 2000 cycles).

25 ENERGY STORAGE↗

Continuous MOF Membrane-Based Sensors via Functionalization of Interdigitated Electrodes

Three M-MOF-74 (M = Co, Mg, Ni) metal-organic framework (MOF) thin film membranes have been synthesized through a sensor functionalization method for the direct electrical detection of NO 2 . The two-step surface functionalization procedure on the glass/Pt interdigitated electrodes resulted in a terminal carboxylate group, with both steps confirmed through infrared spectroscopic analysis. This surface functionalization allowed the MOF materials to grow largely in a uniform manner over the surface of the electrode forming a thin film membrane over the Pt sensing electrodes. The growth of each membrane was confirmed through scanning electron microscopy (SEM) and X-ray diffraction analysis. The Ni and Mg MOFs grew as a continuous but non-defect free membrane with overlapping polycrystallites across the glass surface, whereas the Co-MOF-74 grew discontinuously. To demonstrate the use of these MOF membranes as an NO 2 gas sensor, Ni-MOF-74 was chosen as it was consistently fabricated as the best thin and homogenous membrane, as confirmed by SEM. The membrane was exposed to 5 ppm NO 2 and the impedance magnitude was observed to decrease 123× in 4 h, with a larger change in impedance and a faster response than the bulk material. Importantly, the use of these membranes as a sensor for NO 2 does not require them to be defect-free, but solely continuous and overlapping growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impacts of PTL coating gaps on cell performance for PEM water electrolyzer

The anode porous transport layer (PTL) is a critical component of polymer electrolyte membrane (PEM) water electrolyzers, providing electrical conduction and water/oxygen transport to the anode catalyst layer. Platinum group metal (PGM) coatings are applied to titanium PTLs to prevent oxidation and preserve conductivity. To implement PEM water electrolysis on a large scale, it is essential to minimize the cost of mass-manufactured cell components while ensuring that defects in materials and components do not adversely affect the performance of the cell. In this study, we created gaps in the Pt coatings that are typically applied to PTLs to understand their effects on cell performance and inform on fabrication tolerances. The PTL coatings were fabricated by sputter deposition of Pt, intentionally leaving uncoated regions in either large patches or thin strips. For either geometry, the cell performance decreased with the increasing fraction of the uncoated regions. However, PTLs containing multiple thin uncoated strips caused a less severe performance effect than PTLs with continuous uncoated regions of the same relative total area. Through analysis of cell performance, impedance, and 3D charge transport modelling, here we demonstrate that both the anode catalyst layer and membrane play a role in distributing current to mitigate the impact of coating defects at a short length scale. These results allow to draw conclusions about the tolerance requirements with regards to PTL coating uniformity in terms of both the size and total area of defects.

08 HYDROGEN↗

Electrochemical Healing of Dendrites in Garnet-Based Solid Electrolytes

Garnet oxides are a promising material family for solid-state batteries (SSBs). Dendrite formation in solid electrolytes critically limits the applicability of SSBs because of limiting Coulombic efficiency and power capability. In this study, the authors report operando electrochemical healing of dendrites in a garnet-based solid electrolyte (SE). Dendrites were deliberately formed at high operational current density (2 mA cm –2 ) beyond the critical current density (0.55 mA cm –2 ) of the used garnet SE. Electrochemical impedance spectroscopy and scanning electron microscopy were used to confirm dendrite growth in the SE. Dendrites were subsequently healed electrochemically via plating and stripping at 20 and 1 μA cm –2 current densities. Removal of dendrites was shown by an increase in bulk and interfacial resistance and a progressive increase in polarization during galvanostatic plating and stripping. High local current density at the dendrite tips was identified as the mechanism for preferentially removing dendrites electrochemically. The dendrite detection and healing methods discussed here are crucial for extending the life of SSBs.

25 ENERGY STORAGE↗

Electrochemical Characterization of Degradation Modes of High-Voltage Li x Ni 0.33 Mn 0.33 Co 0.33 O 2 Electrodes

While deeply charged high-voltage cathodes can improve battery energy density, understanding and preventing any accelerated cell degradation is crucial to practical success. Here, to analyze the degradation of LiNi x Mn y Co 1–x–y O 2 (NMC) type material charged to 4.3 and 4.5 V, a physics-based model is applied to cycling data to obtain parameter estimates indicative of degradation modes, which are validated by simple electrochemical measurements and further interpreted by materials characterization. Growth rates of interfacial impedance and active material loss are greater at 4.5 V, as might be expected. However, when charged to 4.5 V, degradation rates are initially lower at a cycling C-rate of 1.0 C than at 0.5 C. Once degradation mode changes are quantified, simulations evaluate the contribution of individual degradation mode to performance losses and provide estimates of the energy-power correlation (Ragone plots) of cells after cycling.

25 ENERGY STORAGE↗