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At least 73 records · Page 4

Surrogate Model Development of Spent Fuel Degradation for Repository Performance Assessment

In model simulations of deep geologic repositories, UO 2 fuel matrix degradation typically begins as soon as the waste package breaches and groundwater contacts the fuel surface. The initial degradation rate depends on the timing of these events, burnup of the fuel, temperature, and concentrations of dissolved reactants. Estimating the initial rate of degradation is fairly straightforward, but as UO 2 corrosion products precipitate on the fuel surface and the movement of dissolved species between the fuel surface and environment is impeded by the precipitated solids, the rate is more difficult to quantify. At that point, calculating the degradation rate becomes a reactive-transport problem in which a large number of equations must be solved by iteration for a large number of grid cells at each time step. The consequence is that repository simulations, which are already expensive, become much more expensive, especially when hundreds or thousands of waste packages breach. The Fuel Matrix Degradation (FMD) model is the process model of the Spent Fuel and Waste Science and Technology (SFWST) campaign of the US Department of Energy (DOE). It calculates spent fuel degradation rates as a function of radiolysis, redox reactions, electrochemical reactions, alteration layer growth, and diffusion of reactants through the alteration layer. Like other similar fuel degradation process models, it is a complicated model requiring a large number of calculations and iterations at each time step.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Remotely powered line monitor

Improved devices, apparatuses, systems, and methods involving the use of field probes with voltage-controlled variable impedance elements and surface-launched acoustic wave devices, including surface acoustic wave (SAW) devices and SAW sensor-tag wireless interface devices to measure voltage and current in current carrying conductors (CCCs) via measurement of the electric fields and magnetic fields around said CCCs are disclosed. The devices, apparatuses, systems, and methods taught in the present invention include a remotely powered line-mounted measurement unit that requires no connection to electrical ground for operation, and that has no internal energy source, no energy harvesting or power conditioning circuitry, no discrete energy storage components, and no radio. The devices, apparatuses, systems, and methods taught in the present invention also provide for determining the phase (leading or lagging) of the current relative to the voltage in AC power systems, and also provide for measurement of temperature of the conductor.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Carbon Mineralization of Sulfate Wastes Containing Pb: Synchrotron Pb M3-Edge XANES Analysis of Simultaneous Heavy Metal and Carbon Sequestration

Sulfate wastes are produced in large quantities and contain toxic heavy metals such as lead (Pb), posing environmental risks. Because of favorable solubility differences, these wastes can be repurposed for engineered carbon dioxide (CO 2 ) sequestration. Understanding the fate and mobility of heavy metals during this process is important. This study focuses on Pb and the effect of zinc (Zn) on Pb in carbon mineralization. Synthesized gypsum was treated with a carbonate-rich solution at pH 11.5 to convert the sulfates to carbonates. Aqueous solutions and mineral solids were analyzed. Synchrotron-based micro-X-ray fluorescence and a novel application of Pb M3-edge X-ray absorption near-edge structure provided detailed insights into Pb distribution and mineral forms. Results showed significant reductions in aqueous Pb and Zn concentrations, indicating effective metal sequestration. Carbon mineralization transformed Pb from soluble anglesite (PbSO 4 ) into insoluble cerussite (PbCO 3 ) and hydrocerussite (Pb 3 (CO 3 ) 2 (OH) 2 ). Pb primarily precipitated onto calcium carbonate surfaces through surface-mediated precipitation reactions. While the presence of Zn modified crystallization dynamics, it did not impede Pb sequestration and potentially enhanced surface reactivity, facilitating greater Pb immobilization. These findings highlight carbon mineralization as a sustainable approach to immobilize toxic metals in sulfate wastes while advancing CO 2 sequestration efforts.

54 ENVIRONMENTAL SCIENCES↗

In Situ Characterization of Surface Recombination in p-Si/SiO x Based Photoelectrochemical Cells

Time-resolved infrared (TRIR) and electrochemical impedance spectroscopy (EIS) were utilized to quantify surface states present at silicon oxide (SiO x ) protected crystalline p-Si electrolyte interfaces. The primary goal was to identify p-Si/SiO x photoelectrodes with both low surface recombination rates and efficient multi-electron transfer to an acceptor present in the external electrolyte. Three SiO x layers were investigated: native oxide (nOx), chemical oxide (cOx), and rapid thermal annealed (RTA) thermal oxide (tOx). Comparative study with [Ru(bpy) 3 ](PF 6 ) 2 as the electron acceptor indicated that tOx was most optimal with a small effective recombination rate, multi-electron transfer capability, and photovoltage of 500 ± 50 mV. A secondary goal was to analyze the surface recombination rates with the Shockley–Read–Hall (SRH) kinetic model. Two surface states were identified from this analysis, one closer to the CB edge (V t,1 ) and the other near the midgap (V t,2 ). EIS and SRH analyses revealed that a forming gas (5% H 2 /N 2 ) anneal (FGA) decreased surface recombination for tOx and nOx through a lower density of surface states. In the case of tOx, the infrared data indicated that V t,2 was completely removed. Here, the energetic positions of the band edges were correlated with the surface state density; low densities corresponded to more favorable potentials for inversion layer formation, which is expected to be most optimal for photocatalysis. Collectively this study indicates that the free carrier dynamics provided by TRIR represent a powerful in situ probe of the band edge and the surface state energetics in silicon based photoelectrochemical cells.

Electrochemical Impedance Spectroscopy↗

Direct Recycling of Lithium-Ion Battery Cathodes: A Multi-Stage Annealing Process to Recover the Pristine Structure and Performance

Direct recycling is an alternative low-cost process that retains the structure of the lithium-ion battery cathode rather than going through materials dissolution and repurification. While the process shows promise, various steps need to be better understood and studied to identify possible roadblocks, cost intensive steps, and needed variations in protocol that may be necessary based on the feedstock of recycled cathodes available. In this study, we have evaluated the process of thermal relithiation as it applies to end-of-life cathode materials. For recovered end-of-life cathodes, approximately 20% of the useable lithium has been lost due to solid electrolyte interface formation, parasitic reactions, and particle isolation; this lost lithium contributes to higher cell impedance and a gradual shift in electrode potentials. As a first step in the direct recycling process, this lithium needs to be restored not only to recover capacity but also to eliminate surface vacancies and hinder surface reconstruction that may increase impedance and impact performance. Here, we have optimized a coating method followed by a two-stage annealing process that restores a model delithiated NMC333 material to pristine performance. Comparisons to single-stage processes are made, and new characterization tools have been used to better understand the processes.

25 ENERGY STORAGE↗

In-situ and In-operando Cobalt Oxidation Studied by Atom Probe Tomography

Heterogeneous catalysis is one of the pillars of the chemical industry and the “green chemistry” concept. However, the sparse understanding of surface mechanisms at molecular scale impedes development of high-performance catalysts and requires development of new tools and methodologies. Cobalt is notably able to dissociate CO 2 into CO(g) and O 2 (g), allowing further conversion to higher value compounds such as long-chain hydrocarbons. Such application leads inevitably to Co surface oxidation. Finally, from its pure form (Co(0)) to oxidized ones (CoO and Co 3 O 4 ) the formation mechanism remains unclear as well as the surface structure evolution and its influence on the chemical reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Physical and Electrochemical Characterization of Aluminum Electrodes during Electrocoagulation

Electrocoagulation (EC) of synthetic groundwater was conducted using a sacrificial aluminum electrode in a flow-through EC reactor with short retention times (<1 min) under varying hydrodynamic and electrochemical conditions. The treated water was allowed to settle for 24 h and achieved silicate removal of up to 50 ± 4%, and hardness removal of 11 ± 1%. Physical, chemical, and electrochemical characterization was performed to explore changes in electrode surface morphology and composition. Electrochemical impedance spectroscopy (EIS) showed that chemical reactions at the electrode/water interface are sensitive to changes in the immediate chemical environment. We demonstrate that the most energy-intensive step in EC is aluminum dissolution at the anode, which remained fairly constant due to the continuous renewal of the anode’s surface, a result of aluminum dissolution. At the cathode, a structural change in the oxide layer, from γ-Al 2 O 3 to gibbsite, was detected by grazing-incidence X-ray diffraction, which decreased the resistance to charge transfer at the cathode surface, resulting in decreased electrode resistance. The high flow rate in the system minimized the accumulation of aluminum hydroxide solids and aluminum ions at the electrode/water interface, which minimized the formation of thick scalants and amorphous Al(OH) 3 on the cathode and anode, respectively. In conclusion, it was further demonstrated by EIS that under these conditions the resistance to charge transfer was constant throughout the duration of the experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetic study of hydrogen transport in graphite under molten fluoride salt environment

Here, in this work, a kinetic model, which describes the reactions occurring during the hydrogen charging process on a graphite surface, was optimized on Electrochemical Impedance Spectroscopic (EIS) to study the entry of hydrogen into graphite in high temperature molten FLiNaK salt. The results show that the rate constants of k 1 increases with decreasing applied potential (becoming more negative), and k 2 and k 3 are independent of the applied potential. At the same charging potential, all the three rate constants are independent of the water concentration in the FLiNaK salt. The surface coverage of absorbed hydrogen increases with decreasing the charging potential and increasing the moisture content in the salt. The adsorption efficiency of hydrogen increases with increasingly charging potential and decreases with increasing moisture content of the FLiNaK salt. These results demonstrate that EIS is a promising technique for measuring the kinetic parameters for hydrogen transport in graphite under molten fluoride salt environment.

EIS↗

Surface enhanced performance of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathodes by infiltration Pr-Ni-Mn-O progress

Herein the present study reports the enhancement of electrochemical oxygen reduction activity of porous La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ (LSCF) cathodes by coating a thin film of Pr-Ni-Mn oxide (PNM5) using a multi-step infiltration process. XRD examination reveals that PNM5 mainly contains a multiphase mixture of Pr 6 O 11 , PrNiO 3 , MnO and NiO. SEM morphology shows a thin PNM5 film and small particles are formed on the surface of LSCF backbone particles. Impedance spectrum analysis indicates that PNM5 infiltrated LSCF exhibits dramatically reduced polarization resistance (R p ), reaching R p of 0.244 Ω cm 2 at 973 K, which is one-half of the baseline LSCF cathode. The activation energy of LSCF cathodes infiltrated with PNM5 is 1.45 eV, slightly lower than the baseline LSCF cathode (1.77 eV). Distribution of relaxation time (DRT) function analysis shows PNM5 infiltration layer significantly promotes the oxygen reduction reaction (ORR) of cathode surface. With the increase in firing temperature, the total resistance increases and R p changes from ion transport to oxygen reduction reaction. Degradation rate of the PNM5-infiltrated LSCF is also lower, 0.02168% vs 0.07093% for the baseline LSCF over a 200-h period. A single cell testing indicated that the peak power density of the PNM5-infiltrated cell was increased by 140.66%. Overall, PNM5 could be a potential catalyst for boosting the performance of a commercial LSCF cathode for solid oxide fuel cells (SOFC).

36 MATERIALS SCIENCE↗

Impedance Response Influenced by Variability in the Random Distribution of Physical Properties of Coated Materials in Two-Dimensional Space

Heterogeneous physical characteristics of a system featuring a single-layer film on a metallic surface have been explored via its impedance response. The Nyquist plot showed a distorted semicircle, indicative of the system's unique distribution characteristics. Utilizing a copula-based probability method, a two-dimensional deterministic impedance model was successfully integrated, accounting for spatial physical properties such as permittivity and electrical conductivity. This strategy enabled in-depth exploration and mechanistic quantification of a broad spectrum of properties. A quantitative understanding of impedance signal alterations, characterized by normally or log-normally correlated variables, was achieved through the variation in aspect ratio and characteristic frequency of the impedance spectra. Log-normally distributed electrical properties provided a superior representation of the distorted impedance spectra. As coefficient of variation (CV) values fluctuated, the aspect ratio and characteristic frequency showed heightened sensitivity to log-normal permittivity compared to log-normal electrical conductivity. Notably, a marked positive linear correlation between electrical properties resulted in an impedance response that approximated perfect semicircular spectra. The variability in the electrical properties' distribution was demonstrated by considering the correlation coefficient between electrical conductivity and the z-direction position. Furthermore, the highest aspect ratio of the impedance spectra was observed when the electrical conductivity was randomly distributed across the z-direction space.

36 MATERIALS SCIENCE↗

xLi2MnO3 (1-x)LiMeO2 and Li4Ti5O12 Cell Chemistry for Behind-the-Meter Storage Applications

Li- and Mn-rich layered oxide material (xLi2MnO3 (1-x)LiMeO2, Me = Ni, Mn, and etc., LMR-NM) is paired with Li4Ti5O12 (LTO) in a full cell and evaluated for the Behind-the-Meter Storage (BTMS) applications. The LMR-NM/LTO full cell shows very high capacities and excellent long-term cycle life. It delivers 192 mAh g-1 after 500 cycles at C/2 and 45 degrees C with a capacity retention of 75% and coulombic efficiency higher than 99.95%. It also has impressive rate capabilities. A capacity of 220 mAh g-1 is achieved at 2C which is 88 % of the initial capacity at C/10. The high cycling temperature clearly enhances electrochemical kinetics and activates more Li2MnO3 component, which gives high capacities, low cell impedance, and better rate capabilities. Moreover, it helps to form a relatively thick cathode-electrolyte interphase (CEI) film to suppress transition metal dissolution from the cathode surface. The upper cut-off voltage (UCV) of 3.0 V keeps the structural integrity of the cathode during cycling. A higher UCV of 3.2 V accelerates structural instabilities of the cathode as well as growth of the solid-electrolyte interphase (SEI) via transition metal dissolution and deposition on the anode surface. It results in higher cell impedance, worse capacity retention and faster capacity fade.

behind-the-meter storage↗

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↗

Electroanalytical Investigation of the Electrode–Electrolyte Interface of Quaternary Ammonium Ionic Liquids: Impact of Alkyl Chain Length and Ether Functionality

The influence of ionic associations and potential-dependent interactions on the electrode–electrolyte interfacial structure of ionic liquids (ILs) is studied by electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS) for a variety of asymmetric quaternary ammonium ILs. Specifically, the impact of cation alkyl chain length (C = 4, 8 and 16) and ether functionality on the interfacial structuring of ILs at the glassy carbon electrode surface is examined. Ammonium cations with alkyl chain length of 8 and 16 carbons are found to stabilize the formation of the bis(trifluorosulfonyl)imide, [TFSI], anion dense Stern layer at positive electrode potentials leading to larger capacitances. The longer alkyl chain of the cation is believed to screen the ion–ion repulsion among the anions by intruding into the interfacial anion layer. SERS suggests the presence of carbon-containing rings at the interface at both positive and negative electrode potentials, which can be explained by the buckling of the long alkyl chains. Inclusion of an ether functionality allowed for more symmetry in the camel-shaped potential-dependent differential capacitance curves, suggesting similar excess ion density at both positive and negative potentials. This work contributes to understanding and predicting the interfacial electrode capacitance in ILs by understanding the balance of ionic interactions and the associated repulsions at electrode–electrolyte interfaces that are pertinent to electrochemical energy storage, electrocatalysis, and electrochemical sensors.

25 ENERGY STORAGE↗

Electric field reversals resulting from voltage waveform tailoring in Ar/O 2 capacitively coupled plasmas sustained in asymmetric systems

The etching of nanometer scale high-aspect-ratio (HAR) features into dielectric materials in low pressure radio frequency excited plasmas is often accompanied by charge accumulation inside the features which can slow etching rates and produce distortions such as twisting. The intra feature charging is at least partially produced by differences in electron and ion energy and angular distributions (EADs). Positive ions, accelerated to high energies having narrow angular spreads by the sheath electric field, can penetrate deeply into HAR features. Electrons typically arrive at the wafer with nearly thermal and isotropic distributions and do not penetrate deeply into HAR features. These disparities lead to differential charging of the inside of the feature, which can lead to reductions in etch rate and feature distortion due to ion deflection. With in-creasing aspect ratio of features, charging challenges are expected to continue for the foreseeable future. In this work, the use of tailored voltage waveforms in geometrically asymmetric capacitively coupled plasmas sustained in Ar/O 2 at 40 mTorr was computationally investigated with the goal of shaping the EAD of electrons incident onto the substrate to address differential charging. The tailored waveform consisted of a sinusoidal wave and its higher harmonics with a fundamental frequency of 1 MHz. Further, we found that electric field reversals in the sheath and presheath can occur during the anodic portion of the cycle. The electric field reversal increases the energy and decreases the angular spread of electrons incident onto the substrate. The magnitude of the electric field reversal can be controlled by the phase angle of the even harmonics and the gas composition. Due to its electronegative nature, increasing mole fractions of O 2 impedes electron transport to the surface which further increases the electric field reversal.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Mitigating CO 2 Corrosion of Natural Gas Steel Pipelines by Thermal Spray Aluminum Coatings

We report internal pipeline corrosion due to carbon dioxide (CO 2 ) is a major challenge facing the oil and gas industry. The objective of this study was to investigate the corrosion behavior of aluminum (Al)-based alloys as sacrificial coatings to protect pipelines in a CO 2 -saturated aqueous electrolyte (3.5 wt% NaCl) at 4 bar CO 2 partial pressure (3 bar) and 40°C. The corrosion resistance of Al-based alloys and thermal spray coatings was evaluated in an electrochemical reaction autoclave using electrochemical methods (potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy). Post-corrosion surface characterization was performed by scanning electron microscopy equipped with energy-dispersive x-ray spectroscopy. The obtained data show Al-based alloys demonstrated promising protection against CO 2 corrosion with no breakaway degradation issues.

36 MATERIALS SCIENCE↗

Trace Fe activates perovskite nickelate OER catalysts in alkaline media via redox-active surface Ni species formed during electrocatalysis

The accurate description of activity trends among perovskite-oxide oxygen-evolution-reaction (OER) catalysts using electronic-structure descriptors requires that the bulk structure of the catalyst is comparable to that of the surface. Few studies have addressed the dynamic nature of the catalyst's structure during the OER and the consequential implications for understanding activity. Here, we use a combination of electrochemical and materials-characterization techniques to study the surface reconstruction and the associated formation of a new redox-active phase on LaNiO 3 particles, LaNiO 3 epitaxial films, and an analogous Ruddlesden-Popper phase, La 2 NiO 4 . Small, but characteristic, redox features corresponding to Ni redox in nominally amorphous NiO x H y are observed during cyclic voltammetry of these initially fully crystalline materials. The size of these redox features grows with prolonged cycling and contributes to an increased surface area as determined from electrochemical impedance spectroscopy (EIS). Here we find the OER activity is strongly dependent on soluble Fe species in the electrolyte, common impurities in alkaline media. These observations are consistent with the reconstruction of the crystalline surface to form NiO x H y species and subsequent activation by adsorption of Fe forming the well-known and extremely active NiFeO x H y OER catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Extended Aqueous Processing on Structure, Chemistry, and Performance of Polycrystalline LiNi x Mn y Co z O 2 Cathode Powders

The prospect of aqueous processing of LiNi x Mn y Co z O 2 (NMC) cathodes has significant appeal to battery manufacturers for the reduction in materials cost, toxicological risk, and environmental impact compared to conventional N -methyl-2-pyrrolidone (NMP)-based processing. However, the effects of aqueous processing of NMC powders at industrial timescales are not well studied, with prior studies mostly focusing on relatively brief water washing processes. Here, we investigate the bulk and surface impacts of extended aqueous processing of polycrystalline NMC powders with different compositions. We demonstrate that at timescales of several hours, polycrystalline NMC is susceptible to intergranular fracture, with the severity of fracture scaling with the NMC nickel content. While bulk crystallinity and composition are unchanged, surface sensitive techniques such as X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) indicate that the exposure of water leads to a level of delithiation, nickel reduction, and reconstruction from the layered to rock-salt structure at the surface of individual grains. Dynamic single NMC microparticle compression testing suggests that the resulting mechanical stresses weaken the integrity of the polycrystalline particle and increases susceptibility of intergranular fracture. The initially degraded surfaces along with the increased surface area lead to faster capacity fade and impedance growth during electrochemical cycling. From this work, it is demonstrated that NMC powders require surface or grain boundary modifications to make industrial-scale aqueous cathode processing viable, especially for next-generation nickel-rich NMC chemistries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗