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DOE OSTI2025

Implementing hydrogen oxidation reaction on Pt for controlling counter electrode processes

The search for active, stable, and durable materials for electrochemical energy technologies requires increasing levels of precision to establish true structure-function relationships and guide materials design from atomic and molecular scale. This increases the level of control required over the experimental system for proper materials evaluation. The choice of counter electrode material become crucial, as Pt dissolution at high voltages may cause contamination to the working electrode, especially when studying reductive processes in reactions such as oxygen reduction reaction (ORR), H 2 evolution reaction (HER), and the CO 2 reduction reaction. The learnings from “old school” electrochemistry groups lead us to leverage H 2 reactions over Pt to construct a counter electrode system with controlled potential that eliminates Pt ion contamination concerns. In here we discuss the construction of such Pt|H 2 counter electrode where key experimental aspects such as the H 2 flow rate and effective distribution determines the maximum current this counter electrode can accommodate before switching to high voltage and triggering Pt dissolution. Lastly, we demonstrate the use of the Pt|H 2 counter electrode in aqueous electrolytes during HER occurring on the working electrode at varying currents, showing that the Pt content in the cell remains below parts per trillion (ppt) up to 10 mA, and below 50 ppt at 100 mA up to 1 h of constant current hold. This work provides a guide to the implementation of Pt|H 2 counter electrodes to improve the precision of electrochemical experiments in search of highly active, selective, and durable materials for energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Removal of Na + and Ca2 + with Prussian blue analogue electrodes for brackish water desalination

Desalination of brackish water sources is critical to addressing the growing global freshwater demand. One promising approach is electrically driven desalination using intercalation electrodes. While intercalation electrodes have been widely researched for energy storage applications, only a small subset of those materials is suitable for desalination. In this work, we report the synthesis, characterization, and in-device testing of three Prussian blue analogue intercalation compounds: copper, manganese, and zinc hexacyanoferrate with formulas K x M[Fe(CN) 6 ] z ·nH 2 O (M = Cu, Mn, Zn). The desalination performance for each of these materials against carbon electrodes is reported for Na + intercalation and for Ca 2+ intercalation using 1000 ppm NaCl and 1000 ppm CaCl 2 feed solutions, respectively. While the copper and manganese analogs showed promising performance for Na + and Ca 2+ intercalation, the zinc compound was unstable and underwent rapid dissolution. Manganese hexacyanoferrate showed the best desalination performance in terms of salt removal capacities and salt removal rates with NaCl while copper hexacyanoferrate performed the best with CaCl 2 . The manganese analog proved to be the most stable intercalation material, retaining 83% and 72% of its salt removal capacity after 280 cycles in NaCl and CaCl 2 feed solutions respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Chemical durability and surface alteration of lanthanide zirconates (A 2 Zr 2 O 7 : A = La-Yb)

Chemical durability of lanthanide zirconates (A 2 Zr 2 O 7 ) (A = La-Yb) under near-field environments is important for evaluating their application as potential nuclear waste forms. In this work, A 2 Zr 2 O 7 (A = La-Yb) are synthesized by spark plasma sintering with controlled microstructure and their chemical durability are evaluated in a nitric acid solution (pH = 1). Scanning transmission electron microscopy analysis reveals an amorphous passivation film either enriched with Zr or lanthanide. The complex chemistry of the passivation films can be correlated with a transition in corrosion mechanisms from a preferential release of lanthanide in La 2 Zr 2 O 7 to a preferential release of Zr in Er 2 Zr 2 O 7 and Yb 2 Zr 2 O 7 . These results suggest a dominant mechanism of incongruent dissolution and surface reorganization for the formation of passivation films. Strong correlations are identified between the leaching rates and cation ionic size, ionic potential, electronegativity differences between A-site cation and Zr, and bonding valence sum of oxygen, suggesting important impacts of structural and bonding characteristics in controlling chemical durability of lanthanide zirconates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2025

CFD modeling and simulation for corrosive wear of refractory in molten slag

The development of high-wear resistant refractories having minimal production costs is facilitated by characterizing the wear mechanisms associated with their corrosive wear. Static cup testing is a commonly used method for comparing the corrosion resistance performance of two or more refractory materials. Although the static cup test conditions are not as severe as dynamic tests, this study shows that the thermal gradient present within the system during heating and cooling stages serves to generate movement of the slag leading to mechanical wear. The thermal gradient within the refractory, and between the slag and the refractory, occurs during the ramp stage of the test and lasts until the soaking stage is reached bringing the system to a thermal equilibrium. Using computational fluid dynamics (CFD) capabilities embedded within ANSYS software, this study modelled and quantified the convection currents within the slag and associated shear stresses generated on the refractory walls due to the thermal gradient. A traditional ladle furnace was employed as a case study to verify the results of the studied CFD model. The corrosion rate of the refractory lining was found to depend on the mass transfer coefficient of the refractory dissolution into the slag, and a velocity term which governs the extent of corrosion at any given location. This velocity term is a function of slag viscosity, as well as the concentration gradient and/or temperature gradient at the triple points. In this study, wall shear stress was used as a reliable proxy for identifying high-velocity regions prone to excessive corrosive wear. Elevated wall shear stress near the slag/air and slag/molten steel interfaces align with observed corrosion grooves, which reflects the intensified corrosive wear at these locations.

Ramteke, Rajat Rajat Durgesh Ramteke [University o↗

NASA NTRS1993

Rates of oxidative weathering on the surface of Mars

A model of acid weathering is proposed for the iron-rich basalts on Mars. Aqueous oxidation of iron sulfides released SO4(2-) and H(+) ions that initiated the dissolution of basaltic ferromagnesian silicates and released Fe(2+) ions. The Fe(2+) ions eventually underwent ferrolysis reactions and produced insoluble hydrous ferric oxide phases. Measurements of the time-dependence of acid weathering reactions show that pyrrhotite is rapidly converted to pyrite plus dissolved ferrous iron, the rate of pyrite formation decreasing with rising pH and lower temperatures. On Mars, oxidation rates of dissolved Fe(2+) ions in equatorial melt-waters in contact with the atmosphere are estimated to lie in the range 0.3-3.0 ppb Fe/yr over the pH range 2 to 6. Oxidation of Fe(2+) ions is estimated to be extremely slow in brine eutectic solutions that might be present on Mars and to be negligible in the frozen regolith.

Burns, Roger G.↗

DOE OSTI2023

Free‐Standing α‐MoO 3 / Ti 3 C 2 MXene Hybrid Electrode in Water‐in‐Salt Electrolytes

While transition‐metal oxides such as α‐MoO 3 provide high capacity, their use is limited by modest electronic conductivity and electrochemical instability in aqueous electrolytes. Two‐dimensional (2D) MXenes, offer metallic conductivity, but their capacitance is limited in aqueous electrolytes. Insertion of partially solvated cations into Ti 3 C 2 MXene from lithium‐based water‐in‐salt (WIS) electrolytes enables charge storage at positive potentials, allowing a wider potential window and higher capacitance. Herein, we demonstrate that α‐MoO 3 /Ti 3 C 2 hybrids combine the high capacity of α‐MoO 3 and conductivity of Ti 3 C 2 in WIS (19.8 m LiCl) electrolyte in a wide 1.8 V voltage window. Cyclic voltammograms reveal multiple redox peaks from α‐MoO 3 in addition to the well‐separated peaks of Ti 3 C 2 in the hybrid electrode. This leads to a higher specific charge and a higher rate capability compared to a carbon and binder containing α‐MoO 3 electrode. These results demonstrate that the addition of MXene to less conductive oxides eliminates the need for conductive carbon additives and binders, leads to a larger amount of charge stored, and increases redox capacity at higher rates. In addition, MXene encapsulated α‐MoO 3 showed improved electrochemical stability, which was attributed to the suppressed dissolution of α‐MoO 3 . The work suggests that oxide/MXene hybrids are promising for energy storage.

36 MATERIALS SCIENCE↗

DOE OSTI2021

High Temperature Oxidation Behavior of Fe- and Ni-Based Alloy Foils in Water Vapor at 850 °C

Operating temperatures above 700°C are desired to improve the efficiency of power generation systems such as microturbines. Therefore, the use of creep-resistant Ni-based or Fe-based alloys, which can form protective Cr2O3 and Al2O3 scales, is required. In this paper, Fe- and Ni-based alloy foils were oxidized in air + 10 % H2O for up to 3,000 h at 850°C to identify the most promising alloys. The thickness and chemical composition of the spinel oxide formed on top of the Cr2O3 scale varied between S3100, N08120 and N06230 alloy foils. In addition, the rate of Cr and Mn loss (spinel and Cr2O3 oxidation and volatilization) or Al loss (oxidation) and the dissolution of strengthening precipitates, were found to be a function of the nature of the formed oxide (Fe or Ni-rich spinel, Cr2O3, Al2O3). Alloys N06230 and alumina-forming austenitic (AFA) steels were found to be well-suited for the applications as microturbine recuperator foil materials up to 850°C.

Romedenne, Marie↗

DOE OSTI2024

Catch bond kinetics are instrumental to cohesion of fire ant rafts under load

Dynamic networks composed of constituents that break and reform bonds reversibly are ubiquitous in nature owing to their modular architectures that enable functions like energy dissipation, self-healing, and even activity. While bond breaking depends only on the current configuration of attachment in these networks, reattachment depends also on the proximity of constituents. Therefore, dynamic networks composed of macroscale constituents (not benefited by the secondary interactions cohering analogous networks composed of molecular-scale constituents) must rely on primary bonds for cohesion and self-repair. Toward understanding how such macroscale networks might adaptively achieve this, we explore the uniaxial tensile response of 2D rafts composed of interlinked fire ants ( S. invicta ). Through experiments and discrete numerical modeling, we find that ant rafts adaptively stabilize their bonded ant-to-ant interactions in response to tensile strains, indicating catch bond dynamics. Consequently, low-strain rates that should theoretically induce creep mechanics of these rafts instead induce elastic-like response. Our results suggest that this force-stabilization delays dissolution of the rafts and improves toughness. Nevertheless, above 35 % strain low cohesion and stress localization cause nucleation and growth of voids whose coalescence patterns result from force-stabilization. These voids mitigate structural repair until initial raft densities are restored and ants can reconnect across defects. However mechanical recovery of ant rafts during cyclic loading suggests that—even upon reinstatement of initial densities—ants exhibit slower repair kinetics if they were recently loaded at faster strain rates. These results exemplify fire ants’ status as active agents capable of memory-driven, stimuli-response for potential inspiration of adaptive structural materials.

Science & Technology - Other Topics↗

NASA NTRS1995

Influence of variable rates of neritic carbonate deposition on atmospheric carbon dioxide and pelagic sediments

Short-term imbalances in the global cycle of shallow water calcium carbonate deposition and dissolution may be responsible for much of the observed Pleistocene change in atmospheric carbon dioxide content. However, any proposed changes in the alkalinity balance of the ocean must be reconciled with the sedimentary record of deep-sea carbonates. The possible magnitude of the effect of shallow water carbonate deposition on the dissolution of pelagic carbonate can be tested using numerical simulations of the global carbon cycle. Boundary conditions can be defined by using extant shallow water carbonate accumulation data and pelagic carbonate deposition/dissolution data. On timescales of thousands of years carbonate deposition versus dissolution is rarely out of equilibrium by more than 1.5 x 10(13) mole yr-1. Results indicate that the carbonate chemistry of the ocean is rarely at equilibrium on timescales less than 10 ka. This disequilibrium is probably due to sea level-induced changes in shallow water calcium carbonate deposition/dissolution, an interpretation that does not conflict with pelagic sedimentary data from the central Pacific.

NASA Discipline Exobiology↗

DOE OSTI2024

Enabling High Stability of Co-Free LiNiO 2 Cathode via a Sulfide-Enriched Cathode Electrolyte Interface

Cobalt-free lithium nickel oxide (LNO) has garnered significant interest as the end member of high-nickel layered oxide cathodes for next-generation batteries. However, its practical performance notably underperforms expectations because of the structural degradation and unstable interfacial chemistry with electrolytes during cycling. Here, in this study, we report that a durable cathode-electrolyte interface (CEI), enriched by in situ formed sulfides and borides, can inhibit LNO structural degradation and suppress Ni ion dissolution. With the CEI protection, the stability of LNO can be remarkably extended, and batteries demonstrate a capacity retention rate of 84% (30 °C) and 79% (50 °C) after 200 cycles at 1C, respectively. These results demonstrate that enriching CEI with sulfur-containing species can effectively stabilize the interfacial chemistry of LNO, particularly at an elevated temperature of 50 °C. This finding provides valuable perspectives on designing electrolytes for cobalt-free LNO and other high-Ni cathodes toward the development of next-generation high-energy-density lithium-ion batteries.

25 ENERGY STORAGE↗

DOE OSTI2021

Direct visualization of radiation-induced transformations at alkali halide–air interfaces

Radiation driven reactions at mineral/air interfaces are important to the chemistry of the atmosphere, but experimental constraints (e.g. simultaneous irradiation, in situ observation, and environmental control) leave process understanding incomplete. Using a custom atomic force microscope equipped with an integrated X-ray source, transformation of potassium bromide surfaces to potassium nitrate by air radiolysis species was followed directly in situ at the nanoscale. Radiolysis initiates dynamic step edge dissolution, surface composition evolution, and ultimately nucleation and heteroepitaxial growth of potassium nitrate crystallites mediated by surface diffusion at rates controlled by adsorbed water. Finally, in contrast to in situ electron microscopy and synchrotron-based imaging techniques where high radiation doses are intrinsic, our approach illustrates the value of decoupling irradiation and the basis of observation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

High Performance Computing to Quantify the Evolution of Microscopic Concentration Gradients During Flash Processing

During the Flash process, the cross section of a plain-carbon or a low-alloy steel is austenitized through rapid heating and transformed on rapid cooling to a predominantly martensite + bainite structure with small amounts of retained austenite. Unlike conventional heat treating, homogeneity is intentionally avoided during Flash processing of steels. The Flash process assembly consists of a pair of rolls that transfer the steel sheets through the heating and cooling stage of the thermal cycle. The initial microstructure of the steel consists of ferrite (body-centered cubic iron) + carbide ((Fe,X)mCn) mixture. The heating rate through the peak temperature is a function of temperature and reaches a peak of about 300-400°C/s and the cooling rate has a maximum value of 3,000-4,000°C/s. The on-heating phase transformations include carbide dissolution, austenite (face-centered cubic iron) nucleation and growth, and diffusion of carbon and other substitutional elements in the steel. The on-cooling phase transformations include formation of martensite (body-centered tetragonal phase containing supersaturated solute) and bainite (ferrite plates with or without fine carbides). In this project, the focus is on Fe-C-Cr steels that are currently Flash processed for armor applications. The modeling effort proposed here will help optimize the Flash thermal cycle for these low alloy steels to achieve the target performance, which is an ongoing effort at SFP Works. A significant feature of Flash processed Fe-C-Cr steels is the presence of scatter in the through-thickness in the sheet. The variability in hardness results from a variability in the bainite + martensite microstructure that is sensitive to the local chemical concentration of C and Cr. Such a chemical inhomogeneity is intentionally obtained in the Flash process. Although such a microstructural gradient is presumably responsible for the exceptional properties of the Flash processed steel, it is very important to quantify the gradients as a function of Flash variabilities in processing parameters and the input microstructure. Understanding the mechanistic pathway that leads to microstructural gradients could be ground-breaking and instrumental for achieving better process control and optimized microstructural state to meet application-specific strength-ductility requirements. Since the final microstructure depends on setting up precise solute concentration gradients through a rapid heating process, and transforming these regions into various phases, it is important to understand how small changes in steel chemistry, input microstructure (carbide size and distribution), and process variables (Flash thermal cycle) will impact the solute concentration gradients.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1988

Extended period of K/T boundary mass extinction in the marine realm

The Cretaceous/Tertiary (K/T) boundary mass extinction has been widely recognized as a nearly instantaneous catastrophy among marine plankton such as foraminifera. However, the suddenness of this extinction event may have been overemphasized because most pelagic K/T boundary sequences are stratigraphically incomplete and generally lack the earliest Tertiary (Zones P0 and P1a) either due to carbonate dissolution and/or non-deposition. Stratigraphically complete sections appear to be restricted to continental shelf regions with high sedimentation rates and deposition well above the CCD. Such sections have been recovered from El Kef, Tunisia (1) and Brazos River, Texas. Quantitative foraminiferal analysis of these sections indicate an extinction pattern beginning below the K/T boundary and ending above the boundary. These data imply that the mass extinction event was not geologically instantaneous, but occurred over an extended period of time. Evidence supporting this conclusion is discussed.

Keller, G.↗

DOE OSTI2024

Rapid dissolution without elemental fractionation by laser driven hydrothermal processing

Traditional dissolution of geologic samples often requires a significant time investment. Here, we present an alternative method for the dissolution of geologic materials using laser-driven hydrothermal processing (LDHP). LDHP uses laser energy directed onto a submerged sample, which increases the temperature and pressure at the liquid–sample interface and drives the hydrothermal dissolution coupled with photomechanical spallation, an ablative process. This uses focused 527 nm laser energy at 40 W average power, 1 kHz pulse repetition rate, and 115 ns pulse duration. Importantly, when LDHP is performed on basalt geostandards (BCR-2 and BHVO-2) using the conditions outlined, we show that LDHP does not produce significant elemental fractionation and, thus, can be considered an alternative processing method to traditional mechanical crushing and acid digestion. Additionally, it is possible using LDHP to utilize the spatially confined beam to target and selectively isolate individual phases in a rock, potentially alleviating the need for mechanical separation of inclusions that are difficult to physically isolate. Furthermore, using this outlined method of LDHP, we demonstrate full dissolution of 120 mg of obsidian in 85 minu, meaning that LDHP is a potentially very useful method when sample processing is time sensitive.

58 GEOSCIENCES↗

DOE OSTI2021

Thin Water Films Enable Low-Temperature Magnesite Growth Under Conditions Relevant to Geologic Carbon Sequestration

Injecting supercritical CO2 (scCO2) into basalt formations for long-term storage is a promising strategy for mitigating CO2 emissions. Mineral carbonation can result in permanent entrapment of CO2; however, carbonation kinetics in thin H2O films in humidified scCO2 is not well understood. We investigated forsterite (Mg2SiO4) carbonation to magnesite (MgCO3) via amorphous magnesium carbonate (AMC; MgCO3·xH2O, 0.5 < x < 1), with the goal to establish the fundamental controls on magnesite growth rates at low H2O activity and temperature. Experiments were conducted at 25, 40, and 50 °C in 90 bar CO2 with a H2O film thickness on forsterite that averaged 1.78 ± 0.05 monolayers. In situ infrared spectroscopy was used to monitor forsterite dissolution and the growth of AMC, magnesite, and amorphous SiO2 as a function of time. Geochemical kinetic modeling showed that magnesite was supersaturated by two to three orders of magnitude and grew according to a zero-order rate law. The results indicate that the main drivers for magnesite growth are sustained high supersaturation coupled with low H2O activity, a combination of thermodynamic conditions not attainable in bulk aqueous solution. This improved understanding of reaction kinetics can inform subsurface reactive transport models for better predictions of CO2 fate and transport.

Kerisit, Sebastien N.↗

DOE OSTI2026

Effects of Dissolution Regimes on Flow Channelization and Solute Transport in 3D Fracture Networks: Insights From Graph‐Based Reactive Transport Modeling

We investigate how mineral dissolution reshapes flow pathways and solute transport in three‐dimensional discrete fracture networks using a computationally efficient graph‐based reactive transport model. The DFNs are inspired by field‐site observations of fractured carbonate and represent realistic connectivity and structural heterogeneity. Flow is simulated with the Reynolds equation, and dissolution follows first‐order kinetics with diffusive limitations captured through an effective mass‐transfer coefficient. By systematically varying two key dimensionless parameters, the effective Damköhler number (Da), governing reaction versus advection rates, and a transport parameter (Da), analogous to the Thiele modulus, distinct flow channelization regimes emerge: mildly channelized at low G, highly channelized at intermediate Da, and extreme wormhole formation at high Da and low G. Eulerian and Lagrangian analyses, including breakthrough curves, particle tortuosity, dispersivity, and flow channeling indicators quantitatively characterize the progression of dissolution‐driven network restructuring. Across all regimes, initial fracture heterogeneity persists. The results underscore how the interplay between this initial structure, advection, reaction, and diffusion critically shapes subsurface flow pathways, with implications for applications ranging from groundwater remediation to enhanced geothermal systems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

The growth and nanothermite reaction of 2Al/3NiO multilayer thin films

Nanothermite NiO–Al is a promising material system for low gas emission heat sources; still, its reactive properties are highly dependent on material processing conditions. In the current study, sputter deposition is used to fabricate highly controlled nanolaminates comprised of alternating NiO and Al layers. Films having an overall stoichiometry of 2Al to 3NiO were produced with different bilayer thicknesses to investigate how ignition and self-sustained, high temperature reactions vary with changes to nanometer-scale periodicity and preheat conditions. Ignition studies were carried out with both hot plate and laser irradiation and compared to slow heating studies in hot-stage x-ray diffraction. Ignition behavior has bilayer thickness and heating rate dependencies. The 2Al/3NiO with λ ≤ 300 nm ignited via solid/solid diffusion mixing (activation energy, E a = 49 ± 3 kJ/mole). Multilayers having λ ≥ 500 nm required a more favorable mixing kinetics of solid/liquid dissolution into molten Al (E a = 30 ± 4 kJ/mole). This solid/liquid dissolution E a is a factor of 5 lower than that of the previously reported powder compacts due to the elimination of a passivating Al oxide layer present on the powder. The reactant mixing mechanism between 300 and 500 nm bilayer thicknesses was dependent on the ignition source's heating rate. The self-propagating reaction velocities of 2Al/3NiO multilayers varied from 0.4 to 2.5 m/s. Pre-heating nanolaminates to temperatures below the onset reaction temperatures associated with forming intermediate nickel aluminides at multilayer interfaces led to increased propagation velocities, whereas pre-heating samples above the onset temperatures inhibited subsequent attempts at laser ignition.

36 MATERIALS SCIENCE↗

DOE OSTI2023

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↗