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DOE OSTI2026

Achieving high rate performance in hybrid pristine-recycled cathodes using model-informed electrode designs

Direct recycling lithium-ion battery cathodes, a process that retains the engineered oxide structures from end-of-life materials, presents a cost-effective and energy-efficient alternative to other battery recycling methods. However, while direct-recycled cathodes have demonstrated performance comparable to that of pristine materials at low cycling rates, their high-rate performance remains uncertain. Morphology changes in cathode particles, a main mode of degradation, directly impact rate performance by limiting surface kinetics and solid-phase diffusion. If direct recycling processes do not sufficiently restore pristine-like morphologies, the recycled materials may retain structural defects that hinder high-rate performance. The present work uses a physics-based pseudo-2D model to simulate hybrid electrodes with pristine and artificially “aged/recycled” NMC materials to investigate potential impacts of incorporating performance-limited aged cathode materials into cells. The study highlights how differences in transport and kinetic properties can influence rate capabilities in mixed electrodes — particularly in high-loading cells in high-demand applications. However, model results also reveal a possible mitigation strategy via dual-layer electrode architectures with lower-performing materials positioned near the current collector. Simulations of 4.0 mAh cm −2 cells cycled at 4C using a dual-layer architecture provided approximately 5%–30% more capacity in constant-current protocols compared to homogeneously blended electrode architectures with the same loadings and mixed-material compositions. These findings highlight the importance of strategic electrode design in minimizing potential performance losses and facilitating the integration of recycled materials into high-performance batteries, advancing sustainable and cost-effective battery manufacturing.

25 ENERGY STORAGE↗

DOE OSTI2020

Ensembles of Metastable States Govern Heterogeneous Catalysis on Dynamic Interfaces

Heterogeneous catalysis is at the heart of chemical industry. Being able to tune and design efficient catalysts for processes of interest is of an utmost importance, and for this, the molecular-level understanding of heterogeneous catalysts is the first step, and indeed a prime focus of the modern catalysis research. For a long time, a single most thermodynamically stable structure of the catalytic interface attained in reaction conditions had been envisioned as the reactive phase. However, some catalytic interfaces continue to undergo structural dynamics in the steady state, triggered by high temperatures, pressures, and binding and changing reagents. Among particularly dynamic interfaces are such widely-used catalysts as crystalline and amorphous surfaced supporting (sub-)nano metallic clusters. Recently, it became clear that this dynamic fluxionality causes the supported clusters to populate many distinct structural and stoichiometric states in catalytic conditions. Hence, the catalytic interface should be viewed as an evolving statistical ensemble of many (not one) structures. As such, every member in the ensemble contributes to the properties of the catalyst differently, and in proportion to its probability to be populated. This new notion flips the established paradigm and calls for new theory, modeling approaches, operando measurements, and updated design strategies. The statistical ensemble nature of surface-supported sub-nano cluster catalysts can be exemplified by oxide-supported and adsorbate-covered Pt, Pd, Cu, CuPd clusters, catalytic toward oxidative and non-oxidative dehydrogenation. They have access to a variety of 3D and quasi-2D shapes. The compositions of their thermal ensembles are dependent on the cluster size, leading to size-specific catalytic activities and the famous “every atom counts” phenomenon. The support and adsorbates affect catalyst structures, and state of the reacting species causes the ensemble to change in every reaction intermediate. The most stable member of the ensemble dominates the thermodynamic properties of the corresponding intermediate, whereas the kinetics can be determined by more active but less populated metastable catalyst states, and that suggests that many earlier studies might have overlooked the actual active sites. Both effects depend on the relative time-scales of catalyst restructuring and reaction dynamics. The catalyst may routinely operate off-equilibrium. Ensemble phenomena lead to surprising exceptions from established rules of catalysis, such as scaling relations, and Arrhenius behavior. Catalyst deactivation is also an ensemble property, and its extent of mitigation can be predicted through the new paradigm. These findings were enabled by advances in theory, such as global optimization and subsequent utilization of multiple local minima, and pathways sampling, as well as operando catalyst characterization. The fact that the per-site and per-species resolution is needed for the description and predicting of catalyst properties gives theory the central role in catalysis research, as most experiments provide ensemble-average information and cannot detect the crucial minority species that may be responsible for the catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Synoptic Drivers of Atmospheric River Induced Precipitation Near Dronning Maud Land, Antarctica

Atmospheric rivers (ARs) that reach the Antarctic Ice Sheet (AIS) transport anomalous moisture from lower latitudes and can impact the AIS via extreme precipitation and increased downward longwave radiation. ARs contribute significantly to the interannual variability of precipitation over the AIS and thus are likely to play a key role in understanding future changes in the surface mass balance of the AIS. Dronning Maud Land (DML) is one of four maxima in AR frequency over coastal East Antarctica, with AR precipitation explaining 77% of the interannual variability in precipitation for this region. We employ a 16-node self-organizing map (SOM) trained with MERRA-2 sea-level pressure anomalies to identify synoptic-scale environments associated with landfalling ARs in and around DML. Node composites of atmospheric variables reveal common drivers of precipitation associated with ARs reaching DML including anomalous high-low surface pressure couplets, anomalously high integrated water vapor, and coastal barrier jets. Using a quasi-geostrophic framework, we find that upward vertical motion associated with the occlusion process of attendant cyclones dominates atmospheric lift in AR environments. We further identify mechanisms that explain the variability in AR precipitation intensity across nodes, such as the lift associated with the occlusion process of attendant cyclones and the spatial coincidence of ascent induced by the occlusion process and frontogenesis. Here, the latter suggests that ARs making landfall during the mature phase of cyclogenesis result in higher precipitation intensity compared to landfalling ARs that occur during the occluded phase.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Unravelling the mechanism of pressure induced polyamorphic transition in an inorganic molecular glass

The atomic structure of a germanium doped phosphorous selenide glass of composition Ge 2.8 P 57.7 Se 39.5 is determined as a function of pressure from ambient to 24 GPa using Monte-Carlo simulations constrained by high energy x-ray scattering data. The ambient pressure structure consists primarily of P 4 Se 3 molecules and planar edge shared phosphorus rings, reminiscent of those found in red phosphorous as well as a small fraction of locally clustered corner-sharing GeSe 4 tetrahedra. This low-density amorphous phase transforms into a high-density amorphous phase at ~6.3 GPa. The high-pressure phase is characterized by an extended network structure. The polyamorphic transformation between these two phases involves opening of the P 3 ring at the base of the P 4 Se 3 molecules and subsequent reaction with red phosphorus type moieties to produce a cross linked structure. The compression mechanism of the low-density phase involves increased molecular packing, whereas that of the high pressure phase involves an increase in the nearest-neighbor coordination number while the bond angle distributions broaden and shift to smaller angles. The entropy and volume changes associated with this polyamorphic transformation are positive and negative, respectively, and consequently the corresponding Clapeyron slope for this transition would be negative. This result has far reaching implications in our current understanding of the thermodynamics of polyamorphic transitions in glasses and glass-forming liquids.

42 ENGINEERING↗

DOE OSTI2022

Silver Nanowire-Indium Zinc Oxide Composite Flexible Transparent Conducting Electrodes Made by Spin- coating and Photonic Curing

Realizing high-throughput, low-cost perovskite solar cell (PSC) manufacturing is highly sought-after in photovoltaic (PV) research in recent years. To fully achieve roll-to-roll (R2R) manufacturing of PSCs, it is important to consider the flexible transparent electrode (TE). PET/ITO is a commonly used substrate for making flexible PSCs. When optimizing transparent conducting materials, there is a tradeoff between sheet resistance (Rsh) and optical transparency. Because commercial PET/ITO substrates are made with slow (~1 m/min) vacuum deposition processes, they tend to be expensive. Therefore, it would be advantageous to develop a high-throughput, R2R compatible, solution-deposition approach for fabricating the TE on PET substrates. While various solution-deposition processes, such as blade coating or slot-die coating, can achieve the desired web speed of > 10 m/min, there is still a need to improve the post-deposition annealing step. One promising post-deposition processing technique is intense-pulsed-light processing, also known as photonic curing. Photonic curing delivers short (0.01 – 100 ms) pulses of broadband (200 – 1500 nm) light from a xenon flash lamp to the samples. Any materials in the sample stack that absorb light will convert the impinging light pulse into heat within the sample, which drives changes in the sample (calcination, phase change, crystallization, etc.). Photonic curing has three main advantages over thermal annealing: 1. Faster processing speed (milliseconds or seconds). 2. Compatibility with plastic substrates. 3. Smaller physical footprint and less wasted energy. Since the light pulses are on for a short time, the intensity can be high while the total energy delivered to the sample is low, minimizing damages to the plastic substrates. In this work, a hybrid TE material is fabricated on PET substrates using photonic curing. The hybrid TE material contains a layer of silver nanowires (AgNWs) and a layer of metal-oxide (InOx, ITO, IZO, etc.). The AgNWs increase the light absorbed by the film during the photonic curing process, which leads to higher processing temperatures, possibly improving the conversion of the metal-oxide layer. The AgNWs also enhance the electrical conductivity of the final TE layer after photonic curing. A AgNW and metal-oxide bilayer is formed by spin coating each solution onto the PET substrate sequentially followed by a single photonic curing process. We use average optical transmittance (Tavg) from 400 to 700 nm and average Rsh to evaluate the TE performance. The following photonic curing parameters are varied to optimize Tavg (maximize) and Rsh (minimize): Pulse voltage, pulse envelope, number of micro-pulses, duty cycle, number of pulses, and pulse repetition rate. Preliminarily, we also observe a significant impact on the TE properties by the volume of AgNW deposited during the spin coating deposition step. Using dispense volumes of 80 µL and 20 µL, we achieve samples with Tavg = 73%, Rsh = 19 Ω/sq, and roughness = 9 nm, and Tavg = 83%, Rsh = 58 Ω/sq, and roughness = 5.6 nm, respectively, after photonic curing.

14 SOLAR ENERGY↗

DOE OSTI2025

Improved interfacial li-ion transport in composite polymer electrolytes via surface modification of LLZO

Composite polymer electrolytes that incorporate ceramic fillers in a polymer matrix offer mechanical strength and flexibility as solid electrolytes for lithium metal batteries. However, fast Li + transport between polymer and Li + -conductive filler phases is not a simple achievement due to high barriers for Li + exchange across the interphase. This study demonstrates how modification of Li 7 La 3 Zr 2 O 12 (LLZO) nanofiller surfaces with silane chemistries influences Li + transport at local and global electrolyte scales. Anhydrous reactions covalently link amine-functionalized silanes [(3-aminopropyl)triethoxysilane (APTES)] to LLZO nanoparticles, which protects LLZO in air. APTES functionalization lowers the poly (ethylene oxide) (PEO)-LLZO interphase resistance to half that of unmodified LLZO and increases effective Li + transference number, while insulating Al 2 O 3 completely blocks ion exchange and lowers transference number and conductivity in PEO-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-LLZO composites. Modeling an inner resistive interphase between LLZO and PEO surrounded by an outer conductive interphase explains non-linear conductivity trends. Solid-state 7 Li & 6 Li nuclear magnetic resonance shows Li + only exchanges between PEO-LiTFSI and some LLZO interphase, with no appreciable Li + transport through bulk LLZO. Surface functionalization is a promising path toward lowering the polymer-ceramic interphase resistance. This work demonstrates that local changes in Li + transport affect macroscopic performance, highlighting the intricate relationships between all interfaces in inherently heterogeneous composite polymer electrolytes.

25 ENERGY STORAGE↗

DOE OSTI2023

Effect of thickness and surface composition on the stability of polarization in ferroelectric Hf x Zr 1 - x O 2 thin films

Using density functional theory, we find that tailoring the surface composition provides a route to stabilize the polar phases of the promising ferroelectric material, Hf x Zr 1-x O 2 . First, we show that for pure Hf O 2 , controlling the positively polarized surface to be relatively oxygen rich adequately screens the ferroelectric surface charges and stabilizes the polar orthorhombic phase. We then demonstrate that the ferroelectric polarization, as measured by the structural polar displacements, increases with decreasing thickness, leading to the emergence of a polar rhombohedral-like phase at the ultrathin limit (1.5 unit cells). Our findings extend to the cases of Hf 0.5 Zr 0.5 O 2 and Zr O 2 , both of which have surface energy landscapes similar to that of Hf O 2 . In conclusion, these findings are consistent with and offer insights into the observed absence of a ferroelectric thickness limit in Hf x Zr 1-x O 2 -based thin films.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Bio-Based Phase Change Materials (PCMs) for Thermal Energy Storage (Final Scientific/Technical Report)

The goal of this project is to develop a novel bio-based phase change material (PCM) derived from squid ring teeth (SRT) proteins, and design a prototype heat exchanger based on these bio-based PCMs for energy storage and dynamic heat exchange for building thermal energy storage systems. The PCMs, derived from SRT proteins, will demonstrate room temperature energy storage capacities and switchable thermal conductivities that redefine the current state-of-the-art (SOA) for building thermal energy storage. Further, in a single material and with a single manufacturing processes, our proposed thermal battery will be developed with “on demand” thermal conductivity for rapid charging/discharging but superior insulation during energy storage periods. More specifically, our bio-based PCMs have demonstrated: 1) the potential for increased energy storage capacity (i.e., greater than paraffines at room temperature); 2) tunability in thermal conductivity with the largest thermal conductivity switching ratios for an intrinsic material reported to date, and 3) a 100% recyclable and biodegradable PCM with low volatility and toxicity and scalability in its manufacture for both residential and commercial applications. The already established ability for roll-to-roll processing of these non-toxic, non-flammable SRT composites along with their carbon-neutral manufacturing processes that has been pioneered by our team make this solution a disruptive and impactful technology to redefine the current SOA of energy storage technologies. The outcomes of this effort have been: 1) the identification of new bio-based PCM that establishes a new SOA for thermal conductivity and energy storage density at room temperature and 2) the development of a new experimental technique to measure the energy storage density via latent heat measurements during melting of thin films. This new technique can be applied to thin films (as thin as < 1 micrometer), and represents a novel approach for thin film energy storage density measurements. Dynamic thermal energy storage is the missing technology that will enable a grid- interactive efficient building (GEB). For a “smart” building capable of connecting with the power grid, the media must be inexpensive and possess thermal switching capabilities to control the time-dependent heat flow into (and out of) the PCM on demand. Unique to the material system in this program, programmable SRT-based PCM show improvements as compared to traditionally used PCMs, and thus its technical performance will represent a leap forward for the future GEB concept.

25 ENERGY STORAGE↗

DOE OSTI2024

Temperature-induced hexagonal–orthorhombic phase transition in lutetium ferrite nanoparticles

The x-ray diffraction, Raman, and infrared spectroscopies and magnetic measurements were used to explore the correlated changes of the structure, lattice dynamics, and magnetic properties of the LuFeO3 nanoparticles, which appear in dependence on their sintering temperature. We revealed a gradual substitution of the hexagonal phase by the orthorhombic phase in the nanoparticles, with sintering temperature increasing from 700 to 1100 °C. The origin and stability of the hexagonal phase in the LuFeO3 nanoparticles are of the special interest, because the nanoparticles in the phase can be a room-temperature multiferroic with a weak ferromagnetic and pronounced structural and ferroelectric long-range ordering. The antiferromagnetic and nonpolar orthorhombic phase is more stable in the bulk LuFeO3. To define the ranges of the hexagonal phase stability, we determine the bulk and interface energy densities of different phases from the comparison of the Gibbs model with experimental results. Using effective parameters of the Gibbs model, we predict the influence of size effects and temperature on the structural and polar properties of the LuFeO3 nanoparticles. Analysis of the obtained results shows that the combination of the x-ray diffraction, Raman and infrared spectroscopies, magnetic measurements, and theoretical modeling of structural and polar properties allows us to establish the interplay between the phase composition, lattice dynamics, and multiferroic properties of the LuFeO3 nanoparticles prepared under different conditions.

Materials Science↗

DOE OSTI2024

4D-STEM Mapping of Nanocrystal Reaction Dynamics and Heterogeneity in a Graphene Liquid Cell

Chemical reaction kinetics at the nanoscale are intertwined with heterogeneity in structure and composition. However, mapping such heterogeneity in a liquid environment is extremely challenging. Here, in this work, we integrate graphene liquid cell (GLC) transmission electron microscopy and four-dimensional scanning transmission electron microscopy to image the etching dynamics of gold nanorods in the reaction media. Critical to our experiment is the small liquid thickness in a GLC that allows the collection of high-quality electron diffraction patterns at low dose conditions. Machine learning-based data-mining of the diffraction patterns maps the three-dimensional nanocrystal orientation, groups spatial domains of various species in the GLC, and identifies newly generated nanocrystallites during reaction, offering a comprehensive understanding on the reaction mechanism inside a nanoenvironment. This work opens opportunities in probing the interplay of structural properties such as phase and strain with solution-phase reaction dynamics, which is important for applications in catalysis, energy storage, and self-assembly.

four-dimensional scanning transmission electron mi↗

DOE OSTI2021

Aircraft measurements of aerosol and trace gas chemistry in the eastern North Atlantic

The Aerosol and Cloud Experiment in the Eastern North Atlantic (ACE-ENA) investigated properties of aerosols and subtropical marine boundary layer (MBL) clouds. Low subtropical marine clouds can have a large effect on Earth's radiative budget, but they are poorly represented in global climate models. In order to understand their radiative effects, it is imperative to understand the composition and sources of the MBL cloud condensation nuclei (CCN). The campaign consisted of two intensive operation periods (IOPs) (June–July 2017 and January–February 2018) during which an instrumented G-1 aircraft was deployed from Lajes Field on Terceira Island in the Azores, Portugal. The G-1 conducted research flights in the vicinity of the Atmospheric Radiation Measurement (ARM) Eastern North Atlantic (ENA) atmospheric observatory on Graciosa Island. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and Ionicon proton-transfer-reaction mass spectrometer (PTR-MS) were deployed aboard the aircraft, characterizing chemistry of non-refractory aerosol and trace gases, respectively. The eastern North Atlantic region was found to be very clean, with an average non-refractory submicrometer aerosol mass loading of 0.6 µg m −3 in the summer and 0.1 µg m −3 in the winter, measured by the AMS. Average concentrations of the trace reactive gases methanol and acetone were 1–2 ppb; benzene, toluene and isoprene were even lower, <1 ppb. Mass fractions of sulfate, organics, ammonium and nitrate in the boundary layer were 69 %, 23 %, 7 % and 1 % and remained largely similar between seasons. The aerosol chemical composition was dominated by sulfate and highly processed organics. Particulate methanesulfonic acid (MSA), a well-known secondary biogenic marine species, was detected, with an average boundary layer concentration of 0.021 µg m −3 , along with its gas-phase precursor, dimethyl sulfide (DMS). MSA accounted for no more than 3 % of the submicron, non-refractory aerosol in the boundary layer. Examination of vertical profiles of aerosol and gas chemistry during ACE-ENA reveals an interplay of local marine emissions and long-range-transported aged aerosol. A case of transport of biomass burning emissions from North American fires has been identified using back-trajectory analysis. In the summer, the non-refractory portion of the background CCN budget was heavily influenced by aerosol associated with ocean productivity, in particular sulfate formed from DMS oxidation. Episodic transport from the continents, particularly of biomass burning aerosol, periodically increased CCN concentrations in the free troposphere. In the winter, with ocean productivity lower, CCN concentrations were overall much lower and dominated by remote transport. These results show that anthropogenic emissions perturb CCN concentrations in remote regions that are sensitive to changes in CCN number and illustrate that accurate predictions of both transport and regional aerosol formation from the oceans are critical to accurately modeling clouds in these regions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Probing of Local Structure in Laves Compound TbFe 2

Abstract The Laves compounds Tb 1‐x Dy x Fe 2 have attracted much interest due to the giant magnetostriction effect appearing at their morphotropic phase boundary compositions. Although previous studies have established the relationship between the average structure and magnetostrictive properties in these compounds, there is a lack of characterization of their local structures. In this paper, as a first step toward this goal, the evolution of the local structure of the terminal compound (TbFe 2 ) of this system is reported, in an attempt to provide useful information about interatomic bonding in this system. The pair distribution function (PDF) results suggest that the compound presents the rhombohedral local crystal symmetry. The lattice at the local scale shows abnormal thermal expansion which is different from the long scale structure. The different role of the Tb─Fe bond and Fe─Fe bond in affecting the crystal lattice is revealed. These findings highlight the important role of local structure in determining the magnetostrictive properties of the Laves compounds.

Kou, Ronghui↗

DOE OSTI2023

Phase equilibria in iron-rich Sm–Fe–Ti and Sm–(Fe,Co)–Ti alloys at 1100–1200 °C

Iron-rich corners of ternary Sm–Fe–Ti phase diagram at 1100 °C and quasi-ternary Sm–Fe 0.8 Co 0.2 –Ti phase diagrams at 1100 and 1200 °C are constructed based on experimental investigation of equilibrated alloys with electron probe microanalysis, X-ray diffraction and thermomagnetic analysis. In addition, the upper boundaries of the temperature ranges of Sm(Fe,[Co,]Ti) 12 and Sm 3 (Fe,[Co,]Ti) 29 phases are determined with differential thermal analysis to update earlier rough estimates. The existence of a high-temperature phase of the Th 2 Ni 17 type, originally reported by Ivanova et al. [J. Alloys Compd. 224 (1995) 29], is confirmed. In the Sm–Fe 0.8 Co 0.2 –Ti system, the composition and equilibria of this hexagonal phase are established for 1200 °C; it is Sm-depleted (≈9.8 at.% Sm) compared to the 2:17 stoichiometry and it coexists with the rhombohedral 2:17 phase. The magnetic anisotropy of the cobalt-substituted Th 2 Ni 17 -type phase is planar, with the easy magnetization direction parallel to [100]. Equilibrium between a Sm-rich liquid phase and the 1:12 phase, which is important for the development of new high-performance permanent magnets, is absent up to 1000 °C, but does exist at 1100 °C (for the 1:12 phase with at least 8.7–8.9 at.% Ti) and at 1200 °C (for the 1:12 phase with as little as 7.4 at.% Ti). The development of magnets may be complicated, however, by an observed tendency of the high-temperature liquid to solidify into ferromagnetic phases including the Th 2 Ni 17 -type phase. The Curie temperatures of the α-(Fe,Ti), Sm(Fe,Ti) 12 , Sm 3 (Fe,Ti) 29 and rhombohedral Sm 2 (Fe,Ti) 17 phases are not only increased by the partial Co substitution for Fe, but their dependence on the Ti concentration is changed by this Co substitution from positive (or, for the 1:12 phase, zero) to negative values.

36 MATERIALS SCIENCE↗

DOE OSTI2023

The Riddle of Dark LLZO: Cobalt Diffusion in Garnet Separators of Solid‐State Lithium Batteries

Abstract Solid‐state batteries (SSBs) with a Li 7 La 3 Zr 2 O 12 (LLZO) garnet electrolyte are attracting much attention as robust and safe alternative to conventional lithium‐ion batteries. Technical challenges in the practical implementation of garnet SSBs are related to the need for high‐temperature sintering, which often leads to undesirable chemical reactions with the cathode material. While these reactions are well understood for composite cathodes, very little is known about similar processes between cathode and separator during battery fabrication. This work focuses on understanding the processes between the composite LiCoO 2 ‐LLZO cathode and the LLZO separator and how they affect the battery performance. The extensive diffusion of Co‐ions within LLZO, which leads to the often‐observed LLZO darkening, is shown to have a significant impact on ionic conductivity, electronic conductivity, and dendrite stability of the separator. Experimental data coupled with large‐scale molecular dynamics simulations uncover the diffusion mechanism for Co‐ions and identify secondary phases that form during these interactions. In addition to extensive Co‐ion diffusion within the grains, a non‐uniform segregation of Co‐ions at grain boundaries is found leading to the formation of three distinct Co‐containing phases. This work offers a general approach to studying the fundamental ion diffusion processes that occur during the fabrication of oxide SSBs.

electrochemical properties↗

DOE OSTI2024

Exploring the impact of Cr-doping on the crystallographic and magnetic structure of Mn 5 Si 3 antiferromagnetic alloy

Here, the role of Cr-doping on the structural and magnetic ground states of Mn 5 Si 3 alloy has been investigated through temperature-dependent neutron powder diffraction (NPD) and X-ray absorption fine structure (XAFS) techniques. All the Cr-doped alloys of nominal composition Mn 5-x Cr x Si 3 (for x = 0.05, 0.1, and 0.2) undergo two first-order magneto-structural phase transitions from hexagonal (space group: P6 3 /mcm) paramagnetic → orthorhombic (space group: Ccmm) collinear antiferromagnetic → orthorhombic (space group: Cc2m) non-collinear antiferromagnetic phase on cooling from room temperature. NPD studies at different constant temperatures indicate that both anti ferromagnetic phases are commensurate in nature and can be represented by q = (0,1,0) magnetic propagation vector for all the Cr-doped alloys. Such doping at the Mn-site results in a significant modification of the non-collinear antiferromagnetic structure (both moment size and orientation) and hence affects the unusual magnetic properties, like inverted hysteresis loop, thermomagnetic irreversibility, etc. The XAFS measurements were performed to interpret the local environment of doped Cr atoms in detail, which is critical for a microscopic understanding of the unusual properties of this class of Cr-doped Mn 5 Si 3 alloys. The analysis confirms the elemental state of Cr in the doped alloys and indicates a high degree of preservation of local crystallographic structure with varying Cr concentration and sample temperature. Doping induces intriguing changes in XAFS patterns, elucidated through different types of scattering mechanisms associated with the central absorbing Cr atom.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Observing Chemical and Morphological Changes in a Cu@TiO x Core@Shell Catalyst: Impact of Reversible Metal-Oxide Interactions on CO 2 Activation and Hydrogenation

A combination of several in-situ techniques (XRD, XAS, AP-XPS, E-TEM) was used to explore links between the structural and chemical properties of a Cu@TiO x catalyst under CO 2 hydrogenation conditions. The active phase of the catalyst involved an inverse oxide/metal configuration, but the initial core@shell motif was disrupted during the pre-treatment in H 2 . As a consequence of strong metal-support interactions, the titania shell cracked and Cu particles migrated from the core to on top of the oxide with the simultaneous formation of a Cu-Ti-O x phase. The generated Cu particles had a diameter of 20-40 nm and were decorated by small clusters of TiO x (< 5 nm in size). Results of in-situ XAS and XRD and images of E-TEM showed a very dynamic system, where the inverse oxide/metal configuration promoted the reactivity of the system towards CO 2 and H 2 . At room temperature, CO 2 oxidized the Cu nanoparticles (CO 2,gas → CO gas + O oxide ) inducing a redistribution of the TiO x clusters and big modifications in catalyst surface morphology. The generated oxide overlayer disappeared at elevated temperatures (> 180 °C) upon exposure to H 2 , producing a transient surface that was very active for the reverse water-gas shift reaction (CO 2 + H 2 → CO + H 2 O) but was not stable at 250 °C. When oxidation and reduction occurred at the same time, under a mixture of CO 2 and H 2 , the surface structure evolved toward a dynamic equilibrium that strongly depended on the temperature. Neither CO 2 nor H 2 can be considered as passive reactants. In the Cu@TiO x system, morphological changes were linked to variations in the composition of metal-oxide interfaces which were reversible with temperature or chemical environment and affected the catalytic activity of the system. Finally, the present study illustrates the dynamic nature of phenomena associated with the trapping and conversion of CO 2 .

36 MATERIALS SCIENCE↗

DOE OSTI2020

Geochemical Changes in Response to CO 2 Injection in a CO 2 -EOR Complex in Northern Michigan (Volume II.1)

The Midwest Regional Carbon Sequestration Partnership (MRCSP) was founded in 2003 as part of the U.S. Department of Energy’s (DOE’s) Regional Carbon Sequestration Partnership initiative. Since its founding, MRCSP has made significant strides toward making CCUS a viable option for states in the region. The public/private consortium, funded through the DOE Regional Carbon Sequestration Initiative, brings together nearly 40 industry partners and 10 states. Battelle, as the project lead, oversees research, development and operations and coordinates activities among the partners. The incremental, phased approach has built a valuable knowledge base for the industry and paved the way for commercial-scale adoption of CCUS technologies. From 2008 to 2020, MRCSP Phase III focused on the development of large-scale injection projects. This report is part of a series of reports prepared under the Midwestern Regional Carbon Sequestration Partnership (MRCSP) Phase III (Development Phase). These reports summarize and detail the findings of the work conducted under the Phase III project. The report describes the geochemical monitoring program under MRCSP to use stable and radiogenic isotope geochemistry in concert with analysis of general geochemical parameters of fluids and gases and analysis of core samples to determine geochemical processes occurring in the reef structure because of CO 2 injection. Specifically, brine and gas samples were collected and analyzed to determine changes occurring between reefs prior to and following CO 2 injection. The analytical results for general geochemical parameters were modeled with chemical equilibrium models to determine if the injection of CO 2 resulted in the mineral dissolution or precipitation. Finally, core samples were collected and analyzed to determine if there was evidence of dissolution features or mineral precipitation.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2023

Lime slurry treatment of soils developing on abandoned coal mine spoil: Linking contaminant transport from the micrometer to pedon-scale

Historical and abandoned coal mine spoil continues to generate acid- and metal(loid)-rich porewaters and represents a geographically large and diffuse non-point source of contamination to local watersheds. A potentially inexpensive approach to treat these materials and soils developing on them is through the application of lime slurries, to neutralize acidity and encourage the (co)precipitation of metal(loids) with Fe(III)-(oxy)hydroxides, and potentially other metal-oxides and/or Ca-bearing phases. Here, the efficacy of this approach was evaluated through parallel field application and laboratory-based flow-through column experiments. The field site is Huff Run sub-watershed 25 located in Tuscarawas County, Ohio and was chosen in part because it was previously classified as one of the most highly AMD-impacted sub-watersheds in the region. Two locations with historical spoil were chosen and suction lysimeters were installed at 25 and 75 cm depth to monitor porewater composition on two sides at the base of each pile. Half of each slope received seven lime slurry treatments from June through October of 2017. A suite of aqueous (ICP-OES, IC, and TOC-L) and solid phase geochemical and mineralogical approaches (quantitative SEM-EDS and synchrotron μ-XRF) were used to determine how composition, texture, morphology, and spatial distribution of mineral coatings differ in pre- and post-lime treated soils, and how that impacts the distribution and transport of trace metal(loid)s. Mine spoil porewater at site 1 was slightly less alkaline (pH ranging from 7.04 to 7.37) than at site 2 (ranging from 7.55 to 7.71), and average electrical conductivity values at site 1 (316–405 μS cm —1 ) were slightly lower than at site 2 (358–464 μS cm —1 ), although differences between the sites were not significant. Porewater pH and electrical conductivity in all lysimeters decreased over the course of the field season but there was no obvious response to lime treatment at either site or any depth. At site 1, both treatment and depth were significant factors affecting Ca, K, Ni, SO 4 2— , and DOC concentrations while only treatment effects were significant for dissolved Al and Cu (p < 0.05). For all soils, there were no trends in metal concentration observed over time although DOC and SO 4 2— decreased over the field season. Pedon-scale changes in metal porewater concentrations in response to treatment were linked to micrometer-scale changes in mineral surface coatings; specifically, higher concentrations of Ca, Fe, Mn, and Zn were observed in the coatings and no changes were observed in Fe redox speciation, whereas total S decreased likely due to oxidation of S in coal fragments. In contrast to the field experiment, the column experiments exhibited a much greater response in effluent composition with respect to lime treatment. The untreated columns had approximately an order of magnitude more H + leached over the course of the experiment (p < 0.001) and resulted in greater Ca, Al, Cu, and DIC leached and less Mn, Zn, and SO 4 2— . Soils treated with the lime slurry in the column experiments exhibited larger and thicker secondary Fe-coatings, including the addition of Fe-sulfates. Despite clear trends in the laboratory-based column experiment where the lime-to-soil ratio was higher, the effects were either muted or undetected in the field pilot project, suggesting that a higher application rate of lime in the field is needed to achieve a similar effect. This work provides evidence that a less alkaline lime slurry could be a practical and inexpensive method of treating coal mine spoil-impacted soils and represents an important step in linking laboratory-based remediation studies to implemented field-based studies.

58 GEOSCIENCES↗