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DOE OSTI2024

Impact of Synthetic Parameters on Structure and Electrochemistry of High-Entropy Layered Oxide LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2

Here, this study explored a high-entropy layered oxide (HELO), LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2 , prepared by coprecipitation followed by heat treatment. Coprecipitation yielded a kinetically favored product, and the subsequent heat treatment under various temperatures and times allowed tuning the material toward more thermodynamically favored structures. Refinement of X-ray powder diffraction (XRD) revealed that after 450 °C treatment, ~12% of the Ni 2+ in the structure was located within the lithium cation layer. After heat treatment at 600, 700, and 800 °C, there was a continued decrease of Ni 2+ in the lithium cation layer to 9.3, 6.3, and 3.7%, respectively. Longer heat treatment times at 800 °C decreased the level to 2.5%. Electrochemical behavior was evaluated by cyclic voltammetry, galvanostatic cycling, rate capability testing, and electrochemical impedance spectroscopy, where increased loaded voltage, functional capacity, rate capability, and decreased impedance were observed for samples treated at higher temperatures with lower cation mixing. X-ray absorption near edge spectroscopy (XANES) data indicated that the redox activity of Ni and Co was dominant in the electrochemistry, while the participation of Mn or Fe was minimal. The level of Ni oxidation state change between charge and discharge related to the heat treatment temperature where the samples with high cation mixing showed lower capacity consistent with some Ni 3+ in the transition metal layer inaccessible for electron transfer. Longer heat treatment times at 800 °C did not continue to provide a benefit in electrochemical function even with some additional reduction in cation mixing.

25 ENERGY STORAGE↗

DOE OSTI2026

Synthesis of NiRu-Layered Double Hydroxide for Enhanced Oxygen Evolution Reaction

Nickel−ruthenium layered double hydroxide (NiRu-LDH) was synthesized by coprecipitation using formamide as both solvent and intercalant. The synthesis was performed at various temperatures to study the impact of temperature on electrochemical performance. Temperature plays a vital role in optimizing LDH synthesis to enhance oxygen evolution reaction (OER) efficiency. The optimal temperature yielded a well-defined morphology with balanced crystallinity, leading to more active sites and improved charge transfer. Electrochemical tests indicated that the NiRu-LDH sample prepared at 50 °C (NiRu-LDH-50) required only 280 mV overpotential versus the reversible hydrogen electrode to achieve 10 mA/cm 2 and exhibited a low Tafel slope of 52 mV/dec, demonstrating excellent catalytic kinetics. This study presents the synthesis of NiRu-LDH via coprecipitation and emphasizes how reaction temperature influences LDH structural properties and OER performance.

Catalysts↗

DOE OSTI2020

M4SF-20LL010302042: Process Model for Radionuclide Incorporation into Corrosion Products

This progress report (Level 4 Milestone Number M4SF-20LL010302042) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-20LL010302041. The research is focused on actinide and radionuclide sequestration in steel corrosion products. Fuel matrix degradation models suggest that the near field is likely to be reducing at the time of canister breaching, steel corrosion, and radionuclide release, but more oxidizing conditions may prevail in the far field. The incorporation of radionuclides into corrosion phases may limit the rate of radionuclide release by sequestering a portion of the radionuclide source term. For these reasons there is a need to evaluate the incorporation of Pu and other radionuclides into various Fe-oxide phases, and to understand the behavior of coprecipitated phases during mineral recrystallization processes and during re-oxidation events. Radionuclide coprecipitation with Fe minerals may impact long-term repository performance and is an ongoing research focus at Lawrence Livermore National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Steel Corrosion Impacts on Radionuclide Immobilization

This progress report (Level 4 Milestone Number M4SF-21LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-21LL01030205. The research is focused on actinide and radionuclide sequestration in steel corrosion products. Fuel matrix degradation models suggest that the near field is likely to be reducing at the time of canister breaching, steel corrosion, and radionuclide release, but more oxidizing conditions may prevail in the far field. The incorporation of radionuclides into corrosion phases may limit the rate of radionuclide release by sequestering a portion of the radionuclide source term. For these reasons there is a need to evaluate the incorporation of Pu and other radionuclides into various Fe-oxide phases, and to understand the behavior of coprecipitated phases during mineral recrystallization processes and during re-oxidation events. Radionuclide coprecipitation with Fe minerals may impact long-term repository performance and is an ongoing research focus at Lawrence Livermore National Laboratory.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Radionuclide Interaction with Hydrothermally Altered Repository Materials (M4SF-23LL010302052)

This progress report (Level 4 Milestone Number M4SF-23LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-23LL01030205. The research is focused on actinide and radionuclide sequestration in hydrothermally altered repository materials. In FY23, a manuscript was in preparation for publication summarizing our analysis of radionuclide sorption and coprecipitation into Fe oxide phases and evaluation of radionuclide partitioning values across a range of radionuclides relevant to performance assessment. We demonstrated our approach in detail using Se sorption and coprecipitation with iron oxide minerals. These data were presented in our FY22 annual report and will not be repeated here. We also initiated experiments to identify radionuclide interaction with hydrothermally altered crystalline repository and backfill materials. Recent research performed at Los Alamos National Laboratory (LANL) and Sandia National Laboratory (SNL) has provided key insights regarding the hydrothermal alteration behavior of bentonite backfill in the presence of repository materials (steel, concrete, etc.). We are now examining how mineral alteration affects retardation behavior of plutonium and a suite of other radionuclides. These experiments also allow us to test the predictive ability of our component additivity approach to surface complexation and ion exchange. Our guiding hypothesis is that a robust surface complexation/ion exchange model and associated database, developed using our L-SCIE approach, can effectively predict changes in radionuclide sorption behavior resulting from the hydrothermal alteration of mineralogy in a repository near field. A short update of results to date is presented below. A manuscript was also in preparation describing a self-consistent model and approach to simulating Se(IV) and Se(VI) sorption to 5 iron oxide phases based on our L-SCIE community database. This will be the first implementation of a multi-mineral and multi-oxidation state sorption model using our new L-SCIE database and workflow. A short summary of these results is presented below.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2024

M3SF-24LL010302052-Comprehensive Analysis of Radionuclide Interaction with Hydrothermally Altered Repository Materials

This progress report (Level 3 Milestone Number M3SF-24LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Work Package Number SF-24LL01030205. The research is focused on actinide and radionuclide sequestration in hydrothermally altered repository materials. In FY24, we completed a rigorous analysis of Se sorption to iron oxide phases using our L-SCIE sorption database. This effort explicitly accounts for surface titration behavior of oxide surfaces that was the subject of a recently published manuscript (Han et al., 2023). With this in mind, our Se sorption analysis now yields a more robust workflow for developing self-consistent surface complexation modeling approaches that can be adapted to specific SCM conceptual and numerical approaches (i.e. non-electrostatic, diffuse layer, triple layer models). In late FY24, we plan to publish the results of our comprehensive surface complexation modeling of Se(IV) and Se(VI) sorption to iron oxide mineral phases and provide a path forward to developing robust radionuclide sorption models for use in performance assessment. In FY24, we also submitted a manuscript summarizing our approach to integrating radionuclide sorption and coprecipitation phenomena and evaluation of radionuclide partitioning values across a range of radionuclides relevant to performance assessment. We demonstrated our approach in detail using Se sorption and coprecipitation with iron oxide minerals as a test case. This manuscript was recently accepted for publication in Applied Geochemistry (Balboni et al., Accepted). We also continued experiments to identify radionuclide interaction with hydrothermally altered crystalline repository and backfill materials. Recent research performed at Los Alamos National Laboratory (LANL) and Sandia National Laboratory (SNL) has provided key insights regarding the hydrothermal alteration behavior of bentonite backfill in the presence of repository materials (steel, concrete, etc.). We are now examining how mineral alteration affects retardation behavior of a suite of radionuclides of interest to repository performance assessment. These experiments also allow us to test the predictive ability of our component additivity approach to surface complexation and ion exchange. Our guiding hypothesis is that a robust surface complexation/ion exchange model and associated database, developed using our L-SCIE approach, can effectively predict changes in radionuclide sorption behavior resulting from the hydrothermal alteration of mineralogy in a repository near field. A short update of results to date is presented below.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2023

Stabilized lithium metal oxide electrode material and method of preparation

A stabilized lithium metal oxide cathode material comprises microparticles of lithium metal oxide in which individual particles thereof a core of lithium metal oxide and a coating of a different lithium metal oxide surrounding the core. There is an interface layer between the cores and the coatings in which there are gradients of metal ions in the direction of coating to core. The materials are made by a three stage process involving coprecipitating precursor metal hydroxide core particles at a controlled pH; coprecipitating a different metal hydroxide coating on the particles without controlling the pH; and then calcining the resulting coated precursor particles with lithium hydroxide to form the stabilized lithium metal oxide material.

Lipson, Albert L.↗

DOE OSTI2024

Stabilized lithium metal oxide electrode material and method of preparation

Lipson, Albert L.↗

DOE OSTI2024

Structural, Electrochemical, and (De)lithiation Mechanism Investigation of Cation-Disordered Rocksalt and Spinel Hybrid Nanomaterials in Lithium-Ion Batteries

Significant demand for lithium-ion batteries necessitates alternatives to Co- and Ni-based cathode materials. Cation-disordered materials using earth-abundant elements are being explored as promising candidates. Here, in this paper, we demonstrate a coprecipitation synthetic approach that allows direct preparation of disordered rocksalt Li 2.4 Fe 1.0 Ti 1.0 O 4.7 (r-LFTO·C) and spinel structured hybrid Li 0.5 Fe 1.0 Ti 0.9 O 3.2 ·C (s-LFTO·C) nanoparticles with a conformal conductive carbon coating. High-angle annular dark-field imaging coupled with electron energy loss spectroscopy mapping shows uniform Fe/Ti distribution with minor compositional variation among particles. Cation disorder was confirmed for both of the materials at an atomic level, with a short-range order more pronounced in r-LFTO·C. Operando X-ray absorption spectroscopy, ex situ hard X-ray photoelectron spectroscopy, ex situ soft X-ray absorption spectroscopy, and ex situ synchrotron X-ray diffraction were used to investigate (de)lithiation in the bulk and at the surface. Structurally, the r-LFTO·C demonstrated reversible partial Fe center migration between octahedral and tetrahedral sites during (de)lithiation. The r-LFTO·C evidenced that the redox of O was coincident with iron redox during initial electrochemical cycling, while iron redox dominated later cycling. In contrast, s-LFTO·C electrochemistry involved iron redox throughout the cycling process. The findings rationalize the differences in the electrochemistry where r-LFTO·C shows higher initial capacity yet poorer capacity retention over a voltage window where O redox can be accessed, while the s-LFTO·C shows lower initial capacity yet improved capacity retention.

25 ENERGY STORAGE↗

DOE OSTI2021

Thermally Stable Single-Atom Heterogeneous Catalysts

Single-atom catalysts (SACs) have attracted extensive attention in fields related to energy, environment, and material sciences because of the high atom efficiency and the unique properties of these materials. Many approaches have hitherto been successfully established to prepare SACs, including impregnation, pyrolysis-involved processes, atom trapping, and coprecipitation. However, under typical reaction conditions, single atoms on catalysts tend to migrate or agglomerate, forming nanoclusters or nanoparticles, which lowers their surface free energy. Efforts are required to develop strategies for improving the thermal stability of SACs while achieving excellent catalytic performance. Here in this Progress Report, recent advances in the development of thermally durable single-atom heterogeneous catalysts are discussed. Several important preparation approaches for thermally stable SACs are described in this article. Fundamental understanding of the coordination structures of thermally stable single atom prepared by these methods is discussed. Furthermore, the catalytic performances of these thermally stable SACs are reviewed, including their activity and stability. Finally, a perspective of this important and rapidly evolving research field is provided.

coordination structure↗

DOE OSTI2025

Decoding Gas Evolution Pathways and Interfacial Chemistry in Layered Oxide Cathodes for Safer Sodium‐Ion Batteries

Sodium-ion batteries (SIBs) are attractive for the low cost and abundance of sodium. Yet, gas evolution—a critical challenge in SIBs—remains underexplored. Here, online electrochemical mass spectrometry is used to probe gas evolution in layered oxide cathodes with various compositions, cutoff voltages, dopants, and particle morphologies. Compared to LiNiO 2 (LNO), NaNiO 2 releases more gas, even at lower states of charge, due to the higher covalency of Ni─O bond caused by the more ionic Na─O bond through the inductive effect. Among Co, Mn, Al, and Mg, Mn and Mg doping suppress gas release most effectively by enhancing the metal-oxygen bond strength. NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (NFM) cathodes synthesized via coprecipitation (CP-NFM) and solid-state routes exhibit distinct particle morphologies; CP-NFM exhibits more gas evolution, yet secondary particle morphology helps reduce it through differential cathode-electrolyte reactivity between inner and outer primary particles. Among Li, Ti, Mg, and Cu doping in NFM, Li has the largest effect, reducing gas levels comparable to LNO. Nuclear magnetic resonance and X-ray photoelectron spectroscopies reveal that electrolyte solvent decomposition mainly produces organic-rich cathode-electrolyte interphase (CEI) rather than soluble species. NaPF 6 salt further exacerbates cathode-electrolyte reactions, forming surface Na 2 O species. The findings provide actionable guidance for designing safer, durable SIBs.

25 ENERGY STORAGE↗

DOE OSTI2022

A Study on Recycled Polymers Recovered from Multilayer Plastic Packaging Films by Solvent–Targeted Recovery and Precipitation (STRAP)

Multilayer plastic film use increased in multiple packaging applications due to its versatility and overall increased performance over monolayer structures. However, the performance gains from multiple layers also make recycling difficult because they contain multiple polymers that can be immiscible and burdensome to traditional mechanical recycling operations. A possible solution is the solvent-targeted recovery and precipitation (STRAP) process, but the effect on the retrieved polymer is still unknown. Here, the STRAP process is applied to two different multilayer films and samples of recovered polymers are evaluated for physical, molecular, and thermal properties. Changes in the molecular weight are not significant, but differences in thermal properties are reported along with the coprecipitation of different polymers. Solvent retention in the polymer matrix from STRAP reduced the glass transition temperature of samples, but enhanced drying recovered it. Heavy metals, such as Cd, Cr, and Pb are not detected, indicating regulatory compliance for different applications.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Stability of mineral-organic matter associations under varying biogeochemical conditions

It is well-recognized and documented in the literature that a considerable fraction of the soil organic matter (SOM) is associated with Fe-oxide minerals. Recent studies have also showed that the persistence of various classes of SOM may depend on soil Fe mineralogy. Other laboratory studies with model mineral-associated organic matter (MAOM) moieties, which were primarily focused on ferrihydrite, either coated or coprecipitated with natural organic matter (NOM), have suggested that the mineral phase transformation and adsorption-desorption of SOM is rather complex but appears to be largely controlled by the C/Fe ratio of the MAOM moiety and geochemical conditions. It is also clear from multiple recent studies that the nature or type of SOM (microbial vs. plant-derived) adsorbed on mineral surfaces and the rate and extent of SOM biodegradation depend on the type of mineral, and/or metal ions, that are associated with the SOM. Modeling studies that are primarily centered on achieving a better understanding of the effect of mineral type on SOM interactions with minerals and degradation are also reported. These studies have improved the understanding of the nature and stability of MAOM in soils of varying types and under different conditions, positioning researchers to better predict the properties and stabilities of organo-mineral associations in soils.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Core–Multishell-Structured Digital-Gradient Cathode Materials with Enhanced Mechanical and Electrochemical Durability

Ni-rich cathode materials provide high energy density, but their structural and surface instability limits their cyclability and thermal stability. As one of the approaches to mitigate this problem, cathode materials comprising Ni-rich high-capacity core wrapped in Mn-rich multiple shells are produced successfully. In contrast to the conventional batch-type process for concentration-gradient materials, a digital-gradient cascade coprecipitation process described here achieves the improvements in productivity and quality consistency needed to move toward large-scale manufacturing. The core-multishell cathode materials produced in this manner not only have longer cycle life and improved rate performance compared to homogeneous Ni-rich cathode materials having the same overall composition, but also show remarkably enhanced thermal stability and low impedance growth characteristics. In a novel attempt to determine the correlation between the mechanical properties of the core-multishell cathode particles and their electrochemical cyclabilities, their breaking force and elasticity were successfully measured using a statistical approach, which indicates that a cathode particle with stable surface composition as well as high breaking force has improved capacity retention and durability. These results guide the realization of long life and high thermal stability in Ni-rich cathode materials through heterogeneous particle engineering.

25 ENERGY STORAGE↗

DOE OSTI2023

Experimentally simulated sea level rise destabilizes carbon-mineral associations in temperate tidal marsh soil

How sea level rise (SLR) alters carbon (C) dynamics in tidal salt marsh soils is unresolved. Changes in hydrodynamics could influence organo-mineral associations, influencing dissolved organic carbon (DOC) fluxes. As SLR increases the duration of inundation, we hypothesize that lateral DOC export will increase due to reductive dissolution of C-bearing iron (Fe) oxides, destabilizing soil C stocks and influencing greenhouse gas emissions. To test this, soil cores (0–8 cm depth) were collected from the high marsh of a temperate salt marsh that currently experiences changes in water level and soil redox oscillation due to spring-neap tides. Mesocosms experimentally simulated SLR by continuously inundating high marsh soils and were compared to mesocosms with Control conditions, where the water level oscillated on a spring-neap cycle. Porewater DOC, lateral DOC, and porewater reduced Fe (Fe 2+ ) concentrations were significantly higher in SLR treatments (1.7 ± 0.5 mM, 0.63 ± 0.14 mM, and 0.15 ± 0.11 mM, respectively) than Control treatments (1.2 ± 0.35 mM, 0.56 ± 0.15 mM, and 0.08 ± 01 mM, respectively Solid phase analysis with Fe extended X-ray absorption fine-structure spectroscopy further revealed that SLR led to > 3 times less Fe oxide-C coprecipitates than Control conditions In addition, the overall global warming potential (GWP) decreased under SLR due to suppressed CO 2 emissions. Our data suggest that SLR may increase lateral C export of current C stocks by dissolving C-bearing Fe oxides but decrease the overall GWP from emissions of soil trace gases. Finally, these findings have implications for understanding the fate of SOC dynamics under future SLR scenarios.

dissolved organic carbon↗

DOE OSTI2023

Hydrothermal catalytic conversion of oleic acid to heptadecane over Ni/ZrO 2

There is growing interest in the substitution of expensive noble metal catalysts with low-cost earth-abundant metals in applications targeting biofuels production from waste organic feedstocks. Here, nickel (Ni) catalysts supported on zirconium dioxide (ZrO 2 ), both with and without copper (Cu) as a co-metal, were tested in hydrothermal reactions of unsaturated and saturated C18 fatty acids as models for waste oil feedstocks. In contrast to recent reports, this study showed no enhancement of nickel's activity for fatty acid conversion to alkane products when Cu was present. Ni/ZrO 2 prepared by metal coprecipitation methods converted 100% of oleic acid with 25% selectivity to heptadecane after 5h of reaction at 350 °C using methanol as a hydrogen donor source, increasing to 41% heptadecane after 20 h. Lower yields were observed with catalysts prepared by wet impregnation and using alternative hydrogen donor sources (glycerol, formic acid). Greater selectivity to heptadecane was also observed at higher temperatures (370 °C) and when the initial fatty acid had greater saturation. Longer term exposure to hydrothermal media led to metal sintering and catalyst deactivation. Findings support a path forward to the development of earth-abundant metal catalysts for the upgrading of waste organic feedstocks.

09 BIOMASS FUELS↗

DOE OSTI2022

RAPID UNSEPARATED RARE EARTH ELEMENT ANALYSES BY ISOTOPE DILUTION MULTICOLLECTOR INDUCTIVELY COUPLED MASS SPECTROMETRY (ID-MC-ICP-MS)

We present a method for analyzing rare earth elements (REEs) by isotope dilution without separation of individual elements. Utilizing a Nu Plasma 2 multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) equipped with an Aridus II desolvation nebulizer, sample introduction tuning parameters (torch position, gas flows) were investigated and used to minimize oxide formation (e.g., NdO/Nd <0.05%) and remove the need to analyze the REEs as separated “cuts.” Ratios for spike/sample isotopes in mixed synthetic standards containing varying amounts of Ce, Nd, Sm, Eu, Gd, Dy, Er, and Yb were measured accurately within 1% of IUPAC values. La and Lu in the standards were more than 2% off from expected values due to more demanding interference corrections. A USGS BCR-2 rock standard was also processed with flux fusion, iron coprecipitation and a single column pass bulk separation followed by analysis. The concentrations for Ce, Nd, Sm, Eu, Dy, Er, and Yb fell within 2% of consensus values. A United States Geological Survey (USGS) BIR-1A rock standard was also processed in triplicate by hydrofluoric and nitric acid digestion, yielding rare earth concentrations within 3% of consensus values with 0.3% relative standard deviation (n=3). This demonstrates the ability to produce high quality REE patterns of comparable quality to traditional methods involving labor and time intensive REE separation, with sample preparation and analytical times that are comparable to analyses against isotope dilution by single-collector ICP-MS.

Shen, Steve D.↗

DOE OSTI2022

Application of Fe-doped biochar in Cr(VI) removal from washing wastewater and residual Cr(VI) immobilization in contaminated soil

High-content Cr(VI)-contaminated soils are challenging to remediate using a single remediation technique. This study combined soil washing and immobilization to remediate high-content (3440 mg kg -1 ) Cr(VI)-contaminated soil, which investigated the effects of operating time, temperature, and liquid-solid ratio (LSR) on the Cr(VI) removal efficiency of soil washing and evaluated the potential of Fe-doped biochar (FeBC) in soluble Cr(VI) removal from the washing wastewater and residual Cr(VI) immobilization in the washed soil. The Cr(VI) removal efficiency of soil washing increased with the operating time, temperature, and LSR, but still cannot remove Cr(VI) to achieve the safety content (<100 mg kg -1 ). FeBC showed satisfactory potential in both Cr(VI) removal and immobilization from wastewater and soil, in which the main mechanisms involve ion exchange, redox, and coprecipitation. These results demonstrate applying soil washing & immobilization to remediate high-content Cr(VI)-contaminated soil is a promising alternative method.

54 ENVIRONMENTAL SCIENCES↗