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DOE OSTI2025

Irreversible Multielement Diffusion and the Resulting Compositional and Processing Flexibility in the Synthesis and Densification of Lithium Aluminum Lanthanum Zirconium Oxide

Despite the broad interest in Al-doped lithium lanthanum zirconium oxide (LLZO), the wide range of reported ionic conductivities suggests that the effect of processing parameters on the resulting phase purity and bulk conductivity is not well-understood. Here, in this work, we synthesized six separate series of LLZO with variations in Al concentration, Li excess, Li addition order, Li source, densification method, and mother powder to determine the effect on the composition, phase purity, density, and bulk conductivity. We found that a wider range of compositions (6.08–7.61 mol of Li and 0.06–0.23 mol of Al) than previously reported can result in cubic phase stability and that nearly all elements (Li, Al, Zr, and La) are lost to the MgO crucible during calcination and sintering. The manner in which different elements are lost is affected by the processing parameters. We observed that Al-doped LLZO shows great compositional flexibility in stabilizing the cubic phase, offering an explanation for the range of electrochemical performance metrics reported in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Thermodynamically consistent semi-compressible fluids: a variational perspective

This paper presents (Lagrangian) variational formulations for single and multicomponent semi-compressible fluids with both reversible (entropy-conserving) and irreversible (entropy-generating) processes. Semi-compressible fluids are useful in describing low-Mach dynamics, since they are soundproof. These models find wide use in many areas of fluid dynamics, including both geophysical and astrophysical fluid dynamics. Specifically, the Boussinesq, anelastic and pseudoincompressible equations are developed through a unified treatment valid for arbitrary Riemannian manifolds, thermodynamic potentials and geopotentials. By design, these formulations obey the 1st and 2nd laws of thermodynamics, ensuring their thermodynamic consistency. This general approach extends and unifies existing work, and helps clarify the thermodynamics of semi-compressible fluids. To further this goal, evolution equations are presented for a wide range of thermodynamic variables: entropy density s, specific entropy η, buoyancy b, temperature T, potential temperature θ and a generic entropic variable χ; along with a general definition of buoyancy valid for all three semicompressible models and arbitrary geopotentials. Finally, the elliptic equation for the pressure perturbation (the Lagrange multiplier that enforces semi-compressibility) is developed for all three equation sets in the case of reversible dynamics, and for the Boussinesq/anelastic equations in the case of irreversible dynamics; and some discussion is given of the difficulty in formulating it for the pseudoincompressible equations with irreversible dynamics.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2022

Nanostructured ZnO-Based Electrochemical Sensor with Anionic Surfactant for the Electroanalysis of Trimethoprim

In this research, detection of trimethoprim (TMP) was carried out using a nanostructured zinc oxide nanoparticle-modified carbon paste electrode (ZnO/CPE) with an anionic surfactant and sodium dodecyl sulphate (SDS) with the help of voltametric techniques. The electrochemical nature of TMP was studied in 0.2 M pH 3.0 phosphate-buffer solution (PBS). The developed electrode displayed the highest peak current compared to nascent CPE. Effects of variation in different parameters, such as pH, immersion time, scan rate, and concentration, were investigated. The electrode process of TMP was irreversible and diffusion controlled with two electrons transferred. The effective concentration range (8.0 × 10 -7 M–1.0 × 10 -5 M) of TMP was obtained by varying the concentration with a lower limit of detection obtained to be 2.58 × 10 -8 M. In addition, this approach was effectively employed in the detection of TMP in pharmaceutical dosages and samples of urine with the excellent recovery data, suggesting the potency of the developed electrode in clinical and pharmaceutical sample analysis.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Thermal Activation of Zirconium(IV) Acetylacetonate Catalysts to Enhance Polyurethane Synthesis and Reprocessing

Carbamate formation and exchange catalysts enable efficient polyurethane (PU) manufacturing, as well as emerging recycling and reprocessing methods for PU thermosets. Zirconium β-diketonate complexes, such as Zr acetylacetonate [Zr(acac) 4 ], are effective alternatives to toxic organotin catalysts that have been used for PU reprocessing. Here, we report that Zr(acac) 4 undergoes a thermally activated process in the PU network during reprocessing that transforms it into a more active carbamate exchange catalyst. This process is associated with the irreversible loss of acetylacetonate ligands and is not observed for the more sterically hindered Zr 2,2,6,6-tetramethyl-3,5-heptanedione [Zr(tmhd) 4 ] complex. Crossover experiments between PU thermoplastics indicated enhanced carbamate exchange after the thermal activation of Zr(acac) 4 in the presence of one of the PUs, whereas a sample of Zr(acac) 4 activated in the absence of the PU had no catalytic activity. Thermal gravimetric analysis suggested that this process is associated with the loss of one protonated acac ligand. Stress relaxation analysis of PU thermosets indicated a distinct change in the characteristic relaxation time associated with the thermal activation of Zr(acac) 4 at temperatures above 140 °C; no such change was observed for samples reprocessed using Zr(tmhd) 4 . Density functional theory and molecular experiments suggest that irreversible ligand exchange of acac with alkoxide or carbamate reduces the activation energy for urethane formation and reversion. Furthermore, the Zr(acac) 4 catalyst activated in the presence of a PU’s polyol precursor provided more porous and less dense PU foams compared to those made using the unactivated Zr(acac) 4 catalyst. Furthermore, these findings are important for developing improved PU synthesis and recycling processes. Thermally activating a catalyst during reprocessing may provide more nuanced control of the in-use and reprocessing characteristics of PU thermosets.

Alcohols↗

DOE OSTI2020

Exploring the Charge Compensation Mechanism of P2-Type Na 0.6 Mg 0.3 Mn 0.7 O 2 Cathode Materials for Advanced Sodium-Ion Batteries

P2-type sodium layered transition metal oxides have been intensively investigated as promising cathode materials for sodium-ion batteries (SIBs) by virtue of their high specific capacity and high operating voltage. However, they suffer from problems of voltage decay, capacity fading, and structural deterioration, which hinder their practical application. Therefore, a mechanistic understanding of the cationic/anionic redox activity and capacity fading is indispensable for the further improvement of electrochemical performance. Here, a prototype cathode material of P2-type Na 0.6 Mg 0.3 Mn 0.7 O 2 is comprehensively investigated, which presents both cationic and anionic redox behaviors during the cycling process. By a combination of soft X-ray absorption spectroscopy and electroanalytical methods, we unambiguously reveal that only oxygen redox reaction is involved in the initial charge process, then both oxygen and manganese participate in the charge compensation in the following discharge process. In addition, a gradient distribution of Mn valence state from surface to bulk is disclosed, which could be mainly related to the irreversible oxygen activity during the charge process. Furthermore, we find that the average oxidation state of Mn is reduced upon extended cycles, leading to the noticeable capacity fading. Our results provide deeper insights into the intrinsic cationic/anionic redox mechanism of P2-type materials, which is vital for the rational design and optimization of advanced cathode materials for SIBs.

25 ENERGY STORAGE↗

DOE OSTI2020

Modeling of thermal pressurization in tight claystone using sequential THM coupling: Benchmarking and validation against in-situ heating experiments in COx claystone

We apply thermoporoelasticity and a sequentially coupling technique for modeling thermally-driven coupled Thermo-Hydro-Mechanical (THM) processes in tight claystone. A THM benchmark case with a corresponding analytic solution for thermoporoelasticity under a constant heat loading verifies the model. Thereafter, two in situ heating experiments are simulated for model validation: a smaller-scale heating experiment (TED experiment) and a larger-scale experiment (ALC experiment) in Callovo-Oxfordian (COx) claystone at the Meuse/Haute-Marne underground research laboratory in France. The model exhibits good performance to match the observed temperature and pore pressure evolution for the smaller-scale TED experiment. For the larger-scale ALC experiment, general trends of thermal-pressurization are captured in the modeling, but pressure is underestimated at some monitoring points during cool-down. This indicates that the THM response in the field may be affected by the variability of rock's properties or irreversible or time-dependent mechanical processes that are not included in the current thermoporoelastic model. The main contributions of this work are as follows: (1) we verify and validate the numerical simulator, TOUGH-FLAC, to be a valuable coupled THM modeling tool; (2) prove that the laboratory determined material parameters can be used as reference values for upscaling experiments. However, to better identify and quantify THM processes with modeling of in situ tests, more emphasize should be dedicated to obtaining high-quality mechanical deformation data.

58 GEOSCIENCES↗

DOE OSTI2020

Role of Intact Hydrogen-Bond Networks in Multiproton-Coupled Electron Transfer

The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole–phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-protoncoupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (~1000 mV s –1 ) a chemically reversible process is observed with an E 1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s –1 ) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. Furthermore, this work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Statistical Complexity of Quantum Learning

Abstract Learning problems involve settings in which an algorithm has to make decisions based on data, and possibly side information such as expert knowledge. This study has two main goals. First, it reviews and generalizes different results on the data and model complexity of quantum learning, where the data and/or the algorithm can be quantum, focusing on information‐theoretic techniques. Second, it introduces the notion of copy complexity, which quantifies the number of copies of a quantum state required to achieve a target accuracy level. Copy complexity arises from the destructive nature of quantum measurements, which irreversibly alter the state to be processed, limiting the information that can be extracted about quantum data. As a result, empirical risk minimization is generally inapplicable. The paper presents novel results on the copy complexity for both training and testing. To make the paper self‐contained and approachable by different research communities, an extensive background material is provided on classical results from statistical learning theory, as well as on the distinguishability of quantum states. Throughout, the differences between quantum and classical learning are highlighted by addressing both supervised and unsupervised learning, and extensive pointers are provided to the literature.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2026

Restoring Escaped Zincate in Rechargeable Alkaline Zinc Batteries with a Seed-in-Nanoshell Design

Rechargeable alkaline zinc batteries are promising candidates for safe and low-cost energy storage, but suffer from ZnO dissolution that causes irreversible active material loss and rapid capacity decay. Here, we report a seed-in-nanoshell ZnO anode architecture that mitigates dissolution by combining physical confinement with electrochemical restoration of dissolved zincate species. ZnO particles are encapsulated within an ion-sieving carbon nanoshell that restricts zincate diffusion, maintains electrical conductivity, and stabilizes repeated solid–solution–solid transformations. Silver (Ag) nanoparticles incorporated into the nanoshell act as zincophilic nucleation seeds, lowering the Zn deposition barrier and directing the redeposition of dissolved zincate back to metallic Zn during charging. This confinement-enabled restoration mechanism converts zincate dissolution from an irreversible loss pathway into a recoverable process, enabling improved performance under harsh test conditions. The anode also delivers 227.9 mAh g −1 at −40 °C. Finally, a scalable tens-of-gram synthesis of ZnO@Ag is demonstrated, underscoring the practical potential of this strategy for advanced aqueous zinc batteries.

25 ENERGY STORAGE↗

DOE OSTI2023

Virtual Time III, Part 1: Unified Virtual Time Synchronization for Parallel Discrete Event Simulation

Algorithms for synchronization of parallel discrete event simulation have historically been divided between conservative methods that require lookahead but not rollback, and optimistic methods that require rollback but not lookahead. In this paper we present a new approach in the form of a framework called Unified Virtual Time (UVT) that unifies the two approaches, combining the advantages of both within a single synchronization theory. Whenever timely lookahead information is available, a logical process (LP) executes conservatively using an irreversible event handler. When lookahead information is not available the LP does not block, as it would in a classical conservative execution, but instead executes optimistically using a reversible event handler. The switch from conservative to optimistic synchronization and back is decided on an event-by-event basis by the simulator, transparently to the model code. UVT treats conservative synchronization algorithms as optional accelerators for an underlying optimistic synchronization algorithm, enabling the speed of conservative execution whenever it is applicable, but otherwise falling back on the generality of optimistic execution. We describe UVT in a novel way, based on fundamental invariants, monotonicity requirements, and synchronization rules. UVT permits zero-delay messages and pays careful attention to tie-handling using superposition. We prove that under fairly general conditions a UVT simulation always makes progress in virtual time. This is Part 1 of a trio of papers describing the UVT framework for PDES, mixing conservative and optimistic synchronization and integrating throttling control.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2020

Ab Initio Studies of Discharge Mechanism of MnO 2 in Deep-Cycled Rechargeable Zn/MnO 2 Batteries

Rechargeable alkaline Zn/MnO 2 batteries are an attractive solution for large-scale energy storage applications. Recently, Bi and Cu additives have been used to increase the cycle life and capacity of rechargeable Zn/MnO 2 batteries, with an equivalent of the full two-electron capacity realized for many cycles, in the absence of zinc. However, the mechanism of the effect of Bi and Cu on the performance of rechargeable Zn/MnO 2 batteries has not been investigated in detail. We apply first-principles density functional computational methods to study the discharge mechanisms of the unmodified and Bi/Cu-modified γ -MnO 2 electrodes in rechargeable alkaline Zn/MnO 2 batteries. Using the results of our calculations, we analyze the possible redox reaction pathways in the γ -MnO 2 electrode and identify the electrochemical processes leading to the formation of irreversible discharge reaction products, such as hausmannite and hetaerolite. Our study demonstrates the possibility of formation of intermediate Bi-Mn and Cu-Mn oxides in deep-cycled Bi/Cu-modified MnO 2 electrodes. The formation of intermediate Bi-Mn and Cu-Mn oxides could reduce the rate of accumulation of irreversible reaction products in the MnO 2 electrode and improve the rechargeability and cyclability of Zn/MnO 2 batteries.

25 ENERGY STORAGE↗

DOE OSTI2022

Overcoming Degradation Pathways to Achieve Stable Blue Perovskite Light-Emitting Diodes

Mixed halide (Br/Cl) perovskite nanocrystals (NCs) that represent an advanced blue emitter commonly suffer from spectral instability and poor lifespan; notably, the lack of understanding of the failure mechanisms of these devices has restricted the future progress. Here, we determine that the degradation of CsPbBr x Cl 3– x NCs containing blue light-emitting diodes (LEDs) is due to the combination of two effects. Cl – drift among adjoining NCs under an electric field is found to induce a Cl-deficient material region in multiple NC layers, which dominates the unstable electroluminescence and causes fast degradation in the corresponding devices. In comparison, the monolayer NC devices that feature restricted anion drift pathways exhibit better operational stability; however, excess hole injection is demonstrated to induce irreversible chlorine loss in NCs. Such a process that largely arises from electrochemical oxidation of Cl – initiates a mild device failure in operation of tens of minutes. Through revealing these mechanisms, we modulate the devices’ construction and operational conditions to achieve a longer lifespan.

14 SOLAR ENERGY↗

DOE OSTI2020

Electron-beam-driven chemical processes during liquid phase transmission electron microscopy

Liquid phase (or liquid cell) transmission electron microscopy (LP-TEM) has been established as a powerful tool for observing dynamic processes in liquids at nanometer to atomic length scales. However, the simple act of observation using electrons irreversibly alters the nature of the sample. A clear understanding of electron beam-driven processes during LP-TEM is required to interpret in situ observations and utilize the electron beam as a stimulus to drive nanoscale dynamic processes. In this review, we discuss recent advances toward understanding, quantifying, mitigating, and harnessing electron beam-driven chemical processes occurring during LP-TEM. We will highlight progress in several research areas, including modeling electron beam-induced radiolysis near interfaces, electron beam-induced nanocrystal formation, and radiation damage of soft materials and biomolecules.

Woehl, Taylor J.↗

DOE OSTI2024

Co(II) Substitution Enhances the Esterase Activity of a de Novo Designed Zn(II) Carbonic Anhydrase

Abstract Carbonic Anhydrases (CAs) have been a target forde novoprotein designers due to the simplicity of the active site and rapid rate of the reaction. The first reported mimic contained a Zn(II) bound to three histidine imidazole nitrogens and an exogenous water molecule, hence closely mimicking the native enzymes’ first coordination sphere. Co(II) has served as an alternative metal to interrogate CAs due to its d 7 electronic configuration for more detailed solution characterization. We present here the Co(II) substituted [Co(II)(H 2 O/OH − )] N (TRIL2WL23H) 3 n+ that behaves similarly to native Co(II) substituted human‐CAs. Like the Zn(II) analogue, the cobalt‐derivative at slightly basic pH is incapable of hydrolyzing p‐nitrophenylacetate (pNPA); however, as the pH is increased a significant activity develops, which at pH values above 10 eventually yields a catalytic efficiency that exceeds that of the [Zn(II)(OH − )] N (TRIL2WL23H) 3 + peptide complex. X‐ray absorption analysis is consistent with an octahedral species at pH 7.5 that converts to a 5‐coordinate species by pH 11. UV‐vis spectroscopy can monitor this transition, giving a pK a for the conversion of 10.3. We assign this conversion to the formation of a 5‐coordinate Co(II)(N imid ) 3 (OH)(H 2 O) species. The pH dependent kinetic analysis indicates the maximal rate (k cat ), and thus the catalytic efficiency (k cat /K m ), follow the same pH profile as the spectroscopic conversion to the pentacoordinate species. This correlation suggests that the chemically irreversible ester hydrolysis corresponds to the rate determining process.

Chemistry↗

DOE OSTI2026

Understanding the Performance Gap between Polycrystalline and Single-Crystal Nickel-Rich Layered Oxide Cathodes

Singe-crystal (SC) nickel-rich layered oxide cathodes, composed of boundary-free particles with high tap density, offer significant advantages in volumetric energy density and mechanical strength compared with polycrystalline (PC) cathode materials. However, as the nickel content increases (≥80%), SC Ni-rich cathodes often suffer from faster performance degradation than PC cathodes of the same composition, and the underlying causes of this discrepancy remain poorly understood. Herein, we reveal the distinct Ni redox behaviors that govern the electrochemical performance of SC and PC Ni-rich cathodes using multiscale and operando characterization techniques. Our results indicate that the increasingly heterogeneous Ni oxidation process in SC cathodes leads to the additional irreversible oxygen redox activity that deteriorates both the mechanical and chemical structures. In contrast, PC cathodes, despite with more pronounced surface reconstruction, exhibit greater chemomechanical stability due to homogeneous redox reactions during charging. Consequently, we find that bulk degradation, more than surface reactions, ultimately leads to fast capacity decay of SC Ni-rich cathodes during cycling. In conclusion, this work offers a comprehensive view on the impact of Ni redox evolutions on the chemomechanical stability in Ni-rich layered oxide cathodes, providing new insights into the longstanding performance gap between SC and PC cathodes, and guiding the rational design of Ni-rich cathode architectures.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Probing three-dimensional mesoscopic interfacial structures in a single view using multibeam X-ray coherent surface scattering and holography imaging

Abstract Visualizing surface-supported and buried planar mesoscale structures, such as nanoelectronics, ultrathin-film quantum dots, photovoltaics, and heterogeneous catalysts, often requires high-resolution X-ray imaging and scattering. Here, we discovered that multibeam scattering in grazing-incident reflection geometry is sensitive to three-dimensional (3D) structures in a single view, which is difficult in conventional scattering or imaging approaches. We developed a 3D finite-element-based multibeam-scattering analysis to decode the heterogeneous electric-field distribution and to faithfully reproduce the complex scattering and surface features. This approach further leads to the demonstration of hard-X-ray Lloyd’s mirror interference of scattering waves, resembling dark-field, high-contrast surface holography under the grazing-angle scattering conditions. A first-principles calculation of the single-view holographic images resolves the surface patterns’ 3D morphology with nanometer resolutions, which is critical for ultrafine nanocircuit metrology. The holographic method and simulations pave the way for single-shot structural characterization for visualizing irreversible and morphology-transforming physical and chemical processes in situ or operando .

47 OTHER INSTRUMENTATION↗

DOE OSTI2021

Oxidative Catalytic Fractionation and Depolymerization of Lignin in a One-Pot Single-Catalyst System

It has been known that the yield of lignin monomers during lignin depolymerization is limited by the irreversible condensations of lignin in the fractionation and/or depolymerization process. In this study, we report a new oxidative catalytic fractionation (OCF) process with a simple and effective one-pot but two-step approach to depolymerize lignin to lignin-derived chemicals (LDCs) using polyoxometalate (POM) as the only catalyst. First, the POM effectively catalyzed the methoxylation of the active a-OH groups of lignin in a methanol and water mixture at low temperature (100 °C), and 96% of the stabilized lignin in the lignocellulose sawdust was extracted to the solution simultaneously. Then the lignin solution was heated to an elevated temperature (140 °C) in the same solvent. As a result, 74.0 wt % of the lignin (based on the weight of the Klason lignin in the wood) was converted to LDCs, including 45.9 wt % aromatic monomers.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2023

ac susceptibility studies of intra- and intergrain properties of high-$J_c$ Bi-2212 wires

Bi 2 Sr 2 CaCu 2 O x (Bi-2212) is the only high-$T_c$ superconductor (HTS) available as a multifilamentary round wire with multiple architectures and it is a very promising conductor for the realization of high-field applications. Despite their relatively simple wire fabrication by the powder-in-tube technique, Bi-2212 wires require a tightly controlled overpressure heat treatment (HT) with a multi-parameter time-temperature schedule to achieve high critical current density, $J_c$. Further, the variation of these HT parameters, changes in the wire design, wire diameter and powder quality can lead to variations in both the microstructure and the superconducting performance. Particularly noticeable are variations in $J_c$ performance and degree of filament bridging. In this work, we focus on the use of different magnetic characterization techniques to estimate the bridging level and assess the balance of INTER-grain and intra-grain superconducting properties including the irreversibility field ($H_{\text{irr}}$) and the pinning energy ($U_0$) in differently processed wires. Regardless of the actual bridging level, we find that the supercurrent flows at the filament bundle level, not just at the individual filament level. Moreover, using AC susceptibility we identify two distinct supercurrent contributions, one related to the intra-grain and one to the INTER-grain properties, whose irreversibility fields are different but without large sample-to-sample variation. Moreover, an additional component of intra-grain pinning mechanism becomes effective at low temperatures with positive effects also on the INTER-grain performance. The work clearly shows that detailed magnetic characterizations can become valuable tools to investigate the performance of differently processed Bi-2212 wires, correlating their microstructure and overall transport $J_c$, to obtain a deeper understanding of the causes of performance variation and paths to achieve further improvement.

2212↗