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DOE OSTI2026

Evaluation of 3D pixel silicon sensors for the CMS Phase-2 Inner Tracker

The high-luminosity upgrade of the CERN LHC requires the replacement of the CMS tracking detector to cope with the increased radiation fluence while maintaining its excellent performance. An extensive R&D program, aiming at using 3D pixel silicon sensors in the innermost barrel layer of the detector, has been carried out by CMS in collaboration with the FBK (Trento, Italy) and CNM (Barcelona, Spain) foundries. The sensors will feature a pixel cell size of 25 × 100 µm 2 , with a centrally located electrode connected to the readout chip. The sensors are read out by the RD53A and CROCv1 chips, developed in 65 nm CMOS technology by the RD53 Collaboration, a joint effort between the ATLAS and CMS groups. This paper reports the results achieved in beam test experiments before and after irradiation, up to a fluence of approximately 2 . 6 × 1 0 16 n eq /cm 2 . Measurements of assemblies irradiated to a fluence of 1 × 10 16 n˙eq/cm 2 show a hit detection efficiency higher than 96% at normal incidence, with fewer than 2% of channels masked, across a bias voltage range greater than 50 V . Even after irradiation to a higher fluence of 1.6 × 10 16 n˙eq/cm 2 , similar performance is maintained over a bias voltage range of 30 V , remaining well within CMS requirements.

3D pixel↗

DOE OSTI2020

Spectral Element Applications in Complex Nuclear Reactor Geometries: Tet-to-Hex Meshing

The spectral element code Nek5000 is an open-source, higher-order computational fluid dynamics code developed at Argonne National Laboratory. It is designed to solve incompressible Navier-Stokes equations, but it also has a low-Mach-number approximation feature available. Large eddy simulation is approached by explicit filtering of the velocity field (and other fields) to mimic the effect of dissipation due to the unresolved scale. The computational domain is decomposed into second-order hexahedral elements that conform to the boundaries. However, generating a high-quality pure-hexahedral mesh can be challenging for some problems. For simple geometries, traditional blocking methods can be used to decompose the domain into smaller blocks to generate a so-called structural mesh. A structural mesh can maintain good orthogonality but can have a highly skewed mesh to conform to the geometry, as well as unnecessary refinement in the far field. Moreover, for geometries with relative complexity, blocking the geometry becomes impossible. To address these issues, we adopted a let-to-hex strategy to generate a pure hexahedral mesh for Nek5000. First, we generate a pure tetrahedral mesh for the geometry; then we divide one tetrahedral element into four hexahedral elements. A pure tetrahedral mesh could be easily generated for complex geometries by using many current meshing codes. In this paper, we use the commercial codes ANSYS meshing and ANSYSICEM to generate the pure tetrahedral mesh and then convert it to a pure hexahedral mesh. Boundary layers are extruded in ANSYSICEM to maintain near-wall resolution.

ANSYS ICEM↗

DOE OSTI2022

UO 2 -liquid metal suspension fuel concept for enhanced passive safety of LWRs: A heat pipe case study

This work proposes a novel fuel concept for use in light-water type reactors (LWRs): UO 2 particles suspended in a low-melting-point liquid metal (LM). This new fuel form offers lower energy density and higher thermal conductivity, thus enhancing the fuel’s thermal performance compared to sintered UO 2 pellets. Two candidate alloys for the LM are proposed based on previous studies into accident-tolerant fuels: Bi-Pb-Sn and Pb-Sn. Ten research questions are provided to guide future development of this fuel. A simple heat pipe model was constructed by coupling a reactor physics code to a heat transport code and other physics modules. Scoping calculations were performed on this model core as a preliminary investigation into five of the research questions. A fuel with 13 wt% UO 2 was shown to maintain a steady-state peak coolant channel wall temperature below 400 °C, and maintain criticality via self-regulating reactivity feedback. Shortcomings of the present model are discussed in this work, along with proposed future model improvements and fuel development. The appendix provides an example of a reactor concept that could be developed to utilize this fuel, but more modeling and experimental work are needed before a full reactor concept can be developed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Development of an accelerator-based neutron source to prototype Mo-99 production, Part II: A liquid LBE loop under a high vacuum

To provide US domestic supply of Mo-99 without using high-enriched uranium (HEU), a subcritical uranium target assembly (UTA) is irradiated by an accelerator-based neutron source to create Mo-99 through fission. Part I of this work discusses the design of a liquid lead–bismuth eutectic (LBE) windowless target for an accelerator-based neutron source development. Part II discusses how to couple this windowless target to an accelerator operating at an ultra-high vacuum and the subcritical UTA cooled by water at room temperature. Due to the windowless design of the target, the liquid LBE flow shares an ultra-high vacuum (<1.3 × 10 -7 Pa or 10 -9 Torr) space with the accelerator. As a result of this shared vacuum space, the LBE system must operate at a high vacuum (10 -3 ~10 -6 Pa or 10 -5 ~10 -8 Torr). A magnetic rotary motion feedthrough unit utilizes magnetic fluid to allow rotation of the pump while maintaining a high vacuum environment. Prior to testing the LBE system under vacuum, a pump curve measurement is performed to estimate flowrate in the system. This measurement also generates data on orifice loss coefficients, which are compared to correlations in literature. The second experiment investigates vacuum level in the LBE system during operation. High vacuum is maintained (10 -3 ~10 -5 Pa or 10 -5 ~10 -7 Torr) during system operation, and a residual gas analyzer (RGA) scan shows that partial pressures of residual gases in the LBE system lower over the duration of LBE system operations. The third experiment investigates the gravity driven liquid LBE flowing out of the target chamber in the return line, which is partially full. If the liquid LBE is not drained quickly enough, flooding in the target chamber could occur. The coefficient n in the Manning equation is found to be around 0.008 s/m 1/3 . The last experiment performed is a demonstration that a vacuum jacket could provide sufficient thermal insulation to allow coupling between 300 °C LBE loop and a water tank at room temperature. In conclusion, the results from these experiments have influenced the development of the neutron source for the future commercial scale Mo-99 production system.

43 PARTICLE ACCELERATORS↗

DOE OSTI2025

Root cause analysis of a molten salt pump in FLUSTFA

The primary salt pump installed in the high-temperature FLUoride Salt Test Facility (FLUSTFA) was successfully operated for some time, but later ceased operation. To understand what occurred, a Root Cause Analysis (RCA) was performed. Steps taken to try to get the pump operational include adjusting the shaft position, increasing the heating power of the tape heaters on the pump volute, and manually rotating the pump shaft. While removing the insulation, corrosion was noted on the outside of the pump volute, and decolorization of the insulation and tape heaters was observed. Significant corrosion products were also observed in the pump itself and the piping connected to the pump. The nitrogen cover gas was maintained from before salt was introduced into the loop until the pump was dismounted and continues to be maintained even after the pump was removed. After considering probable scenarios, causes were assigned and corrective actions were developed to prevent those causes. Then, the RCA was presented to an advisory committee for review, the “Review Committee,” consisting of experts in large molten salt systems: Brandon Haugh, David Holcomb, Kevin Robb, and Vicente Rojas. As a result, the advisory committee provided comprehensive feedback, which have been incorporated into a revised RCA. Findings have then been summarized and reported in this publication.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2020

Scalable line and plane relaxation in a parallel structured multigrid solver

The efficient solution of sparse, linear systems that arise through the discretization of partial differential equations remains a key challenge for a range of high performance scientific simulations. One approach for reducing data movement and improving performance is by exposing and exploiting structure in a problem through the use of robust structured multilevel solvers. By choosing coarsening that preserves the structure of the problem, these methods maintain efficient structured computation and communication throughout the multigrid hierarchy. However, when coarsening is not permitted to be dependent on the operator, anisotropy must be addressed by the smoother — producing error compatible for coarse-grid correction with structured coarsening. Here, the components required in a scalable parallel structured solver are described with a focus on memory and communication efficiency of robust smoothers. While the implementation of communication and memory reduction techniques in smoothers integrated in a complete 3D solver present a significant engineering challenge, a novel approach is proposed that addresses these challenges systematically through a change to the solver’s execution model. Enabled by user-level threading paired with a set of data and communication abstractions, this approach permits seamless aggregation of communication in plane smoothers — directly reusing code for a 2D distributed multilevel cycle. Results show an effective reduction in communication costs for coarse-grid problems, and result in a speedup of 8.7x in smoothing routines shown in Fig. 12 using this approach. This produces a significant improvement to strong scalability while maintaining favorable weak scaling behavior. Finally, a parallel scaling study using a series of refined meshes is included that demonstrates the effectiveness of this approach in an application of interest.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2023

Cyber threat assessment of machine learning driven autonomous control systems of nuclear power plants

We report advanced cyber-attacks against critical infrastructure and the energy sector are becoming more common. With the invention of autonomous control systems (ACS) within advanced nuclear reactor designs, system designers, reactor operators, and regulators must consider cybersecurity during the design and operational phases. This article provides a cyber threat assessment of machine learning (ML)-based digital twinning (DT) technologies in the context of advanced reactor ACS. A cyber–physical testbed was created to emulate nuclear reactor digital instrumentation and controls (I&C) and act as a basis for the ACS. The ACS was designed as two plant-level DTs predicting reactor malfunctions and determining control actions and two component-level DTs responsible for classifying component states and forecasting component inputs and outputs (I/O). Two duplicate ACS designs– one using a traditional ML framework and one using an automated ML (AutoML) framework– were created and tested against cyber-attacks on training data, real-time process data, and ML model architectures to determine their respective qualitative cyber-risk in terms of likelihood and impact. Both frameworks showed similar cyber-resilience against training, real-time, and ML architecture attacks, proving that neither is inherently more secure. Recommended safeguard and security measures are posed to system designers, reactor operators, and regulators to maintain the cybersecurity of ML-based DT technologies such as ACS, prompting a holistic view of shared responsibility for maintaining cyber-secure ML-based systems.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2020

Synthesis and magnetic performance of gadolinium powder produced with rotating disk atomization

Spherical powder is key for achieving good heat transfer and maintaining low pressure drop for heat transfer fluid in magnetocaloric regenerator. Obtaining relatively large spherical powder of rare earth metals that are extremely sensitive to oxygen is challenging. Comparing to gas atomization and plasma rotating electrode methods, rotating disk atomization (RDA) method is more robust for obtaining a small amount of powder with a short turn-around time, thereby, more suitable for research and development of new magnetocaloric materials. In this work, commercially bulk gadolinium was successfully atomized to produce spherical powder in the targeted 150–250 μm range. The obtained powder exhibited the expected magnetocaloric performance with a maximum change of magnetic entropy of 12.1 J/kg K and a maximum adiabatic temperature change of 12.8 K with an applied magnetic field of 7 T.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Understanding the ignition process and flame structure of conventional and oxygenated fuels under engine relevant conditions – An optical study

Renewably generated synthetic fuels such as poly-oxymethylene ethers (OME) have a significant potential to effectively break the soot-NOX trade-off in compression ignition engines by using exhaust gas recirculation (EGR) to maintain low nitrogen oxide (NOX) emissions while maintaining good efficiency and simultaneously contributing to circular carbon economy. However, owing to the fundamental differences in properties of OME when compared to fossil-based diesel fuels, it is critical to fully understand its ignition and combustion phenomenology to take advantage of this fuel to its utmost potential. In this context, this work outlines the results of a systematic experimental study performed in a heavy-duty, single-cylinder, optical engine probing the spatial and temporal progression of fuel decomposition and ignition behavior of OME when compared to n-dodecane, a diesel-fuel surrogate. Thermodynamic analysis and optical diagnostics techniques including simultaneous HCHO-PLIF and OH-PLIF complemented by high-speed OH* chemiluminescence were employed along with parametric sweeps of intake temperature and EGR dilution rates. OME does not exhibit any observable low temperature heat release irrespective of the ambient oxygen concentration. Differences in the observed diffusive flame structure such as longer flame lift-off length, less pronounced combustion recession, faster premixed burn at ignition (“volumetric” ignition), non-sooting behavior suggest that the inherent presence of fuel-bound oxygen in OME can skew the air-fuel ratio (AFR) distribution within the jet thereby reducing the reliance of combustion on mixing and air entrainment. This leads to rapid late-cycle oxidation leading to shorter combustion duration and favorable combustion phasing. Results also suggest that OME exhibits relatively weak negative temperature coefficient (NTC) behavior, however, the OME fuel-decomposition kinetic-pathways produce significant concentration of HCHO, which might be erroneously interpreted as a product of cool-flames.

Air-fuel ratio↗

DOE OSTI2024

Generation and validation of comprehensive synthetic weather histories using auto-regressive moving-average models

As energy system design moves to more complex methods of optimization including machine learning there is a significant need for more weather data than is available. One method to solve this is using synthetic data models such as the auto-regressive moving-average (ARMA) model which has been frequently utilized to create such data. This paper looks at extending the ARMA algorithm to generate solar components through the use of clearsky detrending, maintaining vector relationships and by leveraging physical relationships. The method for the creation of entirely synthetic weather data files including key weather variables for energy system analysis is presented. Furthermore, a detailed comparison of energy system simulations utilizing both real and synthetic data is made using NREL’s System Advisor Model. Whilst good agreement is made for the solar variables, and other weather variables, ARMA methods often fail to capture the standard deviation and skew of annual weather distributions. Vector-ARMA is shown to maintain correlations between variables and thus generate data sets that perform similarly in energy system design. Here, it is finally shown that the ARMA method fails to preserve day-today correlations in weather variables and thus over-predicts optimal energy storage by 21% for a residential solar application.

42 ENGINEERING↗

DOE OSTI2022

Enhanced ZIF-8-enabled colorimetric CO 2 sensing through dye-precursor synthesis

The accumulation of carbon dioxide (CO 2 ) within enclosed spaces, along with volatile organic compounds, under certain humidity, temperature, and ventilation conditions is associated with detrimental human health symptoms such as fatigue. Color-based chemical sensing is a promising approach to detect CO 2 levels relevant to indoor air quality through producing fast, quantifiable output visible to the naked eye. In a prior work, a colorimetric gas sensor was fabricated through synthesizing the metal-organic framework, ZIF-8, as the adsorbent, followed by post-synthetic mixing with a dye, phenol red (PSP), and primary amine, ethylenediamine (ED). While this sensor (termed PSP-ED/ZIF-8) maintained its structural integrity in atmospheric conditions and exhibited an increasing fuchsia-to-yellow color change with increasing CO 2 levels in dry environment, the colorimetric response greatly suffered in the presence of humid CO 2 . Here in this work, a significantly improved colorimetric CO 2 sensor (referred to as ED/PSP:ZIF-8) is accomplished through directly incorporating phenol red in the ZIF-8 metal and linker precursor solutions and then blending with ethylenediamine. MATLAB-generated color distributions and in-situ ultraviolet-visible (UV-Vis) spectroscopic studies quantitatively demonstrate an enhanced colorimetric gas response of ED/PSP:ZIF-8 compared to that of PSP-ED/ZIF-8 across an important range of CO 2 for indoor air quality monitoring (500 – 3500 ppm) and across a range of humidity. The new sensor also exhibits high selectivity to CO 2 compared to select volatile organic compounds, such as acetone and ethanol, which contribute to human health symptoms experienced indoors. The enhanced performance is attributed to the proposed incorporation of phenol red within ZIF-8, while maintaining the chemical stability of the MOF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Establishment of FXS-A9 panel with a single human X chromosome from fragile X syndrome-associated individual

Highlights: • We established mouse A9 cells with human X chromosome from FXS carrier and patient. • FXS-associated CGG repeats were stably maintained in established rodent cells. • Epigenetic status of CGG repeat region were maintained in established rodent cells. • Human FMR1 expression in these cells was according to each CGG repeat length. Fragile X syndrome (FXS) is the most common inheritable form of intellectual disability. FMR1, the gene responsible for FXS, is located on human chromosome Xq27.3 and contains a stretch of CGG trinucleotide repeats in its 5′ untranslated region. FXS is caused by CGG repeats that expand beyond 200, resulting in FMR1 silencing via promoter hypermethylation. The molecular mechanism underlying CGG repeat expansion, a fundamental cause of FXS, remains poorly understood, partly due to a lack of experimental systems. Accumulated evidence indicates that the large chromosomal region flanking a CGG repeat is critical for repeat dynamics. In the present study, we isolated and introduced whole human X chromosomes from healthy, FXS premutation carriers, or FXS patients who carried disease condition-associated CGG repeat lengths, into mouse A9 cells via microcell-mediated chromosome transfer. The CGG repeat length-associated methylation status and human FMR1 expression in these monochromosomal hybrid cells mimicked those in humans. Thus, this set of A9 cells containing CGG repeats from three different origins (FXS-A9 panel) may provide a valuable resource for investigating a series of genetic and epigenetic CGG repeat dynamics during FXS pathogenesis.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2021

Three-dimensional spheroid culture induces apical-basal polarity and the original characteristics of immortalized human renal proximal tubule epithelial cells

Highlights: • Immortalized proximal tubule cells (HK-2 cells) formed a tubule-like structure. • The 3D spheroid culture enhanced apical-basal polarity of HK-2 cells. • The 3D spheroid culture induced Na transport function of HK-2 cells. • The 3D spheroid culture promoted up-regulation of kidney development-related genes. The proximal tubules, which are part of the kidney, maintain blood homeostasis by absorbing amino acids, glucose, water, and ions such as sodium (Na), potassium, and bicarbonate. Proximal tubule dysfunction is associated with the pathogenesis of many kidney diseases. Renal proximal tubular epithelial cells (RPTECs) are responsible for the main functions of the proximal tubules. Therefore, in vitro experiments using RPTECs would greatly enhance our understanding of nephron physiology and pathobiology. It is preferable to use immortalized cell lines, such as human kidney-2 (HK-2) cells, because they are derived from humans and maintain growth indefinitely. However, tissue-specific RPTEC phenotypes, including apical-basal polarization, are frequently lost in conventional two-dimensional culture methods in part due to microenvironmental deficiencies. To overcome this limitation, we developed a three-dimensional (3D) spheroid culture method for HK-2 cells using an extracellular matrix. HK-2 spheroids in 3D culture formed a tubule-like architecture with cellular polarity and showed markedly restored Na transport function. 3D culture of HK-2 cells also increased expression of kidney development–related genes, including WNT9B. Models of human renal tubules using HK-2 spheroids will greatly improve our understanding of the physiology and pathobiology of the kidney.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2021

DYRK1A is required for maintenance of cancer stemness, contributing to tumorigenic potential in oral/oropharyngeal squamous cell carcinoma

Highlights: • DYRK1A is essential to maintain cancer stemness in OSCC. • DYRK1A regulates cancer stemness via FGF2 expression. • Levels of DYRK1A and FGF2 expression are positively correlated in OSCC cells. • DYRK1A-FGF2 is a novel molecular axis regulating cancer stemness in OSCC. DYRK1A, one of the dual-specificity tyrosine phosphorylation-regulated kinases (DYRKs), plays an important role in various biological processes by regulating downstream targets via kinase-dependent and independent mechanisms. Here, we report a novel role of DYRK1A in maintaining tumor growth and stemness of oral/oropharyngeal squamous cell carcinoma (OSCC) cells. Deletion of DYRK1A from OSCC cells abrogated their in vivo tumorigenicity and self-renewal capacity, the key features of cancer stem-like cells (CSCs; also referred to as tumor-initiating cells). The DYRK1A deletion also induced the suppression of CSC populations and properties, such as migration ability and chemoresistance. Conversely, ectopic expression of DYRK1A in OSCC cells augmented their CSC phenotype. Among five DYRK members (DYRK1A, 1B, 2, 3, and 4), DYRK1A is the most dominantly expressed kinase, and its expression is upregulated in OSCC compared to normal oral epithelial cells. More importantly, DYRK1A was highly enriched in various CSC-enriched OSCC populations compared to their corresponding non-CSC populations, indicating its pivotal role in cancer progression and stemness. Further, our study revealed that fibroblast growth factor 2 (FGF2) is a key regulator in the DYRK1A-mediated CSC regulation. Functional studies demonstrated that the loss of DYRK1A inhibits CSC phenotype via reduction of FGF2. Overexpression of DYRK1A promotes CSC phenotype via upregulation of FGF2. Our study delineates a novel mechanism of cancer stemness regulation by DYRK1A-FGF2 axis in OSCC. Thus, inhibition of DYRK1A would lead to a potential novel therapeutic option for targeting CSCs in OSCC.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2021

Differential localization patterns of pyruvate kinase isoforms in murine naïve, formative, and primed pluripotent states

Highlights: • PKM1/2 protein abundance is greater in formative mEpiLCs compared to naïve mESCs or primed mEpiSCs. The ratio of PKM1/2 is maintained. • PKM1/2 are localized in both nuclear and cytoplasmic regions relative to GAPDH and OCT4 across the pluripotent continuum. • PKM1 localization is strongly correlated to OCT4 localization, and moderately to GAPDH in formative mEpiLCs. • PKM1/2 localization is moderately correlated to OCT4 and GAPDH localization in naïve mESCs. • PKM1/2 localization are moderately correlated to GAPDH localization in primed mEpiSCs. Mouse embryonic stem cells (mESCs) and mouse epiblast stem cells (mEpiSCs) represent opposite ends of the pluripotency continuum, referred to as naïve and primed pluripotent states, respectively. These divergent pluripotent states differ in several ways, including growth factor requirements, transcription factor expression, DNA methylation patterns, and metabolic profiles. Naïve cells employ both glycolysis and oxidative phosphorylation (OXPHOS), whereas primed cells preferentially utilize aerobic glycolysis, a trait shared with cancer cells referred to as the Warburg Effect. Until recently, metabolism has been regarded as a by-product of cell fate, however, evidence now supports metabolism as being a driver of stem cell state and fate decisions. Pyruvate kinase muscle isoforms (PKM1 and PKM2) are important for generating and maintaining pluripotent stem cells (PSCs) and mediating the Warburg Effect. Both isoforms catalyze the final, rate limiting step of glycolysis, generating adenosine triphosphate and pyruvate, however, the precise role(s) of PKM1/2 in naïve and primed pluripotency is not well understood. The primary objective of this study was to characterize the cellular expression and localization patterns of PKM1 and PKM2 in mESCs, chemically transitioned epiblast-like cells (mEpiLCs) representing formative pluripotency, and mEpiSCs using immunoblotting and confocal microscopy. The results indicate that PKM1 and PKM2 are not only localized to the cytoplasm, but also accumulate in differential subnuclear regions of mESC, mEpiLCs, and mEpiSCs as determined by a quantitative confocal microscopy employing orthogonal projections and airyscan processing. Importantly, we discovered that the subnuclear localization of PKM1/2 changes during the transition from mESCs, mEpiLCs, and mEpiSCs. Finally, we have comprehensively validated the appropriateness and power of the Pearson's correlation coefficient and Manders's overlap coefficient for assessing nuclear and cytoplasmic protein colocalization in PSCs by immunofluorescence confocal microscopy. We propose that nuclear PKM1/2 may assist with distinct pluripotency state maintenance and lineage priming by non-canonical mechanisms. These results advance our understanding of the overall mechanisms controlling naïve, formative, and primed pluripotency.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2020

Multimodal Analysis of Reaction Pathways of Cathode Materials for Lithium Ion Batteries

Conversion mechanism in lithium ion batteries provides higher capacity than intercalation mechanism since multiple numbers of electrons and lithium ions are associated. However, poor cycling stability, large voltage hysteresis, and low energy efficiency have been great challenges of conversion reaction. To address those issues, conversion-type electrode materials have been reformed via doping or substituting other elements. For example, iron fluorides (FeF 2 , FeF 3 ) have modified as iron oxyfluorides (FeF 1-x O x ), showing enhanced long-term stability. Furthermore, co-substituted (both anion and cation substituted) Fe 0.9 Co 0.1 OF (FeCoOF) was demonstrated excellent cycling stability. (capacity of 350 mAh g -1 at a current of 500 mA g -1 for 1000 cycles). Substituting anion and cation in iron fluoride has been suggested as an effective method to achieve better reversibility but understanding of lithiation reactions in co-substituted FeCoOF is not clear. This work takes advantage of ex-situ/ in-situ synchrotron X-ray based techniques and transmission electron microscopy to elucidate structural changes with lithium ion, which may provide fundamental insights into modifying conversion-type materials. Figure 1 presents discharge-charge curves and pair distribution function patterns acquired at each potential. As lithium ions were inserted, structural changes were noticed both at short-range and long-range. However, long-range ordering was nearly maintained even at 1 V, indicating absence of conversion reaction. Figure 2 shows lithiation induced structural evolution of a single FeCoOF nanorod observed in real time. As lithiation proceeds, the width of nanorods shows a stepwise increase, particularly A in figure 2d, which may indicate multiple steps of lithiation occur. Considering that conversion reaction takes place around 2 V in FeF 3 , co-substitution Co and O into iron fluoride may change thermodynamic features of lithiation reactions by lowering the initiation potential for conversion reaction. Instead, phase transformations occur at long-range order, which may help maintaining structural integrity during operation, eventually, achieving cycling stability.

25 ENERGY STORAGE↗

DOE OSTI2023

Phase Stability, Band Gap Tuning, and Rashba Splitting in Selenium-Alloyed Bournonite: CuPbSb(S 1– x Se x ) 3

Recently, bournonite (CuPbSbS 3 ) has been identified as a potential ferroelectric photovoltaic (PV) material with a 1.3 eV band gap, which falls in an appropriate range for single junction PV devices. Progress in applying bournonite has yielded several studies reporting successful thin-film processing, the most recent of which demonstrated a 2.65% power conversion efficiency for a bournonite-based PV device. In an effort to explore bournonite band gap engineering for PV and other prospective applications (e.g., thermoelectric, spintronic), we here consider the solid-state synthesis of selenium-alloyed bournonite, CuPbSb(S 1-x Se x ) 3 , across the full range of x (0.0 ≤ x ≤ 1.0), and report phase purity for 0.0 ≤ x ≤ 0.5. We characterize the crystal structure and band gap of the samples using X-ray diffraction and diffuse reflectance spectroscopy, determining a band gap decrease for single-phase samples from 1.25 eV at x = 0.0 to 1.06 eV at x = 0.5. Formation energies determined using dispersion corrected hybrid density functional theory (DFT) support experimental findings and are consistent with the stability (instability) of the x = 0.5 (x = 1.0) structure relative to starting materials. The computed band structures show a decreasing trend in the band gap with increasing x, again consistent with experiment, with the states at the conduction (valence) band minima (maxima) being principally derived from Pb (S/Se) states. Spin texture analysis and detailed comparison of spin splitting parameters show that Se-alloying modifies the band gap while maintaining Rashba spin splitting character within the electronic structure. Rashba splitting is most pronounced for the conduction band minimum along the Γ-X path in the Brillouin zone. Energy separation between spin states is maintained at ΔE~0.2 eV for the various Se contents, with σz as the spin direction. Furthermore, a smaller spin splitting occurs along Γ-Z (decreasing value with increasing x), with σ x as the spin direction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Potential Adoption and Benefits of Co-Optimized Multimode Engines and Fuels for U.S. Light-Duty Vehicles

Exploring a diverse portfolio of technologies for decarbonization is crucial to understanding the potential impacts of different technological solutions and their associated environmental implications. Using high-octane, high-sensitivity biofuel blends in co-optimized multimode engines can increase engine efficiency and reduce vehicle emissions. Here, the multimode engine research focuses on the benefits of light-duty vehicle engines, which can operate in multiple modes depending on the vehicle's load. Low-temperature combustion can improve efficiency and reduce emissions (such as those from oxides of nitrogen and particulate matter) during low-load operation, while spark ignition performance is maintained in high-load operation. These advanced engines can be optimized to run on blends of biobased fuels. This analysis models scenarios for potential market adoption of co-optimized multimode vehicles fueled by three different bioblendstocks: ethanol, isopropanol, and isobutanol. An integrated modeling approach is used to forecast the energy and environmental impacts of the deployment of co-optimized multimode vehicles and fuels in the light-duty sector over the 2020-to-2050 time horizon. The multidisciplinary approach combines vehicle sales modeling, system dynamics modeling of the biorefining industry, and life cycle assessment to estimate the emissions and energy benefits. The models consider market forces such as consumer preferences for vehicle attributes, biofuel supply and demand dynamics subject to biorefinery capacity build-out and bioresource constraints, and forecasted changes to the U.S. bulk energy system over time. Market adoption of co-optimized vehicles is evaluated across a wide parameter space for incremental vehicle cost and engine efficiency improvement. This analysis reveals that the deployment of co-optimized multimode fuels and vehicles results in up to a 5% reduction in annual sector-wide life cycle greenhouse gas (GHG) emissions by 2050, relative to a business-as-usual scenario, but is also indicates environmental trade-offs, such as higher life cycle water-use. Emission benefits could potentially increase beyond 2050, as the new technologies penetrate the market and gain a foothold. Results also show that, under certain circumstances, vehicles with engines co-optimized for use with high-octane, high-sensitivity biofuel blends can be cost-competitive with conventional gasoline, while reducing GHG emissions. Our modeling results indicate that co-optimized multimode fuels and engines can be strategically leveraged in tandem with electrification to decarbonize the light-duty sector. Co-optimized vehicles could play a role in the early years of the time horizon, while electric vehicles (EVs) could become more competitive in the later years, highlighting the complementary benefits of these technologies for GHG reductions.

Oke, Doris↗