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Cu Doping Increases Capacity Retention in LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) by Altering the Potential of the Ni-Based Redox Couple and Inhibiting Particle Pulverization

To discern the influence of Cu 2+ as a dopant on both the structural and electrochemical characteristics of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), Cu 2+ (aq) was added to the coprecipitation synthesis from the constituent ions. At 5 mol % Cu 2+ , a single-phase Cu-NMC product results, evidenced by an increase in d-spacing along the [003] and [104] directions and a slight increase in the crystal volume of the R–3m hexagonal (rock-salt superstructure) lattice. XRD data and high-resolution TEM imaging support Cu 2+ doping primarily on the transition metal 3b Wyckoff sites. Here, galvanostatic cycling of Cu-NMC shows a reversible gravimetric capacity of 102 mAh/g compared to 136 mAh/g for undoped NMC. Despite the lower capacity, the discharge capacity retention of Cu-NMC is 89% after 100 cycles compared to only 70% for NMC. XPS analysis reveals that this lower capacity is due to an increase in the concentration of Ni 3+ ions at the surface, while XRD data collected at the top and bottom of charge show a smaller decrease in crystalline domain size for Cu-NMC (40.5% decrease) compared to NMC (74.7% decrease), translating to pulverization of the secondary particles.

25 ENERGY STORAGE↗

Revisiting two thiophosphate compounds constituting d 0 transition metal HfP 2 S 6 and d 10 transition metal α-Ag 4 P 2 S 6 as multifunctional materials for combining second harmonic generation response and photocurrent response

Two acentric thiophosphate compounds, HfP 2 S 6 and α-Ag 4 P 2 S 6 , are revisited and studied as infrared nonlinear optical materials. HfP 2 S 6 and α-Ag 4 P 2 S 6 were structurally characterized without any property measurements. Here, in this work, HfP 2 S 6 and α-Ag 4 P 2 S 6 were synthesized via high temperature salt flux reactions. Low-temperature polymorph acentric α-Ag 4 P 2 S 6 was purified and grown as mm-sized crystals with the aid of AgBr flux. The AgBr flux was revealed to play an important role in stabilizing the acentric α-Ag 4 P 2 S 6 . The acentric α-Ag 4 P 2 S 6 transforms to centrosymmetric β-Ag 4 P 2 S 6 at 850(5) K, which is revealed by differential scanning calorimetry (DSC) analysis and powder X-ray diffraction experiments. HfP 2 S 6 and α-Ag 4 P 2 S 6 are discovered by UV-vis spectrum measurements as indirect bandgap semiconductors with bandgaps of 2.2(1) eV and 2.5(1) eV, respectively, which is supported by DFT calculations and TB-LMTO-ASA calculations. The bonding pictures of α-Ag 4 P 2 S 6 were studied by crystal orbital Hamilton population calculations (COHP) coupled with electron localization function (ELF) analysis. DFT calculations predict that HfP 2 S 6 and α-Ag 4 P 2 S 6 would exhibit different optical performances regardless of being constructed from identical [P 2 S 6 ] motifs. HfP 2 S 6 exhibits a low second harmonic generation (SHG) response, ~0.21 × AGS (for the sample of particle size of 25 μm). α-Ag 4 P 2 S 6 possesses moderate SHG response, ~0.61 × AGS (for the sample of particle size of 225 μm) coupled with a high laser damage threshold (LDT) of ~3.2 × AGS. Characteristics of high ambient stability, moderate bandgap and SHG response, type-I phase-matching capability, and high LDT together with the easy growth of large crystals make α-Ag 4 P 2 S 6 attractive for future infrared nonlinear optical applications. Photocurrent measurements found that α-Ag 4 P 2 S 6 and β-Ag 4 P 2 S 6 have high photocurrent response, 165 nA cm -2 and 135 nA cm -2 , respectively. α-Ag 4 P 2 S 6 is a new multifunctional material of the ternary Ag–P–S system, which combines nonlinear optical (NLO) properties and photocurrent response.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tonopah Test Range Air Monitoring: CY2018 Meteorological, Radiological, and Wind Transported Particulate Observations

In 1963, the U.S. Department of Energy (DOE) (formerly the Atomic Energy Commission [AEC]), implemented Operation Roller Coaster on the Tonopah Test Range (TTR) and an adjacent area of the Nevada Test and Training Range (NTTR) (formerly the Nellis Air Force Range). This operation resulted in radionuclide-contaminated soils at the Double Tracks site and Clean Slate I, II, and III sites. This report documents observations made during ongoing monitoring of radiological, meteorological, and dust conditions at stations installed adjacent to the Clean Slate sites and at the TTR Sandia National Laboratories (SNL) Range Operations Center (ROC). The primary objective of the monitoring effort is to support the DOE Environmental Management Nevada Program (EM NV) in the safe remediation of the environmental legacy of nuclear device development and testing by determining if wind blowing across the Clean Slate sites is transporting particles of radionuclide-contaminated soil beyond the physical and administrative boundaries of the sites, and to provide information for designing long-term monitoring of the sites. The monitoring program in 2018 included five stations. Station 400, located within TTR Area 3 and near the ROC, monitors conditions near the local workforce center. Stations 401 and 403 are located on the northern and southeastern perimeter fence lines, respectively, of the Clean Slate III site. Stations 404 and 405 are along the northern and eastern boundary fence, respectively, at Clean Slate II. The stations are generally downwind of the contaminated areas during either northwesterly or southerly winds, which are the predominant wind directions. The stations—which are similar in design to the Community Environmental Monitoring Program (CEMP) stations operating at locations surrounding the Nevada National Security Site and TTR—include meteorological instruments and continuous-flow, low-volume air samplers. Three pressurized ionization chambers for measuring gamma energy are in use at Stations 400, 401, and 403. Saltation sensors and saltation traps are deployed at the stations adjacent to the Clean Slate sites. Detailed meteorological data are recorded on data loggers, with periodic uploads via a satellite system to the Western Regional Climate Center (WRCC) at Desert Research Institute (DRI), to monitor instrument and site conditions. Air filter samples are collected every two weeks and the deposits in the saltation traps are collected when a sufficient sample mass for analysis has accumulated (generally a six- to eight-month interval). Monitoring at TTR in calendar year (CY) 2018 provided surveillance of both ambient conditions, and ground disturbance associated with remediation activities at Clean Slate II and III. The first half of CY2018 data from Stations 404 and 405 at Clean Slate II were collected during remediation activities at that site, and data collected during the final third of the year at Stations 401 and 403 at Clean Slate III coincided with remediation work at the site. Ambient conditions prevailed at Station 400 throughout the year. Dust transport by suspension and saltation is strongly dependent on wind speed. Concentrations of PM 10 (particulate matter of aerodynamic diameter ≤10 micrometers [μm], a size fraction of small particles that are suspended in the air and can be easily inhaled) remain low until winds exceed approximately 32 kilometers per hour (km/hr) (20 miles per hour [mph]). Saltation particle counts also increase above the same general threshold wind speed. Wind speeds in excess of 32 km/hr (20 mph) occur less than three percent of the time at the sites. Ground disturbing remediation activities were carried out at Clean Slate II from October 31, 2017, until July 26, 2018. Station 404 is located closest to the remediation area and is downwind of the area when winds are from the south. By late November, analysis of dust from the air sampler at Station 404 registered increases in plutonium-239+240 ( 239+240 Pu) concentrations. Peak plutonium concentrations, accompanied by elevated gross alpha concentrations and the detection of americium-241 ( 241 Am) by gamma spectroscopy, occurred between March and May 2018. During spring and early summer of 2018, elevated radionuclide concentrations were also measured in dust collected from the air sampler at Station 405, which is more than twice the distance from the remediation activity as Station 404. A minor but sustained increase in gross alpha concentration of suspended dust collected at Stations 400, 401, and 403 was also observed starting in May 2018 and continuing into August. Stations 401 and 403 are approximately 4.8 to 6.4 km (three to four miles) from Clean Slate II and Station 400 is approximately 13 km (eight miles) from that site. The radionuclide content of material that saltated into the passive Big Spring Number Eight (BSNE) traps during the Clean Slate II remediation period increased in both the traps facing toward and away from the fenced contamination area at Station 404, with the largest increases in concentration (almost five times the previous 239+240 Pu concentration) observed in the traps facing the fenced area. The radionuclide concentration in material in the trap facing away from the fence more than doubled from that measured in 2017. A similar increase was observed for the saltation trap facing away from the fenced area at Station 405, although no increase was observed for material captured in the trap facing the fenced area. Particles ranging in size from 50 to 500 µm generally move by saltation processes and are not expected to significantly contribute to dose for someone breathing in the standard respiratory zone for adult humans (1.5 to 1.7 m [4.9 to 5.6 ft] above ground level) because they are too large to be entrained in the air as suspended dust. Remediation activities at Clean Slate III began on September 5, 2018, and continued until a brief hiatus started on December 20, 2018. Although Station 401 is much closer to the remediation area than Station 403, the first increase in gross alpha and 239+240 Pu concentrations was noted in dust from filters collected at Station 403 in early November 2018. The highest radionuclide concentrations of 2018 at the Clean Slate III stations were recorded in air samples taken from Stations 401 and 403 in late December 2018 and these concentrations were comparable between the two station locations. Gamma rate data measured by the PICs was slightly higher than the annual average at Stations 401 and 403 after remediation activities began, but no single measurement was outside of the range observed in 2018 prior to remediation activities. No increase in radionuclide concentration was observed for the Clean Slate III remediation time period on air filters collected from the other stations. Radiological monitoring at Station 400—which is located at the ROC, and therefore the closest regularly staffed work location to the Clean Slate sites—recorded a higher mean gross alpha activity from dust collected on air sampler filters than in previous years. The individual biweekly air filters yielded measurements of gross alpha that were at or below the mean plus one standard deviation measured in CY2017, except for the period from April 25, 2018, through September 12, 2018. Nonetheless, gamma spectroscopy of all air filters from Station 400 identified only naturally occurring radionuclides, with no detection of americium-241 ( 241 Am) (which is used as an indicator of plutonium-241[ 241 Pu]). Alpha spectroscopy of selected air filters collected at Station 400 did not detect plutonium-238 ( 238 Pu) or 239+240 Pu above the analytical detection limit. Gross beta and gamma exposure rate data were comparable to data from regional CEMP stations. No saltation traps are deployed at Station 400. Considering the ambient monitoring periods during CY2018, the monitoring stations adjacent to the Clean Slate sites recorded above-background 238 Pu and 239+240 Pu concentrations (SNL, 1998; Turner et al., 2003) in samples collected by passive saltation traps and on selected air filters. These observations were consistent with previous years and indicated that radionuclide movement occurred under ambient conditions by processes of both saltation and suspension. The presence of radionuclides in all saltation traps, both upwind and downwind of the fenced contamination areas, was consistent with previous radiological survey results (EG&G, 1979) that show lower concentration radiologically contaminated material dispersed outside the fenced area. Although 239+240 Pu concentrations in the air filter samples were sometimes orders of magnitude higher than background, the concentrations were below risk-based action levels defined for an industrial area worker scenario (U.S. DOE, 2014). The interception of airborne dust with above-background radionuclide concentrations demonstrates that dispersal processes are continuing. Strong winds are the driver for both suspension and saltation of dust and soil. The recorded wind speed and PM10 during remediation activities at Clean Slate II and III identified discrete wind events lasting approximately five to eight hours each, which accounted for the greatest PM 10 concentrations at the monitoring stations. These events captured the effect of winds from the northwest and from the south. The observed differences in dust loading and radionuclide concentrations for the monitoring stations when they were either upwind or downwind of the contamination area identify the remediation area as a source of plutonium contaminated dust. The increase in concentration of radionuclides in airborne dust during the remediation activities, compared with measurements under previous ambient conditions (mean 239+240 Pu concentrations during remediation activities are approximately nine to 40 times higher compared to pre-remediation concentrations, depending on monitoring station), highlights the impact of land disturbance on wind-borne contaminant transport from the Clean Slate test areas. The meteorological and particulate matter monitoring indicated that conditions for wind-borne contaminant movement exist at the Clean Slate sites, and that transport of radionuclide-contaminated soil by both suspension and saltation occurred under ambient conditions and accelerated when the sites were disturbed. The 239+240 Pu alpha spectroscopy results indicated that airborne concentrations during remediation activities ranged from 2 × 10-16 to 380 × 10-16 µCi/ml. These results can be compared to the derived air concentration limit for 239 Pu of 6 × 10-11 µCi/ml for occupational workers contained in Code of Federal Regulations 10 CFR 835, Occupational Radiation Protection. Even though the air sampling results document an increase in concentration during remediation activities, the observed concentrations are less than 0.06 percent of the occupational limit. The Corrective Action Unit (CAU) closure strategy uses a risk-based approach, whereby acceptable contaminant concentrations are determined as a function of anticipated human exposure.

54 ENVIRONMENTAL SCIENCES↗

High-speed synchrotron X-ray imaging of directed energy deposition of titanium: effects of processing parameters on the formation of entrapped-gas pores

Laser based directed energy deposition (DED) is a competitive method for repairing and remanufacturing metallic parts used in numerous industries including aerospace and biomedical. However, the numerous dynamic phenomena associated with the DED process often result in defects such as entrapped-gas pores, lack of fusion, and undesirable anisotropic properties. The entrapped-gas pore, being one of the most common issues, not only influences melt-pool dynamics but also reduces the fabrication quality and mechanical properties of parts fabricated by the DED process. To reduce and further understand this issue, the real-time observation of the pore formation process needs to be studied first. To directly observe the phenomena in the melt pool, high-speed techniques are needed because rapid solidification leads to rapid pore formation and movement. In-situ high-speed X-ray has been proven to be an effective method in investigating the melt pool dynamics and pore formation mechanisms in the laser powder bed fusion process, in which the fabrication process is quite different from that in DED. Here, the high-speed X-ray method is extended to study the formation of entrapped-gas pores. The real-time formation and quantitative analysis of pores under each set of processing parameters (particle velocity, laser power, and spot welding dwelling time of stationary laser) in the DED process are investigated. We found that the DED with a higher particle velocity (3.19 m/s) produced a smaller average pore size of 27.8 µm and a lower pore area fraction of 0.52%. The DED under lower laser power (156 W) generated a smaller average pore size of 20.3 µm and a lower pore area fraction of 1.94%. The shorter dwelling time (10 ms) benefited the decrease of both average pore size and pore area fraction.

Defect↗

Structure–Property Relationships of Recycled Lithium-Ion Battery Cathodes: Microstructure Optimization Using Virtual Materials Testing

The increasing demand for sustainable battery technologies requires effective recycling strategies for end-of-life lithium-ion battery cathodes. In this study, virtual materials testing, a well-established framework for modeling conventionally manufactured NMC-based cathodes, is applied to partially recycled cathodes. To this end, virtual cathodes consisting of mixtures of pristine and recycled NMC particles are utilized to systematically analyze structure–property relationships depending on mixing ratios and different spatial arrangement strategies. For this purpose, a stochastic 3D model is developed that is capable of generating virtual cathodes with arbitrary volume fractions of active materials and mixing ratios of pristine and recycled NMC particles. Particularly, the stochastic 3D model can mimic the different size distributions of pristine and recycled particles that are observed in image data. Additionally, the model allows the structuring of pristine and recycled NMC either uniformly mixed or layer-wise arranged, mimicking single- and dual-layer cathodes. Subsequently, a systematic computational analysis is conducted to assess the influence of increasing active material ratios of recycled particles, ranging from 0 % to 100 %, while maintaining a constant overall active material volume fraction. The impact of particle mixing on cathode performance is evaluated by examining transport-relevant geometrical descriptors and effective properties, such as geodesic tortuosity, specific surface area, and tortuosity factor.

25 ENERGY STORAGE↗

Parametric Modeling and Economic Analysis of a 2MW th 3-Stream sCO 2 Heat Exchanger

Here, this paper presents the design and cost optimization of a novel 2MW th 3-stream sCO2 plate-fin heat exchanger. This heat exchanger design is unique in that it uses reduced metal oxide particle-to-sCO2 heat exchanger for cost-effective energy storage applications. The design uses low velocity, laminar air as the re-oxidizing reactant to transfer the heat of the re-oxidizing reaction to a sCO2 power loop. The design of the heat exchanger is based on a 2-D, 3-fluid plate/fin heat transfer model. The model parameterizes the size, shape, and number of passages of the heat exchanger to calculate the temperature profile, pressure drop, and fluid velocities of all three fluids. Global heat exchanger parameters such as the effectiveness and total heat transferred to the sCO2 are then calculated for overall performance. Due to the value and increased use of sCO2 heat exchangers in power cycles, a cost model of the system based on the unique high temperature/high pressure operating conditions was created using quotes from reference projects and market analysis. These quoted air-to-sCO2 heat exchangers are then processed using multiple weighting factors pertinent to heat exchanger design, including heat exchanger type, maximum temperature, differential pressures, fluids, duty, and more. These factors are then used in an exponential function in order to generate a parameterized cost curve. The design and cost of the heat exchanger are then optimized using the SMPSO genetic algorithm in Python. The optimization objectives for the system are to maximize the overall system effectiveness, including an air recuperator for preheating, and to minimize unit costs. Additional constraints are added to the system for the sCO2 and air pressure drops, air velocity to reduce particle entrainment, and the length and volume of the heat exchanger.

Cost Model↗

Bohm Criterion of Plasma Sheaths away from Asymptotic Limits

The plasma exit flow speed at the sheath entrance is constrained by the Bohm criterion. The so-called Bohm speed regulates the plasma particle and power exhaust fluxes to the wall, and it is commonly deployed as a boundary condition to exclude the sheath region in quasineutral plasma modeling. In this work, the Bohm criterion analysis is performed in the intermediate plasma regime away from the previously known limiting cases of adiabatic laws and the asymptotic limit of infinitesimal Debye length in a finite-size system, using the transport equations of an anisotropic plasma. The resulting Bohm speed has explicit dependence on local plasma heat flux, temperature isotropization, and thermal force. Comparison with kinetic simulations demonstrates its accuracy over the plasma-sheath transition region in which quasineutrality is weakly perturbed and the Bohm criterion applies.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Open Specy 1.0: Automated (Hyper)spectroscopy for Microplastics

Microplastic spectral analysis is one of the most time-consuming processes in studying microplastic pollution, often requiring days per sample. Researchers are transitioning to automated batch and hyperspectral image analysis techniques to enhance efficiency. Open Specy, initially aimed at manual single-spectrum analysis, has now integrated automated methods. This updated version, Open Specy 1.0, introduces several new features, including two algorithms for automated processing (smoothing and particle compression), an extensive library containing over 40,000 open-source Raman and FTIR spectra, and two machine learning classifiers (logistic regression and k medoids) developed from this library. Furthermore, it includes a revamped user interface, an R package, and a benchmark data set for testing future advancements in automated techniques. Researchers evaluated various configurations for hyperspectral smoothing, particle identification, compression, and splitting, to achieve combined recovery rates between 50 and 150% particle counts, identities, and sizes with a coefficient of variation (CV) of less than 40% (the accredited standard). Mean absorbance times the standard deviation provided a consistent particle identification. Hyperspectral smoothing led to a 96% combined recovery rate and reduced variability (CV = 38%) compared to the 86% recovery (CV = 83%) of nonsmoothed controls. Additionally, compressing spectra for particles was significantly faster (>3x) and showed similar accuracy but with reduced variability than processing each pixel individually. Key challenges persist in automating spectral analysis, particularly in refining particle splitting algorithms, and improving identification routines to minimize false positives and negatives. In conclusion, new methods in sample preparation for better stabilization and dispersion of particles could overcome some of these issues.

13 HYDRO ENERGY↗

Effect of Plutonium on Uranium Oxide Microstructural Fingerprint

The analysis of particulates from environmental sampling is routinely performed for nuclear forensics applications. In order to increase the tools available for nuclear forensics applications, capability development materials (CDMs), or reference particulates, are necessary for developing and benchmarking new analytical methods. Historically, these CDM particulates have been produced with highly controlled and characterized isotopic and size parameters for applications in developing and benchmarking particle sizers and mass spectrometry analytical methods [1- 4]. However, the development of CDMs with highly characterized particle morphology and phase of the particles is vital for aiding in the development and benchmarking of particle analytical methods for those parameters. In many cases, key properties such as crystallographic phase, morphology, and microstructure, may be correlated to processing history of environmental sampling particulates [5]. To that end, this work investigates determining the structural fingerprint of produced Pu-doped uranium oxide CDMs using transmission electron microscopy (TEM). The particulates, one of which shown in Figure 1, were synthesized to Fig. 1. Single particulate of uranium oxide fabricated using the THESEUS technique. develop capabilities for environmental sampling investigations. These particles are monodisperse at diameter of 1 μm and a range of plutonium concentrations from 0- 1,000 ppm. Given their small diameter, TEM analysis was ideal for studying the particulate structural fingerprint in detail. Previous investigations confirmed the external homogeneity of the particulates at different plutonium concentrations, however this analysis focuses on determining the grain structure, phase distribution, and porosity of the particulates.

Mayer, Jack [Univ. of Florida, Gainesville, FL (Un↗

Effects of Riser Diameter on Solids Holdup and Particle Velocity Profiles in Circulating Fluidized Bed Riser Systems

Tests were performed in a 0.1-m diameter small circulating fluidized bed (SCFB) and 0.3 m diameter cold flow circulating fluidized bed (CFCFB) riser systems located at the National Energy Technology Laboratory (NETL) to study the effects of riser diameter on the riser hydrodynamics. These tests were performed at solids circulation rates of G s = 20 and 75 kg/m 2 s and superficial gas velocities of U g = 5.8 and 6.5 m/s using high-density polyethylene (HDPE) pellets with a density of 0.863 g/cm 3 , particle size range of 600–1400 µm (with a Sauter mean diameter of 871 µm, placing them in the Geldart B classification). Comparisons of riser axial pressure and solids fraction profiles, radial particle velocity profiles, and radial profiles of higher statistical moments and select chaos analysis parameters were considered. The results showed that for a given U g and G s , the smaller diameter riser exhibited characteristics associated with more dilute solids flow than that observed in the larger diameter riser. Additionally, the larger diameter riser exhibited a downward flow of solids near the wall under all test conditions, whereas the smaller diameter riser data exhibited little or no indications of solids downflow near the wall. Overall, these findings suggest that, from an industrial standpoint, a direct scaleup of small-scale tests cannot readily be accomplished as the solids holdup and the solids velocity profiles in small units (those normally tested in the laboratory) are not similar to those of large units and the performance of large units can therefore not be predicted from small-scale tests.

42 ENGINEERING↗

Synchrotron Based Microstructural Characterization Method Development for Pu Oxides

Identification of new plutonium oxide signatures is a high priority focus area of the technical nuclear forensics and nonproliferation communities. Comprehensive materials science studies of plutonium oxide are needed to advance the understanding of the microcrystalline properties and their relationship to macro-scale morphologies and signatures. Plutonium oxide particle growth is depenedent on the microcrystalline strucutures, grain size, and orientation. Microcrystalline structures have been found to vary for plutonium oxide based on the oxidation state of plutonium, concentration of reactants, and the physiochemical conditions of precipitation. Empirical observation confirms the relationship between processing conditions and particle morphology. High sensitivity, non destructive analysis of individual microcrystalline grains requires the use of bright sources of X-rays produced by synchrotron radiation, such as those at the Advanced Photon Source. The light source can reveal higher resolution crystallographic mapping, more sensitive chemical analysis, and higher fidelity morphological information than any current methods at SRNL Progress of FY19 was the analysis of the synchrotron data. Areas of focus included XANES oxidation state and EXAFS to measure bond distances with modeling. Most measurements for XANES indicated that the plutonium was in the +4 oxidation state, however, some indicated that there could also be a +5 oxidation state. The EXAFS measurements showed typical Pu – O bonding distance of 2.33 and Pu – Pu bonding distances of 3.81 A; however, some samples also showed that there could be shorter Pu – O distances of approximately 1.81 A, indicative of plutonium in the +5 oxidation state.

36 MATERIALS SCIENCE↗

Engineered Membrane Vesicle Production via oprF or oprI Deletion Has Distinct Phenotypic Effects in Pseudomonas putida -putative knockouts table

Table S1, putative gene knockout targets in P. putida KT2440 to enhance vesiculation; Table S2, protein sequence identity of OmpA from E. coli K12 to P. putida KT2440 genes; Table S3, strains utilized in this study and corresponding construction details; Table S4, oligonucleotides utilized in this study; Table S5, plasmids utilized in this study; Table S6, sequences for mNeonGreen, tags, and codon-optimized genes; Figure S1, particle count per gCDW for KT2440 and knockout strains corresponding to data presented in Figure 1B; Figure S2, OD600 measurements of extracted MVs from KT2440 and knockout strains; Figure S3, particle count per gCDW for WT, ΔPP_4669, and ΔPP_1502; Figure S4, particle count per gCDW for KT2440 and knockout strains corresponding to data presented in Figure 3C; Figure S5, sizes of MVs corresponding to particle counts in Figure S4; Figure S6, particle count per gCDW for KT2440 grown on 20 mM glucose alone or 20 mM glucose plus 12.5 mM p-coumarate and 12.5 mM ferulate; Figure S7 and Figure S8, principal component analysis of the cellular fractions; Figure S9, heatmap of outer membrane proteins with differential abundance; and Figure S10, mNeonGreen (mNG) fluorescence signal for the cellular fraction and the extracellular fraction

hypervesiculation↗

Developing A Custom-Built Metal Aerosol Processing Chamber: Analysis of Aerosol Coagulation at Low Humidities

We have developed an intermediate size (906 L) aerosol processing chamber, and this work reports on the design and initial characterization of dry aerosol experiments. Specifically, we are determining wall-loss and coagulation correction factors using the observed size distribution measurements for surrogates of common aerosol classes: sodium chloride, sucrose, and biomass burning aerosol smoke. Results show that, on average, sodium chloride, sucrose, and smoke wall-loss rates converge to similar values on relatively short time scales (< 1 h). The fitted coagulation correction factor, W C -1 , for smoke particles (1.23 ± 0.312), indicates that on average they adhere to each other more than sodium chloride (0.969 ± 0.524) and sucrose (1.16 ± 1.38). The relative uncertainty is high for the coagulation correction, but it is consistent with our Monte Carlo error analysis. This study lays the foundation for future experiments at elevated humidity and supersaturation conditions to characterize the influence of particle shape on coagulation and cloud parameters.

54 ENVIRONMENTAL SCIENCES↗

Failure analysis and design principles of silicon-based lithium-ion batteries using micron-sized porous silicon/carbon composite

Significant progresses have been made to overcome the fundamental challenges in silicon (Si)-based lithium-ion batteries (LIBs). However, much less work have been reported on the design and failure analysis these batteries for practical applications. In this work, we analyzed various cell design parameters affecting the performance of pouch cells using micron-sized porous Si with nano-pore structure and coated by pitch-carbon (p-Si/C). The correlation among particle level, electrode level, and cell level properties, especially the effect of electrode density on the volumetric capacity density of Si anode and full batteries have been systematically investigated. It is found that the corrosion of p-Si/C particle surface is the main failure mechanisms on the eventual capacity loss, while Li plating on anode electrode surface is the main reason for the fast capacity loss in later stage of cycling. The volumetric capacity of Si anode highly depends on both electrode density and the Si content. Moreover, the prelithiation of Si anodes is found to increase energy density while decreasing cycle life of Si-based full cells. Finally, the pathways and strategies for adoption of micron-sized p-Si/C anodes in LIBs have been proposed for their practical applications.

25 ENERGY STORAGE↗

Predicting Morphological Evolution during Coprecipitation of MnCO 3 Battery Cathode Precursors Using Multiscale Simulations Aided by Targeted Synthesis

The performance of lithium-ion batteries is intimately linked to both the structure and the morphology of the cathode material, which in turn is critically linked to the synthesis conditions. However, few studies focus on understanding synthesis, especially during the coprecipitation of metal oxide precursors, a process that largely determines the final morphology of the material. In this paper, we go beyond the typical equilibrium particle shape analysis conducted in the literature and incorporate kinetic aspects of morphology evolution. We perform these studies using controlled synthesis on a well-defined metal salt system (MnCO 3 ) combined with multiscale simulations and high-resolution microscopy. Results show that with increasing metal concentration, the particles transition from rhombohedral to cubic to spherical shapes. Computational analysis using density functional theory (DFT) reveals that rhombohedral shaped particles evolve under equilibrium conditions. Phase field techniques indicate that at higher metal concentrations, fast growth kinetics of the precipitates result in the transition to cubic and, subsequently, spherical shapes, accompanied by a decrease in particle size. This study, while limited to the one metal salt system, provides an approach to shed light on the synthesis process of mixed transition metal salts, gradient materials, and other cathode materials of interest to the battery community.

25 ENERGY STORAGE↗

Going Off Grid: A Comparative Study of the Lagrangian and Eulerian Perspectives of New Particle Formation Events

New particle formation and growth (NPF&G) is the process by which ultrafine particles are formed from gas-phase precursors. NPF&G is the dominant source of global aerosol number with important influences on climate. Most observations of NPF&G events are conducted at stationary sites; however, NPF&G observed from stationary sites is influenced by gradual or rapid changes in the air masses passing over the site, complicating NPF&G analysis. In this work, we use observations and a 3D aerosol model to compare aerosol size distributions at a stationary site (Southern Great Plains [SGP] observatory, Oklahoma, USA) and along Lagrangian trajectories crossing the site. The model simulates the NPF&G events reasonably well at SGP. Using the model to compare the Lagrangian and stationary perspectives, we can explain previously unanalyzable days with some evidence of NPF&G as either non-event or analyzable NPF&G days. We find most of the unanalyzable NPF&G days are due to isolated and inhomogeneous NPF&G occurring upwind of the stationary site, often in the outflow of urban regions. Finally, we compare formation rates of 3 nm particles, growth rates, and the survival probability of 3 nm particles growing to 25 nm between the stationary and Lagrangian perspectives. Because of the much larger number of analyzable days along the Lagrangian trajectories, this perspective potentially provides more robust statistics and better characterization of NPF&G event extremes. Our method for extracting chemical/physical properties along Lagrangian trajectories from 3D models can be applied to a wide range of science questions.

O’Donnell, Samuel E. [Colorado State Univ., Fort C↗

Synthesis and Characterization of Mesoporous Silica Nanoparticles Loaded with Pt Catalysts

Coating the catalyst with a nanoporous layer has been demonstrated to be an effective approach to improve catalyst stability. Herein, we systematically investigate two types of core-shell mesoporous silica nanoparticles with a platinum nanocatalyst using a variety of characterization methods. One of the mesoporous particles has a unique amine ring structure in the middle of a shell (Ring-mSiO 2 /Pt-5.0/SiO 2 ), and the other one has no ring structure (mSiO 2 /Pt-5.0/SiO 2 ). Brunauer–Emmett–Teller/Barrett–Joyner–Halenda (BET/BJH) presented a similar surface area for both particles, and the pore size was 2.4 nm. Ultra-Small-Angle X-ray Scattering (USAXS)/ Small-Angle X-ray Scattering (SAXS) showed the size of mSiO 2 /Pt-5.0/SiO 2 and Ring-mSiO 2 /Pt-5.0/SiO 2 were 420 nm and 272 nm, respectively. It also showed that the ring structure was 30 nm above the silica core. Using high-resolution Transmission Electron Microscopy (TEM), it was found that the platinum nanoparticles are loaded evenly on the surface of the silica. In situ SAXS heating experiments and Thermogravimetric Analysis (TGA) indicated that the mSiO 2 /Pt-5.0/SiO 2 were more stable during the high temperature, while the Ring-mSiO 2 /Pt-5.0/SiO 2 had more change in the particle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement report: A comparative analysis of an intensive incursion of fluorescing African dust particles over Puerto Rico and another over Spain

Measurements during episodes of African dust, made with two wideband integrated bioaerosol spectrometers (WIBSs), one on the northeastern coast of Puerto Rico and the other in the city of León, Spain, show unmistakable, bioaerosol-like fluorescing aerosol particles (FAPs) that can be associated with these dust episodes. The Puerto Rico event occurred during a major incursion of African dust during June 2020. The León event occurred in the late winter and spring of 2022, when widespread, elevated layers of dust inundated the Iberian Peninsula. Satellite and back-trajectory analyses confirm that dust from northern Africa was the source of the particles during both events. The WIBSs measure the size of individual particles in the range from 0.5 to 30 µm, derive a shape factor, and classify seven types of fluorescence from the FAPs. In general, it is not possible to directly determine the specific biological identity from fluorescence signatures; however, measurements of these types of bioaerosols in laboratory studies allow us to compare ambient fluorescence patterns with whole microbial cells measured under controlled conditions. Here we introduce some new metrics that offer a more quantitative approach for comparing FAP characteristics derived from particles measured under different environmental conditions. The analysis highlights the similarities and differences at the two locations and reveals differences that can be attributed to the age and history of the dust plumes, e.g., the amount of time that the air masses were in the mixed layer and the frequency of precipitation along the air mass trajectory.

54 ENVIRONMENTAL SCIENCES↗