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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Cocontinuous Nanostructures by Microphase Separation of Statistically Cross-Linked Polystyrene/Poly(2-vinylpyridine) Networks

Cocontinuous polymeric nanostructures have drawn considerable attention due to their ability to combine distinct, percolation-dependent properties of two different polymer domains. Randomly end-linked copolymer networks (RECNs) have previously been shown to support the formation of disordered cocontinuous nanostructures across wide composition windows in a robust way. However, achieving highly efficient linking of telechelic polymers with excellent end-group fidelity often requires complex synthetic routes. As an alternative, we study here statistically cross-linked copolymer networks (SCCNs) composed of polystyrene and poly(2-vinylpyridine) (PS and P2VP) with cross-linkable allyl pendent groups that are conveniently synthesized by controlled radical copolymerization. Via selective extraction of P2VP, coupled with gravimetry, small-angle X-ray scattering, and electron microscopy, we find disordered cocontinuous phases across wide composition ranges (up to ≈ 35 wt %), approaching values previously determined for RECNs. Remarkably, even for samples that appear to exhibit full percolation, a substantial fraction of P2VP (≈ 20–30 wt %) cannot be removed, which we ascribe to short strands between nearby cross-linkers that are physically embedded within PS domains. Here, the resulting PS porous monoliths with residual surface P2VP layers enable facile surface modification to resist protein adsorption and templating of porous gold nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Optimizing Li‐Excess Cation‐Disordered Rocksalt Cathode Design Through Partial Li Deficiency

Li-excess disordered rocksalts (DRXs) are emerging as promising cathode materials for Li-ion batteries due to their ability to use earth-abundant transition metals. In this work, a new strategy based on partial Li deficiency engineering is introduced to optimize the overall electrochemical performance of DRX cathodes. Specifically, by using Mn-based DRX as a proof-of-concept, it is demonstrated that the introduction of cation vacancies during synthesis (e.g., Li 1.3-x Mn 2+ 0.4-x Mn 3+ x Nb 0.3 O 1.6 F 0.4 , x = 0, 0.2, and 0.4) improves both the discharge capacity and rate performance due to the more favored short-range order in the presence of Mn3+. Density functional theory calculations and Monte Carlo simulations, in combination with spectroscopic tools, reveal that introducing 10% vacancies (Li 1.1 Mn 2+ 0.2 Mn 3+ 0.2 Nb 0.3 O 1.6 F 0.4 ) enables both Mn 2+ /Mn 3+ redox and excellent Li percolation. However, a more aggressive vacancy doping (e.g., 20% vacancies in Li 0.9 Mn 3+ 0.4 Nb 0.3 O 1.6 F 0.4 ) impairs performance because it induces phase separation between an Mn-rich and a Li-rich phase.

25 ENERGY STORAGE↗
DOE OSTI2025

Tuning Cation (Dis)Order in Cr‐Based Li‐Excess Oxide Cathode Materials to Improve Li+ Transport Properties

Abstract Li‐excess disordered rocksalts (DRXs) hold promise as next‐generation cathodes for Li‐ion batteries due to their high capacity and energy density, along with the potential to eliminate the need for Co and Ni. However, due to their low Li + diffusivity, DRXs need to be pulverized into nanoparticles to achieve high performance. Herein, a new strategy for overcoming this limitation is demonstrated, involving the design of as‐synthesized partially disordered oxides with a structure that lies between ordered layered and fully disordered, exhibiting a varying degree of local (dis)order. This unique structure activates new Li + diffusion channels, improving percolation and transport properties. This strategy allows a large content of Li + to be accessed in material with large, micron‐sized particles through highly reversible Cr 3+/6+ and O redox, yielding a first discharge capacity of 286 mAh g −1 (881 Wh kg −1 ). The Li + percolation network is further improved by substituting Ti with a mixture of multiple metals, which appears to locally decrease the migration barrier through lattice distortion. Proper tuning of the chemical composition, especially the content of metals with empty d orbitals, is established as a crucial factor for controlling the degree of disorder and mitigating voltage fade and hysteresis growth upon cycling.

Moździerz, Maciej↗
DOE OSTI2023

Influence of the Graft Length on Nanocomposite Structure and Interfacial Dynamics

Both the dispersion state of nanoparticles (NPs) within polymer nanocomposites (PNCs) and the dynamical state of the polymer altered by the presence of the NP/polymer interfaces have a strong impact on the macroscopic properties of PNCs. In particular, mechanical properties are strongly affected by percolation of hard phases, which may be NP networks, dynamically modified polymer regions, or combinations of both. In this article, the impact on dispersion and dynamics of surface modification of the NPs by short monomethoxysilanes with eight carbons in the alkyl part (C 8 ) is studied. As a function of grafting density and particle content, polymer dynamics is followed by broadband dielectric spectroscopy and analyzed by an interfacial layer model, whereas the particle dispersion is investigated by small-angle X-ray scattering and analyzed by reverse Monte Carlo simulations. NP dispersions are found to be destabilized only at the highest grafting. The interfacial layer formalism allows the clear identification of the volume fraction of interfacial polymer, with its characteristic time. The strongest dynamical slow-down in the polymer is found for unmodified NPs, while grafting weakens this effect progressively. The combination of all three techniques enables a unique measurement of the true thickness of the interfacial layer, which is ca. 5 nm. Finally, the comparison between longer (C 18 ) and shorter (C 8 ) grafts provides unprecedented insight into the efficacy and tunability of surface modification. It is shown that C 8 -grafting allows for a more progressive tuning, which goes beyond a pure mass effect.

36 MATERIALS SCIENCE↗
DOE OSTI2025

SOC Microstructural Property Estimator

This pre-trained ML model is a tool that uses basic compositional parameters for porous solid oxide cell (SOC) electrodes - the phase fractions and mean particle/pore diameters – as inputs and uses them to estimate additional electrochemical performance parameters: active (i.e., connected) TPB density, all tortuosity factors, and phase pair specific interfacial areas. The electrode is assumed to be composed of two solid phases and a pore phase. The property calculations are performed using neural network regression models trained on a large bank of synthetic electrode microstructural data that NETL has generated using the program DREAM3D (that bank is also hosted on EDX: https://edx.netl.doe.gov/dataset/soc-synthetic-microstructure-bank). This means the generated parameters are based on training from actual measured properties from 3D microstructures, not estimated from geometric simplifications. This tool was developed and is intended to replace percolation theory calculations in models that use hypothetical electrode properties. An example use case would be running SOC performance simulations across a parametric sweep of electrode designs (e.g., varying phase fractions and particle sizes) and assessing how it impacts the electrochemical performance of the SOC. Within the parameter space of the training data (statistics of that parameter space is provided in the readme file), this model achieves sub-5% mean absolute percent errors, an order of magnitude less error than percolation theory across the same parameter space. However, be aware that this tool was developed with parametric simulations in mind, and users are encouraged to assess accuracy for their own specific use case rather than taking accuracy metrics at face value. More info, including a usage guide, is in the included readme file. This tool should be cited with the DOI number provided.

Electrode Microstructure↗
DOE OSTI2024

Effect of solid-electrolyte pellet density on failure of solid-state batteries

Abstract Despite the potentially higher energy density and improved safety of solid-state batteries (SSBs) relative to Li-ion batteries, failure due to Li-filament penetration of the solid electrolyte and subsequent short circuit remains a critical issue. Herein, we show that Li-filament growth is suppressed in solid-electrolyte pellets with a relative density beyond ~95%. Below this threshold value, however, the battery shorts more easily as the density increases due to faster Li-filament growth within the percolating pores in the pellet. The microstructural properties (e.g., pore size, connectivity, porosity, and tortuosity) of $$75\%{{{{{\rm{L}}}}}}{{{{{{\rm{i}}}}}}}_{2}{{{{{\rm{S}}}}}}-25\%{{{{{{\rm{P}}}}}}}_{2}{{{{{{\rm{S}}}}}}}_{5}$$ 75 % L i 2 S − 25 % P 2 S 5 with various relative densities are quantified using focused ion beam–scanning electron microscopy tomography and permeability tests. Furthermore, modeling results provide details on the Li-filament growth inside pores ranging from 0.2 to 2 μm in size. Our findings improve the understanding of the failure modes of SSBs and provide guidelines for the design of dendrite-free SSBs.

25 ENERGY STORAGE↗
DOE OSTI2025

A Percolating Path to Green Iron

About 1.9 gigatonnes of steel is produced every year emitting 7% (2.7 gigatonnes) of global CO 2 in the process. More than 50% of the CO 2 emissions come from a single step of steelmaking, known as ironmaking. Hydrogen based direct reduction (HyDR) of iron oxide to iron has emerged as an emissions free ironmaking alternative. However multi-scale phenomena ranging from nanometers to meters inside HyDR reactors exhibit detrimental microstructure evolution which resists gaseous transport of H 2 /H 2 O, slows reaction rates and disrupts continuous reactor operation. To resolve the conundrum between atomic and reactor scales, we devise a percolation-theory model to reconcile nanoscale porosity with macroscopic properties relevant to reactor design models. Using synchrotron nano X-ray computed-tomography, we quantify the evolution of pores in iron oxide pellets, and demonstrate how nano-scale pore networks influence micro and macro-scale flow properties such as permeability, diffusivity and tortuosity. Our new modeling framework bridges the gap between scales and offers the criteria to accelerate HyDR by at least 5x via feedstock-reactor synergies based on percolation.

Paul, Subhechchha↗
DOE OSTI2023

Carbon Coating Influence on the Formation of Percolating Electrode Networks for Silicon Anodes

Previous studies have demonstrated that chemical vapor deposition carbon coating on silicon (Si@C) can enhance the electrochemical performance of lithium-ion batteries with Si-based anodes. However, the underlying mechanisms contributing to this improvement have not been fully explored. Here, we address this knowledge gap by applying a suite of characterization methods to evaluate Si@C anodes prepared by reducing acetylene on ball-milled Si particles. Raman mapping measurements show that the C coating (<5 nm thick) enables a homogeneous Si and carbon distribution during the slurry casting process, thereby promoting Si utilization during cycling. The coating’s microstructure and morphology were evaluated using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy, and neutron reflectivity experiments. Electrochemical impedance spectroscopy measurements upon cycling indicate that carbon coating also reduces the overall resistance as benchmarked against bare Si anodes. Galvanostatic cycling in half-cell studies revealed higher initial Coulombic efficiency and specific capacities with increasing carbon coating time. However, solid electrolyte interphase (SEI) investigations using XPS showed that the coated and uncoated samples have very similar characteristics, suggesting that the SEI may only play a minor role in enhancing the performance of Si@C. Full-cell evaluation of the Si electrodes was consistent with half-cell results relating to performance and SEI properties, further supporting the conclusion that electronic and ionic percolation, enabled by effective electrode manufacturing, are the dominant factors contributing to the favorable performance of Si@C.

25 ENERGY STORAGE↗
DOE OSTI2023

Doped Lanthanum Chromite-refractory Based Composites Sensors for High Temperature Monitoring in Harsh Environments Systems

In order to test and monitor the operational stability and conditions of various energy, and manufacturing systems and their components, development of accurate sensors capable of operating at temperatures in excess of 1000 °C in various environments for long durations is required. In addition, many of these harsh-environment systems do not permit sensors to be directly inserted, so these sensors need to be embedded into thermal protective materials. In this work were developed high-temperature embedded thermocouples composed of various doped lanthanum chromites-refractory based composites synthesized by a mixed-oxide route and directly embedded into a Al2O3 based refractory. The electrical properties were specifically manipulated by altering the level of percolation of the conductive phase within the refractory constituent. Chemical stability of sensors was determined by phase development analysis by X-ray diffraction and X-ray photoelectron spectroscopy; Seebeck coefficients were determined by thermoelectric voltages measurements at temperature up to 1400 oC.

Perovskite LaCrO3, High-temperature conductivity, ↗
DOE OSTI2023

Smart Refractory Sensors Development for Corrosion and Erosion Monitoring in High Temperature Systems

To optimize the operation and functioning of high temperature systems such as slagging gasifiers, coal boilers and glass/steel melters, it is important to monitor corrosion and erosion of refractory used in such systems. Corrosion test strategies are generally based on continuous gravimetric and chemical reactivity monitoring at operational temperatures (750°-1500°C). Both thermocouples and failure sensors and arrays would be useful to monitor the health of any refractory or coatings in these systems. Many of such type of sensors are installed into the systems through open access ports within the refractory; however, there are some disadvantages of this approach where corrosive/erosive gas and molten materials can penetrate and compromise the system. The current work presents the development and performance demonstration of smart refractory with embedded high temperature sensors such as thermocouples, thermistors, and various spallation/crack monitoring sensors, which may be used within a variety of refractory brick in different high temperature processes and applications. The main feature of this technology is that electroceramic based sensors are embedded into smart refractory without significantly impact to the intrinsic properties of the refractory. This technology circumvents the need to insert an isolated monolithic, stand-alone sensor into the refractory via an access port. This technological approach guarantees the integrity and the chemical stability of the materials used in the sensor fabrication within the harsh environment and does not introduce molten material (such as slag) penetration pathways within the refractory. One interesting and important aspect of this innovation is that these embedded sensors can be used to in situ monitoring processes such as chemical reactions and at the same time give information and a deeper understanding of the corrosion and erosion process of the refractory within the system. As stated above, the objective of our work is to develop high-temperature sensors composed of electroceramic materials that are chemically stable at high temperatures (750°-1500°C) and high pressures (up to 1000 psi) that can be used in monitoring corrosion and erosion process in refractory used in high energy systems. The high-temperature sensors investigated in this work were composed of various oxide composites directly embedded into the refractory oxides. The composites used for this work were synthesized by a mixed-oxide route. Metal oxides were inserted within a matrix material composed of refractory oxides (Al2O3, ZrO2, etc.). The physical and electrical properties were specifically manipulated by altering the level of percolation of the conductive species (metal oxides) within the refractory constituent (refractory oxide). Prior to the development of the high-temperature sensors, the oxides composites developed in this study were sintered up to 1600°C under oxidizing atmosphere in order to investigate densification, microstructural evolution, phase development, and their thermoelectrical performance as a function of the composition. The 4-point DC conductivity measurements were performed between 100°-1500°C. The sensors were fabricated from the composite materials by 3D-printing or screen-printing methods into the refractory brick during the consolidation process. An example of one of these embedded sensors consisted of an electroceramic-based thermocouple fabricated with two separate oxide composite compositions which were patterned to produce a couple within the interior of a refractory matrix. The thermocouple successfully displayed thermoelectric voltage trend (as a function of temperature), and the voltage was 220.0 mV around 1400 °C. Corrosion tests on the refractory embedded sensors were performed. To evaluate corrosion in the refractory brick an in-house glass composition was prepared and pressed into pellets and delivered into a pre-cut cavity in the brick. Corrosion experiments results showed the glass penetrated the brick over a 90 h period, and the penetration of the glass through the brick could be monitored by both an amperometric and voltametric based sensor. With this experiment, it was demonstrated that the embedded sensor could dynamically monitor the corrosion process.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2023

Oxide Semiconductor Sensors for Monitoring Advanced Energy Conversion and Manufacturing Processes at High Temperature

To optimize the operation and functionality of high temperature systems such as slagging gasifiers, coal boilers and glass/steel smelters, it is important to monitor temperature, corrosion and erosion of the refractory used in such systems. Both thermocouple and failure sensors (and arrays of these) would be useful to monitor the health of any refractory or coatings in these systems. Many of such type of sensors are installed into the systems through open access ports within the refractory; however, there are some disadvantages of this approach where corrosive/erosive gas and molten materials can penetrate and compromise the system. The current work presents the development and performance of refractory with embedded high temperature sensors such as thermocouples, thermistors, and various spallation/crack monitoring sensors, which may be used within a variety of refractory brick in different high temperature processes and applications. The objective of our work is to develop high-temperature sensors composed of electroceramic materials that are chemically stable at high temperatures (750°-1500°C) and high pressures (up to 1000 psi) that can be used in monitoring temperature, corrosion and erosion process in refractory used in high energy systems. The high-temperature sensors investigated in this work were composed of various oxide composites directly embedded into the refractory oxides. The composites used for this work were synthesized by a mixed-oxide route. Metal oxides were inserted within a matrix material composed of refractory oxides (Al2O3, ZrO2, etc.). The physical and electrical properties were specifically manipulated by altering the level of percolation of the conductive species (metal oxides) within the refractory constituent (refractory oxide). An example of one of these embedded sensors consisted of an electroceramic-based thermocouple fabricated with two separate oxide composite compositions which were patterned to produce a couple within the interior of a refractory matrix. The thermocouple successfully displayed thermoelectric voltage trend (as a function of temperature), and the voltage was 220.0 mV near 1400 °C. In addition, corrosion tests on the refractory embedded sensors were performed. To evaluate corrosion in the refractory was exposed to high-temperature glass compositions over a 90 h period. The penetration of the glass through the refractory could be monitored by both an amperometric and voltametric based sensor. With this experiment, it was demonstrated that the embedded sensor could dynamically monitor the corrosion process, and thus, provide real-time feedback on both temperature and the refractory health.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2024

A recyclable self-healing composite with advanced sensing property

Polymer-based composites frequently encounter damage, often lurking beneath the surface and proving challenges to their early detection and repair. While material-based sensors show promise for encoding self-sensing properties within these composites, their in situ healing and reprocessability remain significant challenges. Therefore, the overarching goal of this study is the creation of a reprocessable polymeric composite encoded with self-healing attributes and the ability to autonomously sense damage. At the core of this innovation are vitrimers, a polymeric material characterized by a covalently adaptive dynamic network responsive to external factors such as heat. They combine thermoset-like resilience with thermoplastic-like flowability on demand under external stimuli. We nanoengineer a polyester-based vitrimeric polymer by incorporating piezoresistive carbon nanotubes (CNTs) as reinforcing elements that not only enhance its mechanical strength but also create a percolation network within the composite, thereby enabling piezoresistive self-sensing properties, all the while preserving the intrinsic self-healing capabilities offered by the vitrimeric matrix. The fabrication process of the composite involves a solvent-free in situ polymerization method that combines epoxy and anhydride-containing monomers with ~ 0.1 wt.% of CNTs. Once it was established that the introduction of CNTs into the polymeric matrix did not compromise the mechanical properties of the composite, their strain-sensing properties were characterized by applying cyclic loading while measuring their electrical resistance. Strikingly, CNT-enhanced vitrimer composite consistently retains its mechanical and sensing properties through repeated cycles of reshaping and reprocessing, underscoring its potential as a robust distributed strain sensor. This polyester-based vitrimeric composite is also easily recyclable without harsh chemical treatments. Preliminary findings from this study conclusively demonstrate that the bulk composite boasts both self-sensing capabilities and in situ detect healing properties, charting a promising course towards the development of a mechanically resilient multifunctional composite that seamlessly integrates selfsensing and healing capabilities.

Rohewal, Sargun Singh↗
DOE OSTI2023

Reaching percolation and conformal limits in neutron stars

Generating an ensemble of equations of state that fulfill multimessenger constraints, we statistically determine the properties of dense matter found inside neutron stars (NSs). We calculate the speed of sound and trace anomaly and demonstrate that they are driven towards their conformal values at the center of maximally massive NSs. The local peak of the speed of sound is shown to be located at values of the energy and particle densities, which are consistent with deconfinement and percolation conditions in QCD matter. Here, we also analyze fluctuations of the net-baryon number density in the context of possible remnants of critical behavior. We find that the global maxima of the variance of these fluctuations emerge at densities beyond those found in the interiors of NSs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Filled Elastomers: Mechanistic and Physics-Driven Modeling and Applications as Smart Materials

Elastomers are made of chain-like molecules to form networks that can sustain large deformation. Rubbers are thermosetting elastomers that are obtained from irreversible curing reactions. Curing reactions create permanent bonds between the molecular chains. On the other hand, thermoplastic elastomers do not need curing reactions. Incorporation of appropriated filler particles, as has been practiced for decades, can significantly enhance mechanical properties of elastomers. However, there are fundamental questions about polymer matrix composites (PMCs) that still elude complete understanding. This is because the macroscopic properties of PMCs depend not only on the overall volume fraction (ϕ) of the filler particles, but also on their spatial distribution (i.e., primary, secondary, and tertiary structure). This work aims at reviewing how the mechanical properties of PMCs are related to the microstructure of filler particles and to the interaction between filler particles and polymer matrices. Overall, soft rubbery matrices dictate the elasticity/hyperelasticity of the PMCs while the reinforcement involves polymer–particle interactions that can significantly influence the mechanical properties of the polymer matrix interface. For ϕ values higher than a threshold, percolation of the filler particles can lead to significant reinforcement. While viscoelastic behavior may be attributed to the soft rubbery component, inelastic behaviors like the Mullins and Payne effects are highly correlated to the microstructures of the polymer matrix and the filler particles, as well as that of the polymer–particle interface. Additionally, the incorporation of specific filler particles within intelligently designed polymer systems has been shown to yield a variety of functional and responsive materials, commonly termed smart materials. We review three types of smart PMCs, i.e., magnetoelastic (M-), shape-memory (SM-), and self-healing (SH-) PMCs, and discuss the constitutive models for these smart materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Palladium-Percolated Networks Enabled by Low Loadings of Branched Nanorods for Enhanced H 2 Separations

Nanoparticles (NPs) at high loadings are often used in mixed matrix membranes (MMMs) to improve gas separation properties, but they can lead to defects and poor processability that impede membrane fabrication. Herein, it is demonstrated that branched nanorods (NRs) with controlled aspect ratios can significantly reduce the required loading to achieve superior gas separation properties while maintaining excellent processability, as demonstrated by the dispersion of palladium (Pd) NRs in polybenzimidazole for H 2 /CO 2 separation. Increasing the aspect ratio from 1 for NPs to 40 for NRs decreases the percolation threshold volume fraction by a factor of 30, from 0.35 to 0.011. An MMM with percolated networks formed by Pd NRs at a volume fraction of 0.039 exhibits H 2 permeability of 110 Barrer and H 2 /CO 2 selectivity of 31 when challenged with simulated syngas at 200 °C, surpassing Robeson's upper bound. In conclusion, this work highlights the advantage of NRs over NPs and nanowires and shows that right-sizing nanofillers in MMMs is critical to construct highly sieving pathways at minimal loadings. In conclusion, this work paves the way for this general feature to be applied across materials systems for a variety of chemical separations.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Nonlocal Effect of Percolated Particle Networks on Viscoelasticity of Polymer–Filler Nanocomposites: A Mesoscale Simulation Study

With nanoparticles (NPs) as fillers, polymer nanocomposites (PNCs) usually exhibit enhanced mechanical properties. However, a direct connection between the microscopic structural relaxation and macroscopic mechanical properties of PNCs remains to be established. To investigate the micro-to-macro connection, we develop a mesoscale model, in which the NPbridging polymer chains are represented by a dynamic bonded interaction between NPs, and the bulk polymer matrix is implicitly modeled by overdamped Langevin dynamics. Extensive equilibrium simulations are performed to quantify the microscopic dynamics of model PNCs. Systematic analyses of modified Rouse dynamics, dynamic structure factor, and relaxation modulus uncover that the microscopic relaxation dynamics of PNCs are significantly decelerated across different length scales because of nonlocal effects of percolated particle networks a phenomenon that has not been adequately captured in prior simulation studies. We find that NPvolume- fraction and NP-bonding-energy barrier are the two critical variables that affect bulk viscoelasticity the most. The proposed mesoscale model is versatile and provides a powerful framework for studying structure−property relations of different PNCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Soil water percolation and nutrient fluxes as a function of topographical, seasonal and soil texture variation in Central Amazonia, Brazil

Abstract Understanding soil water dynamics and transport of nutrients is challenging in tropical rainforests due to the uniqueness of several properties related to soils, vegetation and seasonality that make relating patterns found in temperate environments to tropical sites difficult. We address the need for better edaphic characterization in tropical environments by investigating soil water percolation rates and chemistry across topographic, soil texture and seasonal gradients in a mature tropical rainforest in Central Amazonia, Brazil. We utilized a passive wick flux meter (e.g., drainage lysimeter) to directly measure real‐time percolation fluxes at 60‐cm depth, and to sample a suite of chemical species across plateau, slope and valley topographic positions. We found percolation flux volume and chemical exports generally increase with decreasing elevation and clay content, which was lowest in the valley. Daily percolation flux was observed to be 2.39 ± 0.44 in plateau, 3.01 ± 0.50 in slope and 6.16 ± 0.83 mm in valley. Most solutes were present in small amounts of <1 mg L −1 , such as PO₄ 3− , Fe 2+ /Fe 3+ and Mn 2+ ; however, NO 3 − concentrations were >20 mg L −1 , even exceeding 100 mg L −1 in the valley. Based on additional isotopic analysis, we speculate high NO 3 − concentrations are partially an artefact of root decomposition following installation of the flux meters. The empirical relationships we show among percolation volume and nutrient exports under varying topographies and soil textures can improve Earth System Model performance by better constraining ecohydrological relationships to nutrient fluxes, which can in‐turn better illuminate the important factors that govern their behaviour.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Percolating Interfacial Layers Enhance Conductivity in Polymer–Composite Electrolytes

Here, this study investigates the impact of the ceramic particle size on the bulk and interfacial ion transport properties of composite polymer electrolytes. The ceramic particles used for this study are micrometer-sized commercial lithium lanthanum titanate (LLTO) powders and LLTO nanorods (NR) prepared in the laboratory. The polymer matrices are vinylene carbonate (VEC) based single-ion-conducting (SIC) and dual-ion-conducting (DIC) polymer electrolytes. Our results reveal that the addition of LLTO NR results in improved ion transport, while the addition of commercial LLTO is ineffective or even detrimental. We ascribe these results to the formation of an interfacial polymer layer around the LLTO particles with enhanced Li + mobility and estimate the thickness of the interfacial layer to be ∼5 nm. The high surface-to-volume ratio of the LLTO NR leads to the percolation of the interfacial region at a relatively low ceramic loading of 30 wt %. This study highlights the importance of achieving percolation of the interface region (as opposed to the particles themselves) within the composite electrolyte when the interfacial layer is the enhancement mechanism.

Ock, Ji-young↗