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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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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption

Multi-carbon alcohols such as ethanol are valued as fuels in view of their high energy density and ready transport. Unfortunately, the selectivity toward alcohols in CO 2 /CO electroreduction is diminished by ethylene production, especially when operating at high current densities (>100 mA cm –2 ). Here we report a metal doping approach to tune the adsorption of hydrogen at the copper surface and thereby promote alcohol production. Using density functional theory calculations, we screen a suite of transition metal dopants and find that incorporating Pd in Cu moderates hydrogen adsorption and assists the hydrogenation of C 2 intermediates, providing a means to favour alcohol production and suppress ethylene. We synthesize a Pd-doped Cu catalyst that achieves a Faradaic efficiency of 40% toward alcohols and a partial current density of 277 mA cm –2 from CO electroreduction. The activity exceeds that of prior reports by a factor of 2.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Mechanically robust and superior conductive n-type polymer binders for high-performance micro-silicon anodes in lithium-ion batteries

Compared with nanostructured silicon (Si), the Si microparticle (SiMP) has more commercial prospects due to its low cost. However, SiMPs suffer from unavoidable fracture during electrochemical cycling owing to their significant volume change. Here we develop a series of novel n-type conductive polymer binders (CPBs) for SiMP anodes in lithium-ion batteries owing to their superior properties. Extraordinary electrochemical performance of cells with such unique binders could be achieved, which is because these designed polymers contain electron-withdrawing oxadiazole ring groups and easily ionizable sulfonate polar groups, exhibiting excellent ionic conductivity, outstanding wettability to the electrolyte, and improved electronic conductivity after doping. Moreover, the coexistence of rigid and flexible chains enables them to have exceptional strength and ductility. Besides, a unique electrochromic approach has been utilized to investigate the energy gap of the CPBs in n-doping states. The ionic and electronic conductivities of prepared CPBs in an eigenstate and n-doping state have been systematically studied by the electrochemical method, filling the current research gap in this field. Due to the high conductivity of b-POD, the capacity of SiMPs (4200 mA h g –1 ) can be almost entirely released during the first cycle of discharge, while the SiMP anodes prepared with the PAALi or CMC binder show a much lower initial capacity. Here, the high conductivity of b-POD also endows it with better cycling performance than non-conductive binders especially at high current densities, demonstrating its excellent fast-charging ability. More essentially, this work provides polymer binders without any intricate structural designs to obtain high-performance SiMP batteries, significantly enhancing their practical applications.

25 ENERGY STORAGE↗
DOE OSTI2024

MEMS RF accelerators for nuclear energy and advanced manufacturing

Energetic ions are widely used to develop radiation hard structural materials and fuels for advanced nuclear energy. Ion beams are also used to generate neutrons for nuclear materials testing, as well as in a series of high impact, high value adding manufacturing processes (ranging from doping of semiconductors to hardening of materials against wear and to increase bio-compatibility of materials). But to date, high power beams of high energy ions are simply too expensive because they are delivered from large single beam accelerators. We have recently demonstrated that MEMS technology enables massively parallel, low cost batch fabrication of ion beams. We propose to scale intense ion accelerators based on MEMS (micro-electro mechanical systems) to high beam power (>10 kW). With our approach, hundreds to thousands of ion beamlets will be densely packed on silicon wafers. Ions are injected and accelerated across gaps formed in stacks of wafers, leading to uniquely high current densities for intense ion accelerators with variable kinetic energy (0.1 to 10 MeV) and variable ion species. Our team brings together experts in high power ion accelerators from Lawrence Berkeley National Laboratory and leading experts in MEMS technology from Cornell University. We will deliver a disruptive technology of low cost, flexible and massively scalable ion accelerators that will enable the rapid development of radiation hard nuclear materials for advanced nuclear energy and enable new applications in manufacturing.

43 PARTICLE ACCELERATORS↗
DOE OSTI2020

Flue Gas CO 2 Capture via Electrochemically Mediated Amine Regeneration: Desorption Unit Design and Analysis

We analyzed the performance of an electrochemical desorption unit to be implemented in an electrochemically mediated amine regeneration (EMAR) process, which separates CO 2 and regenerates the amine upon modulation of a targeted species that complexes with the amine molecules. Using a simplified one-dimensional boundary layer model, we combined the kinetic expressions of the faradaic reactions with mass transfer effects to analyze the polarization behavior of the flow cell. Mass transfer limitations become dominant at high current densities, leading to increases in energy consumption. An understanding of scaling laws with key parameters, such as the Sherwood number, is required to achieve high power operation with minimal mass transfer losses. Because the EMAR chemistry is sensitive to temperature, heat distribution in the unit is also examined. Our results indicate that the desorption performance increases with addition of a high-temperature heat source. Additionally, incorporation of membrane crossover suggests energy losses because of diffusion and migration of active species. Furthermore, these findings inform on scaling laws for at-scale desorber design and provide a model for scaling up the EMAR system for larger scale operations.

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

Influence of Supporting Electrolyte on Hydroxide Exchange Membrane Water Electrolysis Performance: Catholyte

Alkaline or hydroxide exchange membrane water electrolysis (HEMWE) is a promising technology for green hydrogen production using platinum group metal-free catalysts and stainless steel, an advantage of alkaline water electrolysis (AWE), and a gas-impermeable membrane, a parallel to proton exchange membrane electrolysis (PEMWE). However, the HEMWE requires supporting electrolytes and there is minimal understanding of their role on the respective reactions. Without SELs, HEMWE performance and durability are worse than PEMWE systems. Herein, consistently feeding potassium hydroxide anolyte, we systematically study the effects of catholyte SELs in HEMWEs including dry vs. wet operation, cation effects, anion effects, and cation/OH ratios on cell potential and stability. We report that (i) hydration of the cathode improves high current density operation by preventing dehydration of the hydroxide exchange membrane (HEM), (ii) there was no correlation between cation type and cell potential, (iii) cell potential and high frequency resistance did not correlate with SEL conductivity, (iv) cathodic carbonate SEL had a significant negative effect on cell performance, (v) increased cation/OH ratio also caused increased cell potentials. Overall, this study concludes that feeding water or potassium hydroxide solution is desirable to improve the AEMWE performance.

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

Fabrication of Advanced Nanocarbon-Metal Composites for Improved Energy Efficiency

We fabricated nanocarbon metal composites (NCMC) of Al alloys with a process called “electrocharging assisted process” (EAP). This method consists of the application of a high current to a mixture of liquid metal and carbon particles. We investigated aluminum alloys (6061 and 1350) and used activated carbon and graphite powder as the source of carbon. The high current induces the formation of carbon chains and ribbons in the liquid metal. Upon solidification of the metal an epitaxial relation between the carbon nanostructures and the metal lattice is produced. The purpose of the project was to find the parameters during the reaction that would give rise to a high density of nanoribbons extending throughout the metal such that the electrical conductivity and the mechanical strength of the composite increased and that the method could be extended to large scale manufacturing. For this purpose, we designed two reactors for the incorporation of nanocarbon ribbons in aluminum metal. The first reactor was designed to have more control of the region with the high current density. However, there were problems with getting good mixing of the carbon in small volumes. A second reactor was designed with a stirrer that allowed for better mixing of the carbon by the introduction of argon gas through the shaft of the stirrer. NCMC were fabricated with a series of parameters to understand the role of current, time of applied current, type and shape of the cathode electrode and stirring speed of the mixture. We analyzed the composites by Raman scattering to gain information on the crystallite size of the nanocarbon, XRD to obtain the crystal structure of the composite, SEM and TEM to characterize the grain size of the aluminum grains and the quality of the crystal structure. We also measured the electrical conductivity and mechanical properties of selected samples. The nanocomposites showed increase in crystallite size of the nanocarbon with a linear dependence of the crystallite size on the duration of the applied current. There is a minimum current density necessary for the crystallite size to increase compared to the ~ 10 nm size of the activated carbon source used in the fabrication. The electrical conductivity of the nanocomposites increased with crystallite size of the nanocarbon and with the concentration of converted carbon. The maximum increase in electrical conductivity was 5.7% above the baseline for samples with ~ 4 wt % nanocarbon with crystallite size larger than 30 nm. These samples presented a hardness ~ 8% higher than the baseline samples with no carbon.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2023

Particle size effect of graphite anodes on performance of fast charging Li-ion batteries

Charging energy-dense lithium-ion batteries (LIBs) with thick graphite electrodes at high current densities are typically accompanied by poor performance and safety issues. The root cause is the onset of Li plating at the surface of graphite when lithiated to a high capacity within a short time period. Here, we investigated the behavior of graphite electrodes with various particle sizes under fast charge operations. Results from the electrochemical characterization on graphite electrodes exhibit the superiority of smaller particles over bigger particles in terms of suppressing the onset of Li plating and growth of plated Li particles. Observations from scanning electron microscopy also corroborate the presence of plated Li in electrodes with big graphite particles and its absence in graphite electrodes with small particles, when the cells were lithiated to 90% of the state of charge (SOC). Further, the improved performance of cells with the small particles might be associated with the low Li-ion concentration at the surface of graphite and thus reduced overpotential in graphite electrodes. The simulated results revealed that, compared to bigger particles, smaller particles have lower surface intercalation at any given cell SOC, which may significantly reduce the overpotential in the graphite electrodes and mitigate the onset of Li plating. This agrees well with experimental observations.

25 ENERGY STORAGE↗
DOE OSTI2020

Single crystal cathodes enabling high-performance all-solid-state lithium-ion batteries

All-solid-state lithium-ion batteries (ASSLIBs) are receiving significant attention owing to their improved safety and energy density over liquid counterparts. However, single-crystal cathodes have never been investigated in ASSLIBs. In this work, single-crystal Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 (SC-NMC532) is used as the cathode material for ASSLIBs, which exhibits 6~14 times higher Li + diffusion coefficient than polycrystalline Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 (PC-NMC532). As a result, SC-NMC532 exhibits an initial specific capacity of 156.4 mAh.g -1 while PC-NMC532 shows an initial capacity of only 127.5 mAh.g -1 . After 150 cycles, SC-NMC532 retains the capacity of 94.5 mAh.g -1 . More impressively, under a high current density of 1.3 mA.cm -2 , SC-NMC532 exhibits a capacity of 82 mAh.g -1 , much higher than that of PC-NMC532 (2.1 mAh.g -1 ). This work demonstrates that single-crystal NMC cathodes could enable both high power density and high energy density of ASSLIBs.

25 ENERGY STORAGE↗
DOE OSTI2025

Sub-angstrom strain in high-entropy intermetallic boosts the oxygen reduction reaction in fuel cell cathodes

The strain effect of high-entropy intermetallic (HEI) catalysts on oxygen reduction reaction (ORR) performance remains largely unexplored, primarily due to the significant challenges associated with characterizing and calculating the intricate local coordination environments. Here, we design a nitrogen (N)-doped L1 0 -ordered PtCoNiFeCu intermetallic catalyst supported on Ketjenblack carbon (N-HEI/KB), and reveal the origin of the sub-angstrom strain in N-HEI and its impact on ORR performance by combining atomic-scale characterization and theoretical calculations. The synergistic interplay of the sub-angstrom strain, the pinning effect of metal-N bonds, and the high-entropy effect contribute to the competitive stability of N-HEI/KB catalysts, providing high current density of 1388 mA cm -2 at 0.7 V after 90,000 cycles even under harsh heavy-duty vehicle conditions. These findings broaden the avenues for designing high-performance high-entropy intermetallic cathode electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Achieving 5,000-h and 8,000-h Low-PGM Electrode Durability on Automotive Drive Cycles

Whereas total Pt loading in anode and cathode catalysts below 0.125 mg cm −2 is required to meet the stringent cost target for automotive fuel cell systems (FCS) for light duty vehicles, low-loaded cathode catalysts are susceptible to unacceptable aging-related performance losses at high current densities. A framework model, validated by accelerated stress test data, has identified cell voltage, relative humidity (RH) and temperature as the key operating variables that affect degradation of a high-activity d-PtCo/C cathode catalyst with 0.1 mg cm −2 Pt loading. Drive cycle simulations indicate that these can be controlled by properly selecting the minimum FCS power, compressor-expander module (CEM) turndown, and stack coolant temperature. The optimum system parameters are 4-kW e minimum power for an 80-kW e FCS, CEM turndown of 12.5, and 66 °C average coolant exit temperature that combine to limit the maximum cell voltage to 850 mV and outlet RH to 90%–100%. Depending on Pt loading, the mismatch between actual and allowable degradation for 10% power loss over 5,000-h lifetime requires the stack to be oversized by 2.4%–5%, resulting in 8.4%–41% lower Pt utilization and 7.1%–20.5% penalty in stack cost. The corresponding results for 8,000-h lifetime are 10.3%-14% stack oversizing, 23%–51.8% lower Pt utilization, and 24.1%–35.4% stack cost penalty.

08 HYDROGEN↗
DOE OSTI2021

High Performance Air Breathing Flexible Lithium–Air Battery

Lithium–oxygen (Li–O 2 ) batteries possess the highest theoretical energy density (3500 Wh kg –1 ), which makes them attractive candidates for modern electronics and transportation applications. In this work, an inexpensive, flexible, and wearable Li–O 2 battery based on the bifunctional redox mediator of InBr 3 , MoS 2 cathode catalyst, and Fomblin-based oxygen permeable membrane that enable long-cycle-life operation of the battery in pure oxygen, dry air, and ambient air is designed, fabricated, and tested. The battery operates in ambient air with an open system air-breathing architecture and exhibits excellent cycling up to 240 at the high current density of 1 A g –1 with a relative humidity of 75%. The electrochemical performance of the battery including deep-discharge capacity, and rate capability remains almost identical after 1000 cycle in a bending fatigue test. Furthermore, this finding opens a new direction for utilizing high performance Li–O 2 batteries for applications in the field of flexible and wearable electronics.

25 ENERGY STORAGE↗
DOE OSTI2022

Using Membranes with Internal Microchannels to Prevent Drying-out during CO 2 Electrolysis

Scaling up CO 2 electrolysis is a vital aspect in the transition to manufacturing sustainable fuels and chemical compounds, satisfying the demand for chemicals and demand for storing renewable electricity. Depending on the employed catalyst, different products can be produced, such as carbon monoxide and ethylene, by applying a voltage on a CO 2 and H 2 O fed electrolyzer. CO is a desirable product according to techno-economic analysis, because it can be produced selectively using a silver catalyst and is a precursor for hydrocarbons in the Fischer–Tropsch process. In a state-of-the-art CO 2 electrolyzer, two electrodes are directly pressed against an ion-exchange membrane – this is called a zero-gap configuration. Therefore, the membrane is a crucial component for the system, since it has the role of providing a conductive medium between the electrodes. One of the challenges in CO 2 electrolysis is that water is consumed in the reaction. At high current density, this may cause the membrane's surface near the cathode to dry out, lowering efficiency or perhaps stopping the process entirely, since there is no longer a conductive medium. As a result, water management is critical for this process. In this work, we approach the drying-out challenge by studying the novel concept of a membrane with internal microchannels. These channels allow the circulation of water or an electrolyte inside the membrane, which reduces the water diffusion path and affects the membrane’s conductivity. The effects of channel geometry, location, and concentrations of electrolyte inside on water content, conductivity and overall performance are studied in a 2D COMSOL model. In addition, the effect of internal concentration of electrolyte on the membrane’s resistance, on the process performance and the K + cross-over to cathode side were investigated experimentally. Our modeling results prove that the presence of the channels can keep the membrane hydrated. The highest current densities are observed when the channel is closest to the cathode, and with smaller pores. Smaller pores are advantageous due to the trade-off between enhanced membrane conductivity and the lower conductivity of the liquid itself. If water is circulated in a large channel, it increases the membrane’s ionomer conductivity due to hydration but the overall conductivity is decreased since water is not highly conductive. Nonetheless, the results also show that a higher concentration of electrolyte inside the microchannels can significantly increase the total conductivity of the membrane, and therefore the energy efficiency of the process. These effects are most significant at higher current densities. In the experimental results, we’ve observed similar effects in terms of membrane conductivity and current density of the process – the higher the electrolyte concentration the higher the current density. Furthermore, a low concentration decreases the amount of potassium which crosses over to the cathode side, inhibiting salt deposition. We’ve concluded that a small channel, up to 90 µm wide, close to the pore with an electrolyte with a concentration of up to 10 mM could be very beneficial for the water management and energy efficiency of the process. This helps to keep the membrane hydrated at higher current densities, improves the conductivity of the membrane, and it doesn’t have significant impacts on the salt deposition.

Petrov, Kostadin Veselinov↗
DOE OSTI2025

Project Title: Demonstration High Temperature Superconducting NonPlanar Stellarator Magnet with Advanced Manufactured Assemblies

This is the final report for the project “Demonstration High Temperature Superconducting Non- Planar Stellarator Magnet with Advanced Manufactured Assemblies”, funded by DOE, and performed by Type One Energy from September, 2020, to March 2024 involving the Fusion Technology Institute at the University of Wisconsin–Madison, the Plasma Science and Fusion Center (PSFC) at the Massachusetts Institute of Technology (MIT) and Commonwealth Fusion Systems (CFS) to design and fabricate the first non-planar HTS (REBCO) coil for a high-field stellarator based on the SPARC tokamak’s VIPER cable concept. Stellarators at high fields make high-temperature superconducting magnets necessary for a compact fusion device. But the asymmetric and non-planar nature of its components, especially the magnets make it difficult for scalable producibility. To address these challenges, two promising technologies have emerged: advanced manufacturing (AM) for the supporting plates for forming the magnets, and high-temperature superconducting (HTS) cables inside the plates. AM has advanced enough to produce stellarator components with the necessary geometric complexity, size, and the precision, leading to potentially significant reductions in production time, cost, and waste. The cost of HTS tape has decreased dramatically, and progress in HTS planar magnet development has reached a point where it can be proposed for application to complex 3D non-planar magnets. The main objective of this project is to develop, demonstrate and pre-commercialize a novel, non-planar HTS coil shape that remains superconducting to achieve production scalable reductions in time and cost and performance. The proposed technology is based on the novel concept of a precision sub-scale HTS nonplanar coil assembly. This project focuses on the design, fabrication, material optimization of cable design, and validation and demonstration of the high current carrying capability of superconducting magnets and their support in a complex 3D shape needed for application to stellarator magnetic plasma confinement. The specific objectives of this research program include: (1) The successful application of metal AM to build a precision sub-scale HTS nonplanar coil, (2) An HTS cable and cross-section design that can conform to the required nonplanar coil shape (bend radii as tight as 10-cm) and remains superconducting at an engineering current density of 1.35 kA/cm 2 at 77 K and 1 tesla at the conductor (5 kA in the cable). To achieve the above challenging goals, we have formed a multidisciplinary research team consisting of members from Type One Energy and UW-Madison, MIT PSFC and CFS with complementary skills and strong facilities. The team worked collaboratively on fundamental and applied research on the following three major technical areas: (1) Design, fabrication, and optimization of non-planar HTS Cable The ultimate goal of the project is to determine if commercial REBCO tapes and additive manufacturing can be used to fabricate high field (≥ 10T) non-planar coils with tight bending radii (≃ 100mm) and with a degradation of the critical current (Ic) smaller than 20% with respect to the expected performance. We started with shorter length cable to evaluate the scalability of the production process and eventually reached multiple turns for higher magnetic fields. Our findings suggest that a stellarator coil system of a relevant size, characterized by its asymmetric and non-planar components, can be fabricated using a formed cable in plate method. This system can be simulated using a large-scale modeling approach. The use of hybrid modeling 3 techniques will be pivotal in reducing the complexity of the model and in assessing expected performance in designs. (2) Modeling and simulation of the non-planar HTS Cable Multiphysics simulations are performed using the commercial software and are carried out in self-field conditions, involving 2D and 3D models and twisted around one slot of twist-pitched VIPER cable. Multiphysics simulations are mainly focused on the coil for the critical current evaluation, the magnetic field map, self-Lorentz forces and mechanical, and magnetothermal behavior and the quench dynamics. The detailed model and prediction of the superconducting performance of a stellarator-relevant demonstration cable from numerical simulations supports the results from the actual testing backing the results. A detailed description and results are provided in the later sections. (3) Design, fabrication, and optimization of support for the non-planar HTS Cable The team developed an additive manufactured (AM) coil positioning plate that formed into the required non-planar geometry (with bend radii as tight as 10-cm) and to acceptable tolerances required for a stellarator magnet: (+0.25-mm from ideal on dimensions of coil positioning plates and up to +1-mm from ideal for position of wound coil). The plate materials is also included in this selection process from fabrication and 3D printing perspective and commensurate with eventual application to a fusion reactor. From the cost effectiveness point of view, the HTS coil and plate has the potential to cost less than that made in conventional methods with less waste (<75% waste) reducing time (<50%) and cost (<50%), especially as the AM field matures. The application of advanced manufacturing in the construction of the support plates will also lead to cost reduction, as the cables can be easily replaced, thereby making the assembly modular. With such high primary cost and time savings, high current densities and magnetic field, the funded R&D work has validated the designs, proven the feasibility, and characterized the performance of the HTS coil and plate assembly, paving the way for a relevant-size stellarator coil system.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

0D-1D Hybrid Silicon Nanocomposite as Lithium-Ion Batteries Anodes

Lithium ion batteries (LIBs) are the enabling technology for many of the societal changes that are expected to happen in the following years. Among all the challenges for which LIBs are the key, vehicle electrification is one of the most crucial. Current battery materials cannot provide the required power densities for such applications and therefore, it makes necessary to develop new materials. Silicon is one of the proposed as next generation battery materials, but still there are challenges to overcome. Poor capacity retention is one of those drawbacks, and because it is tightly related with its high capacity, it is a problem rather difficult to address with common and scalable fabrication processes. Here we show that combining 0D and 1D silicon nanostructures, high capacity and stability can be achieved even using standard electrode fabrication processes. Capacities as high as 1200 mAh/g for more than 500 cycles at high current densities (2 A/g) were achieved with the produced hybrid 0D/1D electrodes. In this research, it was shown that while 0D nanostructures provide good strain relaxation capabilities, 1D nanomaterials contribute with enhanced cohesion and conductive matrix integrity.

0D↗
DOE OSTI2020

High-Performance, Long-Life, Rechargeable Li–CO 2 Batteries based on a 3D Holey Graphene Cathode Implanted with Single Iron Atoms

A highly efficient cathode catalyst for rechargeable Li-CO 2 batteries is successfully synthesized by implanting single iron atoms into 3D porous carbon architectures, consisting of interconnected N,S-codoped holey graphene (HG) sheets. The unique porous 3D hierarchical architecture of the catalyst with a large surface area and sufficient space within the interconnected HG framework can not only facilitate electron transport and CO 2 /Li+ diffusion, but also allow for a high uptake of Li 2 CO 3 to ensure a high capacity. Consequently, the resultant rechargeable Li-CO 2 batteries exhibit a low potential gap of approximate to 1.17 V at 100 mA g -1 and can be repeatedly charged and discharged for over 200 cycles with a cut-off capacity of 1000 mAh g -1 at a high current density of 1 A g -1 . Density functional theory calculations are performed and the observed appealing catalytic performance is correlated with the hierarchical structure of the carbon catalyst. This work provides an effective approach to the development of highly efficient cathode catalysts for metal-CO 2 batteries and beyond.

(2) batteries↗
DOE OSTI2022

Electrocatalytic water oxidation performance in an extended porous organic framework with a covalent alliance of distinct Ru sites

The rational synthesis of durable, earth-abundant efficient electrocatalysts for the oxygen evolution reaction (OER) from water is one of the most important routes for storing renewable energy and minimizing fossil fuel combustion. The prime hurdles for effectively utilizing commercial RuO 2 as (OER) electrocatalysts are its very low stability, catalyst deactivation, and high cost. In this work, we explored a Ru-integrated porous organic polymer (Ru@Bpy-POP) by a facile one-pot Friedel–Crafts alkylation strategy between redox-active (Ru(demob) 3 Cl 2 ) and a carbazole unit, which is composed of unique features including an extended framework unit, isolated active sites, and tunable electrode kinetics. Ru@Bpy-POP can serve as a bridge between a Metal–Organic Framework (MOF) and POP-based catalytic systems with a balanced combination of covalent bonds (structural stability) and open metal sites (single site catalysis). Ru@Bpy-POP, deposited on a three-dimensional nickel foam electrode support, exhibits a promising electrocatalytic OER activity with an ultra-low ruthenium loading compared to a benchmark RuO 2 catalyst, providing an overpotential of about 270 mV to reach 10 mA cm –2 in an alkaline medium. Moreover, a high current density of 248 mA cm –2 was achieved for the Ru@Bpy-POP catalyst at only 1.6 V (vs. RHE), which is much higher than 91 mA cm –2 for commercial RuO 2 . The robust, albeit highly conjugated, POP framework not only triggered facile electro-kinetics but also suppressed aggregation and metallic corrosion during electrolysis. In particular, the benefits of covalent integration of distinct Ru sites into the framework can modulate intermediate adsorption and charge density, which contributes to its exceptional OER activity. All of the critical steps involved in OER are complemented by Density Functional Theory (DFT) calculations, which suggest that electrocatalytic water oxidation proceeds from a closed-shell configuration to open-shell electronic configurations with high-spin states. Finally, these open-shell configurations are more stable than their closed-shell counterparts by 1 eV, improving the overall catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Interface-engineered (CrMnTiZnCo) 3 O 4 @polypyrrole nano-hybrids for superior lithium storage

High-entropy oxides (HEO) have emerged as promising anode materials for lithium-ion batteries (LIBs) due to their high theoretical specific capacity. However, their practical application is hindered by several challenges, including significant volume expansion, electrode pulverization, and substantial irreversible capacity loss during initial cycles. To address these limitations, this study designed a novel core-shell composite material, denoted as HEO@PPy, which consists of a (CrMnTiZnCo) 3 O 4 -based HEO core and a polypyrrole (PPy) shell. This composite demonstrates remarkable electrochemical performance: it maintains a specific capacity of 1090.1 mAh/g after 100 cycles at 100 mA/g and retains 521.8 mAh/g after 1000 cycles at 1 A/g, highlighting its superior cycling stability. Furthermore, it exhibits excellent rate capability, delivering a capacity of 372.1 mAh/g even at a high current density of 5 A/g. These findings confirm that the strategic compositional and structural design of HEOs, combined with hybridization with conductive polymers like PPy, provides a viable pathway for developing advanced anode materials for next-generation, high-performance lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Harmonic generation in a terawatt x-ray free-electron laser

Abstract Terawatt x-ray free-electron lasers (XFELs) represent the frontier in further development of x-ray sources and require high current densities with strong transverse focusing. In this paper, we investigate the implications/potentialities of TW XFELs on the generation of harmonics at still shorter wavelengths and higher photon energies. The simulations indicate that significant power levels are possible at high harmonics of the XFEL resonance and that these XFELs can be an important coherent source of hard x-rays through the gamma ray spectrum. For this purpose, we use the MINERVA simulation code which self-consistently includes harmonic generation. Both helical and planar undulators are discussed in which the fundamental is at 1.5 Å and study the associated harmonic generation. While tapered undulators are needed to reach TW powers at the fundamental, the taper does not enhance the harmonics because the taper must start before saturation of the fundamental, while the harmonics saturate before this point is reached. Nevertheless, the harmonics reach substantial powers. Simulations indicate that, for the parameters under consideration, peak powers of the order of 180 MW are possible at the fifth harmonic with a photon energy of about 41 keV and still high harmonics may also be generated at substantial powers. Such high harmonic powers are certain to enable a host of enhanced applications.

Physics↗