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All sources NASA NTRS DOE OSTI

DOE OSTI2023

A Comparative Evaluation and Selection of High-Temperature Heat Exchangers for Application to Integrated Energy Systems

The following report aims to create a refined and well-structured method for comparatively evaluating heat exchanger technologies for integrated energy systems that caters customers’ specific needs while meeting engineering requirements. For the evaluation, this study elevates previous evaluation metrics, enhances the knowledge base via literature and market surveys, and identifies the figures of merit with robust rationales to enhance the quality of decisions made throughout the proposed heat exchanger evaluation process. The heat exchanger designs evaluated as part of the case study are shell and tube heat exchangers, printed circuit heat exchangers, plate heat exchangers, spiral heat exchangers, and heat pipe heat exchangers. The information presented in this report is meant for industries interested in making a preliminary screening process to identify the most suitable heat exchanger design for their application of interest.

42 - ENGINEERING↗

DOE OSTI2024

From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure–property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg 2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg 2+ (with time scales ranging from 0.5 μs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg 2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. In conclusion, this observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

25 ENERGY STORAGE↗

DOE OSTI2024

Intrinsic exchange biased anomalous Hall effect in an uncompensated antiferromagnet MnBi 2 Te 4

Achieving spin-pinning at the interface of hetero-bilayer ferromagnet/antiferromagnet structures in conventional exchange bias systems can be challenging due to difficulties in interface control and the weakening of spin-pinning caused by poor interface quality. In this work, we propose an alternative approach to stabilize the exchange interaction at the interface of an uncompensated antiferromagnet by utilizing a gradient of interlayer exchange coupling. We demonstrate this exchange interaction through a designed field training protocol in the odd-layer topological antiferromagnet MnBi 2 Te 4 . Our results reveal a remarkable field-trained exchange bias of up to ~ 400 mT, which exhibits high repeatability and can be easily reset by a large training field. Notably, this field-trained exchange bias effect persists even with zero-field initialization, presenting a stark contrast to the traditional field-cooled exchange bias. The highly tunable exchange bias observed in this single antiferromagnet compound, without the need for an additional magnetic layer, provides valuable insight into the exchange interaction mechanism. These findings pave the way for the systematic design of topological antiferromagnetic spintronics.

36 MATERIALS SCIENCE↗

DOE OSTI2022

ORGANIC RANKINE CYCLE TURBINE AND HEAT EXCHANGER SIZING FOR LIQUID AIR COMBINED CYCLE

Cryogenic energy storage offers several opportunities to design turbomachinery and other equipment for novel cycles. This paper presents the design and analysis of turbomachinery and heat exchangers for an Organic Rankine Cycle (ORC) subsystem for a hybrid energy storage concept. The Liquid Air Combined Cycle is an energy storage system that stores air at cryogenic conditions at times with high variable renewable energy to be dispatched along with a gas turbine to recover the exhaust heat. In order to re-vaporize the air, the liquid air is coupled with an ORC as an additional bottoming cycle. The ORC turbine is expected to expand the fluid with a pressure ratio of nearly 30 and a flow rate of approximately 45 kg/s. Sizing calculations for both a radial and axial turbine solution were performed over a range of speeds and stages to determine the optimal design point. The results show that either an axial (8- or 9-stage) or radial (four stages at two shaft speeds) turbine are capable of handling the pressure ratios. Further trades of the two configurations would be required to determine the best option. The ORC system also incorporates five heat exchangers to distribute heat, vaporize the liquid air, or recover exhaust heat from the gas turbine. Three heat exchangers were analyzed to understand the size of heat exchangers and pressure drop for the overall system. Different types of heat exchangers were explored for the different purposes, including plate-fin heat exchangers, gasketed plate heat exchangers and shell-in-tube heat exchangers. It was determined that the ORC recuperator, liquid-air vaporizer, and vaporized air pre-heater would be counter-flow heat exchangers using a gasketed plate design. Keywords: Energy Storage, Liquid Air Energy Storage, Organic Rankine Cycle

Pryor, Owen↗

DOE OSTI2024

Evaluating Microchannel Heat Exchanger Lifetime for Concentrating Solar Power Applications FY24Q4 (RPPR-1)

Microchannel heat exchanger technology is being pursued for next generation CSP concepts for primary power cycle heat addition and power cycle heat recuperation due to the high heat transfer coefficients and pressure containment advantages of small sCO 2 channels. The economics of future CSP plants as dictated by the SETO 2020 or 2030 targets depend on a heat exchanger with a 30-year lifetime (resisting creep, fatigue, corrosion, erosion) and operational characteristics such as fast ramping and the ability to withstand thermal shock. However, the lifetime and operational limits of microchannel heat exchangers operating at high-temperatures, particularly those constructed from high-nickel alloys, are not well known. This uncertainty has resulted in heat exchanger vendors not being able to accurately forecast heat exchanger lifetime as required by customers, specify operational limits as required by process engineers to prevent premature heat exchanger failure, or overdesign heat exchanger which leads to higher cost than necessary. Our goal is to evaluate heat exchanger lifetime and operational limits for the manufacturing and prototype design for next-generation CSP heat exchanger technology through a combination of collecting experimental data and modeling studies.

14 SOLAR ENERGY↗

DOE OSTI2024

High performance heat exchangers for next generation hybrid cooler (CRADA Final Report)

The evaporative cooling process has been successfully deployed in multiple energy conversion processes such as power generation, process cooling, heating, ventilation & cooling (HVAC), and commercial and industrial refrigeration. The heat exchanger is a very common yet extremely critical component of such systems. The device is important since the performance of the overall cooling system heavily relies on the thermal-hydraulic efficiency of the heat exchanger. The possible wet operation as evaporative cooling heat exchanger complicates the issue. Indeed, based on the hybrid nature of operation (fully dry, partially wet, fully wet) the efficiency can vary significantly and can cause performance variation for the whole system. Understanding the importance of the issue, Oak Ridge National Laboratory (Contractor) and Baltimore Aircoil Company (Participant) propose an activity focused on the analysis of the existing heat exchanger technology used in air and evaporative cooling processes and design, development and demonstration of a novel heat exchanger design based on porous materials. The potential candidates include metallic wire meshes and metal foams carefully designed for the proposed application. Prior research has indicated that these materials have great potential for deployment in thermal systems, particularly heat sinks and heat exchangers. It is expected that the successful completion of the project will lead to novel heat exchanger technology for hybrid systems (capable of dry and wet operation) by exploring newly emerging materials and their potential for heat transfer application. The overall goal is to develop a next generation heat exchanger technology which can be deployed in evaporative cooling systems. The impact of the such development is significant since, it will not only make the overall system highly efficient but will also, reduce the total refrigerant charge in the heat exchanger, a critical aspect for the deployment of refrigerants with lower Global Warming Potential (GWP).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

NASA NTRS2012

Prototype Vent Gas Heat Exchanger for Exploration EVA - Performance and Manufacturing Characteristics

NASA is developing new portable life support system (PLSS) technologies, which it is demonstrating in an unmanned ground based prototype unit called PLSS 2.0. One set of technologies within the PLSS provides suitable ventilation to an astronaut while on an EVA. A new component within the ventilation gas loop is a liquid-to-gas heat exchanger to transfer excess heat from the gas to the thermal control system's liquid coolant loop. A unique bench top prototype heat exchanger was built and tested for use in PLSS 2.0. The heat exchanger was designed as a counter-flow, compact plate fin type using stainless steel. Its design was based on previous compact heat exchangers manufactured by United Technologies Aerospace Systems, but was half the size of any previous heat exchanger model and one third the size of previous liquid-to-gas heat exchangers. The prototype heat exchanger was less than 40 cubic inches and weighed 2.6 lb. The water side and gas side pressure drops were 0.8 psid and 0.5 inches of water, respectively. Performance of the heat exchanger at the nominal pressure of 4.1 psia was measured at 94%, while a gas inlet pressure of 25 psia resulted in an effectiveness of 84%. These results compared well with the model, which was scaled for the small size. Modeling of certain phenomena that affect performance, such as flow distribution in the headers was particularly difficult due to the small size of the heat exchanger. Data from the tests has confirmed the correction factors that were used in these parts of the model.

Jennings, Mallory↗

NASA NTRS2017

Design and testing of high-performance mini-channel graphite heat exchangers in thermoelectric energy recovery systems

Recent national energy usage studies by Lawrence Livermore National Laboratory in 2015 [1] show that there is approximately 59 Quads (1015 Btu’s) of waste thermal energy throughout various industrial, residential, power generation, and transportation sectors of the U.S. economy. Thermoelectric energy recovery is one important technology for recovering this waste thermal energy in high-temperature industrial, transportation and military energy systems. Thermoelectric generator (TEG) systems in these applications require high performance hot-side and cold-side heat exchangers to provide the critical temperature differential and transfer the required thermal energy. High performance hot-side heat exchangers in these systems are often metal-based due to requirements for high-temperature operation, strength at temperature, corrosion resistance, and chemical stability. However, the generally selected metal-based hot-side heat exchangers (i.e., Inconels, Stainless Steels) suffer from low thermal conductivity, high thermal expansion, and high density, which degrades their thermal performance, leads to high thermal-expansion-driven stresses, and creates relatively high mass/high volume (i.e., low power density) TEG systems that are then difficult to fabricate and integrate into viable energy recovery systems. This paper describes the design and testing of a new, high-temperature minichannel graphite heat exchanger designed for operation up to 500C that is a critical element of a high-power-density TEG power system for aircraft energy recovery. This high-performance graphite heat exchanger represents a new state-of-the-art standard in high-temperature heat exchangers for TEG systems, which provides higher thermal transport, less thermal expansion at operation, lower system level stresses on TE components, and a lighter weight TEG system. This new heat exchanger creates a new design paradigm in TEG system design for terrestrial energy recovery and potential NASA technology infusion into terrestrial energy system applications. This paper will present and discuss the key heat transfer, pressure drop, pumping power analyses and design tradeoffs that created this unique design. Heat transfer and pressure drop modeling was performed with both empirical models based on known heat transfer and friction factor correlations and COMSOL thermal/fluid dynamic modeling of the graphite heat exchanger structure. We will also discuss resulting thermal transport and heat fluxes predicted at the TEG interface level. Heat exchanger performance testing was performed under simulated operating conditions and correlation with test data at the anticipated operating temperature conditions will be presented and discussed.

Shevade, Abhijit↗

DOE OSTI2025

Experimental investigation on heat transfer performance of drain water heat recovery heat exchangers

Water heating accounts for 18 % of residential energy consumption, and a substantial portion of this energy can be recovered through drain water heat recovery systems. Here, this paper investigates the heat transfer performance of drain water heat recovery heat exchangers. Two heat exchanger configurations were studied: vertical (gravity film exchanger) and horizontal. The heat recovery performance of the exchangers was quantified using sensible effectiveness and characteristic curves following the ε-NTU approach. Depending on the flow conditions, heat exchangers with a vertical configuration offered higher heat transfer effectiveness compared with the horizontal configuration under similar operating conditions. Furthermore, the results showed that properly designed and sized heat exchangers can effectively recover considerable amounts of waste heat from drains, depending on flow rates. Additionally, in the vertical heat exchanger configuration, low flow rates result in partially wet conditions, resulting in lower heat transfer effectiveness. Therefore, two distributor configurations are proposed to improve the heat transfer performance of vertically configured heat exchangers at low flow rates. The proposed distributor configurations and data presented in this paper will be useful in the design and development of drain water heat recovery systems in building applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2025

Advances in high-pressure and high-temperature heat exchangers: Innovations via additive manufacturing and their applications

This paper provides a comprehensive overview of technological developments and applications for high-pressure and high-temperature (HPHT) heat exchangers produced through additive manufacturing (AM) techniques. As the demand for high-efficiency energy systems has been rising, the role of heat exchangers for thermal management and transport is becoming increasingly crucial. In this context, AM has emerged as a promising manufacturing solution to address the challenges posed by higher operating temperatures and/or pressures. This paper delves into three primary areas: the exploration of HPHT regimes supported by conventional heat exchangers, the impact of AM processes on thermal transport devices, and the discussion focused on HPHT heat exchangers produced via AM. The study examines the traditional manufacturing processes, materials, structures and geometries, and limitations of the commonly used heat exchangers for HPHT applications. Furthermore, it highlights the potential of AM in optimizing HPHT heat exchanger design, by reviewing studies that enable uniform flow distribution, minimization of fouling, and thermo-hydraulic performance augmentation without compromising structural stability. While addressing the limitations of cost, size, and other constraints, this study offers insights into the possibilities of AM in revolutionizing HPHT heat exchanger technology. The goal has been to fill the gap in literature by summarizing key studies, findings, and limitations, presenting a detailed examination, and proposing new areas for research. In conclusion, this review contributes to a deeper understanding of AM’s role in advancing HPHT heat exchangers for future energy systems.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Flow maldistribution in plate heat exchangers – Impact, analysis, and solutions

Plate heat exchangers are commonly used in various industrial applications, such as refrigeration, air conditioning, heat pumps, powerplants, and chemical industries. Plate heat exchangers are well known for their superior heat transfer performance, compactness, and low refrigerant charge. Despite offering several advantages, they suffer from flow maldistribution issues. The flow maldistribution can deteriorate both the heat transfer and pressure drop performance, ultimately resulting in a lower system efficiency where plate heat exchangers are deployed. The flow maldistribution issues become more pronounced when the heat exchanger size is relatively large and the number of plates is higher, limiting the deployment of plate heat exchangers in larger industrial systems. Consequently, analyzing and understanding the flow maldistribution behavior in plate heat exchangers and finding ways to mitigate flow maldistribution related issues become essential topics of interest. Further, this review aims to address the effect of flow maldistribution on plate heat exchanger characteristics. First, the experimental and numerical works on flow maldistribution under single-phase and two-phase conditions are detailed. Subsequently, the end-channel and end-plate effects are discussed. Then, the methods to mitigate flow maldistribution in plate heat exchangers are outlined. Finally, based on a thorough literature survey and industrial requirements, future research directions are recommended.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2021

Elastic forces drive nonequilibrium pattern formation in a model of nanocrystal ion exchange

The widely used process of nanocrystal ion exchange operates out of thermodynamic equilibrium and can require mixing components of varying sizes. Here we use theory and computer simulation to study a simple model which captures these two basic features of ion exchange reactions. We show that a strong driving force for exchange among different-sized species creates nonequilibrium patterns within model nanocrystals. We further demonstrate that such patterns can be thermodynamically stable within core/shell nanocrystals. These results help us understand the heterostructures formed in ion-exchanged nanocrystals and suggest strategies for leveraging elasticity to design patterns in nanoscale materials. Chemical transformations, such as ion exchange, are commonly employed to modify nanocrystal compositions. Yet the mechanisms of these transformations, which often operate far from equilibrium and entail mixing diverse chemical species, remain poorly understood. Here we explore an idealized model for ion exchange in which a chemical potential drives compositional defects to accumulate at a crystal’s surface. These impurities subsequently diffuse inward. We find that the nature of interactions between sites in a compositionally impure crystal strongly impacts exchange trajectories. In particular, elastic deformations which accompany lattice-mismatched species promote spatially modulated patterns in the composition. These same patterns can be produced at equilibrium in core/shell nanocrystals, whose structure mimics transient motifs observed in nonequilibrium trajectories. Moreover, the core of such nanocrystals undergoes a phase transition—from modulated to unstructured—as the thickness or stiffness of the shell is decreased. Our results help explain the varied patterns observed in heterostructured nanocrystals produced by ion exchange and suggest principles for the rational design of compositionally patterned nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Facile integration of giant exchange bias in Fe 5 Ge Te 2 / oxide heterostructures by atomic layer deposition

Exchange bias arises from the interfacial exchange coupling in ferromagnet-antiferromagnet bilayers and manifests as a horizontal shift of the magnetic hysteresis loop, constituting a critical component underpinning a broad range of magnetoresistive logic and memory devices. The facile implementation of exchange bias in van der Waals (vdW) magnets would be a key step towards practical devices for emerging vdW spintronics. Here, in this paper, we report an easy approach to establishing strong exchange bias in the vdW magnet Fe 5 GeTe 2 by a single-step process—atomic layer deposition (ALD) of oxides on Fe 5 GeTe 2 . We successfully created exchange bias of 300–1500 Oe in Fe 5 GeTe 2 /Al 2 O 3 , Fe 5 GeTe 2 /ZnO, and Fe 5 GeTe 2 /V 2 O 5 heterostructures, at 130 K. Control experiments showed that increasing the oxidant pulse duration in each ALD cycle or utilizing the stronger oxidant O 3 can enhance the exchange bias strength, revealing the key role of the ALD oxidants. Our systematic work elucidates the essential role of ALD-enabled oxidization of Fe 5 GeTe 2 in the formation of exchange bias, and establishes ALD of oxides as a facile, controllable, and generally effective approach to creating giant exchange bias in vdW magnets, representing an integral advance towards practical vdW spintronic devices.

36 MATERIALS SCIENCE↗

NASA NTRSDate not supplied

Integral Channel Nozzles and Heat Exchangers using Additive Manufacturing Directed Energy Deposition NASA HR-1 Alloy

Heat exchangers for use in propulsion applications are very critical components because they must be efficient, compact and light and often operate with working fluids at extreme temperatures or pressures or both. Various components and systems use heat exchangers such as combustion chambers of gas turbines and internal combustion engines, fuel cells (air supply and thermal management), electric batteries (thermal management), evaporators and recuperators of waste-heat-to-power systems, and rocket engines. Even if the results are more generally applicable, the heat exchangers applications to which this study is more closely related are regeneratively cooled rocket nozzles and chambers, and repressurization systems for the launch vehicles. These components are often thin-walled and contain pressurized fluids, like propellants at cryogenic or elevated temperatures. Given that the environments that these propulsion components must endure are challenging, the manufacturing to meet these specifications often require long lead times due to specialty processes and unique tooling associated with the combined thin-wall integral channel and large-scale structures. Additive manufacturing (AM) offers programmatic advantages for reduction in processing time and cost in addition to various technical advantages, including the possibility to achieve enhanced hardware complexity targeted to superior performance, part consolidation, and the capability of processing of novel alloys. While AM is already being utilized for heat exchanger components in propulsion applications, almost all these AM components are made by means of Laser Powder Bed Fusion (L-PBF). L-PBF allows for fine features but is rather limited with respect to the overall size of the components that can be manufactured. Recent developments are maturing the Laser Powder Directed Energy Deposition (LP-DED) process which may be used, for example, to make integral channel thin-wall regeneratively-cooled rocket nozzles with diameters greater than 1 m. This paper highlights some integral channel heat exchanger demonstrator hardware applications of LP-DED, as well as the characterization of this process in combination with the use of the NASA HR-1 alloy. To properly utilize LP-DED for heat exchanger manufacturing, various aspects are being characterized such as geometry limitations, measurement of surface texture and geometric angled surfaces, surface enhancements for internal channels, and material evaluation. NASA HR-1 (FeNi-Cr) is a high strength hydrogen resistant superalloy developed for use in aerospace applications, such as heat exchangers. Some aspects and considerations about the design of heat exchangers are summarized together with data relevant to LP-DED manufacturing in combination with the NASA HR-1 alloy. Microchannels were successful deposited down to 2.54 mm and 1 mm wall thickness, wall angles of 30°, both with high reproducibility. It was also found that the areal surface roughness is highly dependent on the size of the powder feedstock used for deposition. The characterization of these LP-DED features is critical for fluid flow and heat transfer predictions as it can be exploited to enhance heat transfer at the cost of increased pressure drop.

Additive Manufacturing↗

NASA NTRSDate not supplied

Integral Channel Nozzles and Heat Exchangers using Additive Manufacturing Directed Energy Deposition NASA HR-1 Alloy

additive manufacturing↗

DOE OSTI2026

Seasonal variation of the surface cross-shelf exchange in the northern South China Sea: a Lagrangian perspective

Previous studies on cross-shelf exchange, predominantly adopted an Eulerian perspective, struggled to identify water sources and pathways. Using a high-resolution regional ocean modeling system (ROMS) and Lagrangian particle tracking, this study systematically investigates the seasonal variation and dynamics of surface cross-shelf exchange in the northern South China Sea (NSCS) from a Lagrangian perspective. Based on daily released 30-day drifter trajectories we identify the key pathways, source regions for surface cross-shelf exchange, revealing pronounced seasonal variability. Results show the surface cross-shelf exchange generally following monsoon-driven Ekman transport. However, local dynamics, especially topographic modulation, can outweigh the expected Ekman-driven transport, producing surface exchange patterns opposite to that predicted from the prevailing winds. Topographic effects vary across different scales. In the coastal waters of western Guangdong during winter, despite downwelling-favorable winds, the modulation of alongshore currents by island topography induces an eastward pressure gradient. This gradient, through geostrophic balance, drives offshore flows opposite to wind-driven Ekman onshore transport. Furthermore, the eastern widened shelf exhibits a distinct seasonal variation of cross-shelf exchange, with strong offshore transport (opposite to the direction of Ekman transport) in winter and exceedingly weak exchange in summer. Analysis of the underlying mechanisms reveals that this winter offshore transport is primarily attributed to geostrophic flows driven by surface pressure gradient that is jointly modulated by the Kuroshio intrusion and local widened shelf topography, and enhanced by cumulative submesoscale processes. In summer, a persistent and strong along-isobath jet acts as a dynamic barrier, effectively suppressing the exchange. These findings highlight the important role of topography in regulating surface material transport, and have important implications for predicting the advection and dispersion of plankton or oil spills over the continental shelf influenced by monsoon.

Hao, Dongliang↗

DOE OSTI2025

Ion Size Effects on the Thermodynamic, Kinetic, and Mechanical Properties during Ion Exchange in Solid-State Electrolytes

Ion exchange offers a pathway to impose residual compressive stresses to mitigate the electro-chemo-mechanical cracking of solid-state electrolytes such as lithium lanthanum zirconium oxide. This study uses a coupled multiscale framework (integrating density functional theory (DFT), molecular dynamics (MD), and continuum modeling) to examine how exchange ion size influences stress, diffusion, fracture toughness, and electronic properties. Larger isovalent ions (Na + , Ag + , K + ) were exchanged with Li + , with DFT confirming their preference for octahedral 96h sites and a linear relationship between ion size and chemical free expansion coefficient. MD simulations reveal stress and concentration effects on exchange ion diffusivity at elevated temperatures, with Na + and Ag + maintaining favorable mobility while K + showing concentration-dependent clustering. Continuum modeling predicts the range of fracture strength improvements and the required ion exchange concentration profile. It was shown that a 5% surface exchange concentration can induce ∼0.6 GPa of surface compressive stress using Na + and ∼1.0 GPa of surface compressive stress using Ag + . On the other hand, larger ion exchange species may penalize Li + diffusivity by increasing the activation volume and activation energy. Interestingly, Na + has a negligible penalty on Li-ion diffusivity. The room temperature Li + ion diffusivity is reduced by ∼40% with Ag + ion exchange. Electronic band structure analysis shows no size-dependent change in the bandgap, though Ag + introduces localized defect states near the valence band maximum. This study highlights ion size as a key factor in optimizing LLZO properties, offering a framework to improve the solid-state battery performance.

Jagad, Harsh D. [Brown Univ., Providence, RI (Unit↗

DOE OSTI2026

In Situ Insights into Enhanced Cooperative Ligand Exchange Kinetics via Solvent-Induced Restacking in a 2D Metal–Organic Framework

Understanding the reaction kinetics at catalytically active sites is crucial for integrating catalytic two-dimensional (2D) materials into industrial processes. This study focuses on in situ observation of ligand exchange kinetics and solvent-assisted structural restacking transition in the 2D paddle wheel-based MOF [Cu 2 (dttc) 2 ] n (DUT-134(Cu), dttc = dithieno[3,2-b:2′,3′- d]thiophene-2,6-dicarboxylate). The ligand exchange process, involving the replacement of dimethylformamide (DMF) with nitriles such as acetonitrile (ACN), pentanenitrile, and heptanenitrile, was investigated using advanced in situ characterization techniques with high temporal resolution, including powder X-ray diffraction and Raman spectroscopy. The larger analytes exhibited reduced exchange rates, consistent with enhanced steric hindrance and greater diffusion constraints. Interestingly, the study revealed that the exchange of DMF with ACN induces a structural transition to higher symmetry within few seconds, a transition from AB to AA stacking mode of the layers, and a widening of the interlayer distance. Crucially, this structural transition dramatically accelerates the solvent exchange process through cooperative effects, offering critical advantages for catalytic applications. Notably, the reverse exchange from ACN to DMF proceeds more slowly and does not reverse the structural changes, but a new phase is formed with preserved AA stacking. By isotope labeling of linker molecules in combination with two complementary theoretical vibrational simulation methods, the precise assignment of Raman bands and the vibrational modes associated with the ligand exchange process could be achieved. These pioneering insights into the dynamic behavior of 2D MOFs, coupled with ligand exchange, establish a highly promising and transformative approach to achieving enhanced tunability and responsiveness in future catalytic applications.

Layers↗