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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 127 records · Page 7

Structural Analysis of LaNi 4.25 Al 0.75 Hydride

The lanthanum (La)-nickel (Ni)-aluminum (Al) hydrides (LANA: LaNi 5 − x Al x , x < 1.0) have been extensively studied for their high volumetric storage capacity and improved durability to maintain a single-phase CaCu5 structure through multiple absorption and desorption cycles. Pressure composition temperature (PCT) isotherms obtained for LANA have allowed for an understanding of the hydrogen sorption properties and the tunability of the PCT plateau region via doping. At the Savannah River Site, LaNi 4.25 Al 0.75 (LANA0.75) has been utilized as a hydrogen storage material in the tritium facilities for decades. However, the structure characterization of the LANA0.75 hydride by X-ray diffraction has not yet been reported. This study examines LANA0.75 loaded to different hydrogen-to-metal atom ratios to elucidate both the position of hydrogen sites in the lattice and the structure of a fully hydrided β phase.

hydrogen storage↗

Multiplexing of frequency-modulation spectroscopy by spread-spectrum codes, demonstrated in continuous-wave LIDAR

Frequency-modulation spectroscopy (FMS) is generally suited to code-division multiplexing, and we demonstrate that capacity in a form of continuous-wave LIDAR, utilizing a sharp CO 2 absorption transition at 1.6 µm in simple ranging setups. The approach retains the advantages of FMS, including coherent detection and good rejection of broad absorption backgrounds. Extensions of this multiplexed approach to the continuous, simultaneous detection of several transitions would come by transmitting an encoded combination of frequency-modulated carriers, each tuned to detect a unique absorption transition. Signal analysis at the receiver involves a simple process of de-multiplexing that, in a general application, reveals targets at various distances and the absorption-related FMS signals in between.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Impact of Hydrogen Bonds on CO 2 Binding in Eutectic Solvents: An Experimental and Computational Study toward Sorbent Design for CO 2 Capture

Choline-based amino acid ionic liquids with anions glycinate, β-alaninate, phenylalaninate, and prolinate were synthesized and mixed with ethylene glycol to form lower-viscosity benign eutectic solvents for CO 2 capture. The highest capacity measured was 0.7 moles of CO 2 per mole of ionic liquid (2 moles CO 2 per kg solvent) for a 1 to 2 mole ratio mixture of choline prolinate to ethylene glycol at 1 bar of CO 2 and 25 °C. Under 5000 ppm of CO 2 , half of this capacity was realized. Here, through a combined study of quantitative 13 C NMR spectroscopy, molecular dynamics simulations and density functional theory calculations, we show that hydrogen bonding in the eutectic solvent prevents proton-transfer between prolinate anions upon CO 2 absorption, which occurs in the absence of ethylene glycol and deactivates binding sites. Blocking this proton transfer leads to a higher binding capacity compared to neat choline prolinate. This work demonstrates the impact of hydrogen bonding on the CO 2 binding mechanism and energetics, as well as physical and thermal properties in eutectic solvents, thus addressing an unmet need and informing future studies on the development of benign sorbents for capturing CO 2 from dilute streams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nickel-rich Nickel Manganese Cobalt (NMC622) Cathode Lithiation Mechanism and Extended Cycling Effects Using Operando X-ray Absorption Spectroscopy

Ni-rich NMC materials are a particularly promising class of Li-ion cathodes for various applications. LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) offers a unique balance of thermal stability and energy density, thus attracting attention for electric vehicle implementation. However, upon extended cycling, capacity fade is prevalent due to structural degradation, which is a major drawback for layered oxide cathodes. Therefore, exploring the underlying phenomena that drive detrimental structural response can lead to future improvements. For the first time, operando X-ray absorption spectroscopy (XAS) was performed on NMC622 pouch cells at three different stages. An extensive description of the first cycle (de)lithiation mechanisms was achieved through X-ray absorption near-edge structure analyses and extended X-ray absorption fine structure modeling. Transition metal specific electrochemical participation and structural variation revealed that much of the delivered capacity and distortion is a result of Ni redox behavior, while the local structure of Co and Mn are impacted due to their interdependencies. Key mechanistic components were identified, as the local structural variation from redox processes and Ni 3+ Jahn–Teller distortion were decoupled. Further, operando XAS was used to investigate the structural response of NMC622 to extended cycling and was supported by X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy analyses. In this work, reduced capacity was found in the cell after 100 cycles and is attributed to structural degradation and cathode–electrolyte interphase buildup from repeated Li (de)insertion processes, which limit the electrochemical reversibility of Ni and Co through increased polarization. These results expand the understanding of a Ni-rich NMC material under extended cycling, which is vital to the future design of electrode materials.

25 ENERGY STORAGE↗

Elucidating Sodium-Sulfur Battery Chemistry using Operando Transmission X-ray Microscopy and X-ray Absorption Spectroscopy

Room-temperature sodium-sulfur (Na-S) batteries offer a beneficial and cost-effective solution for powering modern electric grids and devices. However, Na-S batteries suffer from performance decay during battery cycling due to the sluggish kinetics and polysulfide shuttling. Revealing the conversion mechanism of the Na-S chemistry is critical to designing high-capacity and stable Na-S batteries. In this study, we employed operando X-ray microscopy and operando X-ray absorption spectroscopy to elucidate the sulfur conversion in a carbon host using an ether-based electrolyte. We reveal the structural and chemical evolution of the sulfur cathode during cycling, which results in volume expansion and the dissolution of active material, ultimately affecting the battery performance. Our work provides fundamental insight into the sulfur reaction scheme, addressing the lingering challenges before establishing inexpensive Na-S batteries for broad applications, including portable electronics and large-scale energy storage.

Jagadeesan, Sathya Narayanan [SLAC National Accele↗

Large Destabilization of (TiVNb)-Based Hydrides via (Al, Mo) Addition: Insights from Experiments and Data-Driven Models

High-entropy alloys (HEAs) represent an interesting alloying strategy that can yield exceptional performance properties needed across a variety of technology applications, including hydrogen storage. Examples include ultrahigh volumetric capacity materials (BCC alloys → FCC dihydrides) with improved thermodynamics relative to conventional high-capacity metal hydrides (like MgH 2 ), but still further destabilization is needed to reduce operating temperature and increase system-level capacity. Here, in this work, we demonstrate efficient hydride destabilization strategies by synthesizing two new Al 0.05 (TiVNb) 0.95–x Mo x (x = 0.05, 0.10) compositions. We specifically evaluate the effect of molybdenum (Mo) addition on the phase structure, microstructure, hydrogen absorption, and desorption properties. Both alloys crystallize in a bcc structure with decreasing lattice parameters as the Mo content increases. The alloys can rapidly absorb hydrogen at 25 °C with capacities of 1.78 H/M (2.79 wt %) and 1.79 H/M (2.75 wt %) with increasing Mo content. Pressure-composition isotherms suggest a two-step reaction for hydrogen absorption to a final fcc dihydride phase. The experiments demonstrate that increasing Mo content results in a significant hydride destabilization, which is consistent with predictions from a gradient boosting tree data-driven model for metal hydride thermodynamics. Furthermore, improved desorption properties with increasing Mo content and reversibility were observed by in situ synchrotron X-ray diffraction, in situ neutron diffraction, and thermal desorption spectroscopy.

36 MATERIALS SCIENCE↗

Advanced Supported Liquid Membranes for CO2 Control in Extravehicular Activity Applications

Developing a new, robust, portable life support system (PLSS) is currently a high priority for NASA in order to support longer and safer extravehicular activity (EVA) missions. One of the critical PLSS functions is maintaining the carbon dioxide (CO2) concentration in the suit at acceptable levels. Although the Metal Oxide (MetOx) canister has worked well, it has a finite CO2 adsorption capacity. Consequently, the unit would have to be larger and heavier to extend EVA times. Therefore, new CO2 control technologies must be developed to meet mission objectives without increasing the size of the PLSS. Although recent work has centered on sorbents that can be regenerated during the EVA, this strategy increases the system complexity and power consumption. A simpler approach is to use a membrane that selectively vents CO2 to space. A membrane has many advantages over current technology: it is a continuous system with no theoretical capacity limit, it requires no consumables, and it requires no hardware for switching beds between absorption and regeneration. Unfortunately, conventional gas separation membranes do not have adequate selectivity for use in the PLSS. However, the required performance could be obtained with a supported liquid membrane (SLM), which consists of a micro porous material filled with a liquid that selectively reacts with CO2 over oxygen (O2). In a current Phase II SBIR project, Reaction Systems has developed a new reactive liquid, which has effectively zero vapor pressure making it an ideal candidate for use in an SLM. The SLM function has been demonstrated with representative pressures of CO2, O2, and water (H2O). In addition to being effective for CO2 control, the SLM also vents moisture to space. Therefore, this project has demonstrated the feasibility of using an SLM to control CO2 in an EVA application. 1 President

Wickham, David T.↗

Advanced Supported Liquid Membranes for CO2 Control in Extravehicular Activity Applications

Developing a new, robust, portable life support system (PLSS) is currently a high priority for NASA in order to support longer and safer extravehicular activity (EVA) missions. One of the critical PLSS functions is maintaining the carbon dioxide (CO2) concentration in the suit at acceptable levels. Although the Metal Oxide (MetOx) canister has worked well, it has a finite CO2 adsorption capacity. Consequently, the unit would have to be larger and heavier to extend EVA times. Therefore, new CO2 control technologies must be developed to meet mission objectives without increasing the size of the PLSS. Although recent work has centered on sorbents that can be regenerated during the EVA, this strategy increases the system complexity and power consumption. A simpler approach is to use a membrane that selectively vents CO2 to space. A membrane has many advantages over current technology: it is a continuous system with no theoretical capacity limit, it requires no consumables, and it requires no hardware for switching beds between absorption and regeneration. Unfortunately, conventional gas separation membranes do not have adequate selectivity for use in the PLSS. However, the required performance could be obtained with a supported liquid membrane (SLM), which consists of a micro porous material filled with a liquid that selectively reacts with CO2 over oxygen (O2). In a current Phase II SBIR project, Reaction Systems has developed a new reactive liquid, which has effectively zero vapor pressure making it an ideal candidate for use in an SLM. The SLM function has been demonstrated with representative pressures of CO2, O2, and water (H2O). In addition to being effective for CO2 control, the SLM also vents moisture to space. Therefore, this project has demonstrated the feasibility of using an SLM to control CO2 in an EVA application.

Wickham, David T.↗

Continued Advancement of Supported Liquid Membranes for Carbon Dioxide Control in Extravehicular Activity Applications

The Development of a new, robust, portable life support system (PLSS) is currently a high NASA priority in order to support longer and safer extravehicular activity (EVA) missions that will be necessary as space travel extends to near-Earth asteroids and eventually Mars. One of the critical PLSS functions is maintaining the carbon dioxide (CO2) concentration in the suit at acceptable levels. The Metal Oxide (MetOx) canister has a finite CO2 adsorption capacity and therefore in order to extend mission times, the unit would have to be larger and heavier, which is undesirable; therefore new CO2 control technologies must be developed. While recent work has centered on the use of alternating sorbent beds that can be regenerated during the EVA, this strategy increases the system complexity and power consumption. A simpler approach is to use a membrane that vents CO2 to space but retains oxygen(O2). A membrane has many advantages over current technology: it is a continuous system with no theoretical capacity limit, it requires no consumables, and it requires no hardware for switching beds between absorption and regeneration. Conventional gas separation membranes do not have adequate selectivity for use in the PLSS, but the required performance could be obtained with a supported liquid membrane (SLM), which consists of a microporous film filled with a liquid that selectively reacts with CO2 over oxygen (O2). In a recently completed Phase II Small Business Innovative Research project, Reaction Systems developed a new reactive liquid that has effectively zero vapor pressure, making it an ideal candidate for use in an SLM. Results obtained with the SLM in a flat sheet configuration with representative pressures of CO2, O2, and water (H2O) have shown that the CO2 permeation rate and CO2/O2 selectivity requirements have been met. In addition, the SLM vents moisture to space very effectively. The SLM has also been prepared and tested in a hollow fiber form, which will be necessary to meet size requirements in the PLSS. In initial tests, the required CO2 permeance values have been obtained, while the current CO2/O2 selectivity values are somewhat lower than needed. However, the performance of the SLM is a strong function of the method used to impregnate the sorbent in the hollow fiber walls and rapid progress is being made in that area.

Wickham, David T.↗

Elucidating the mechanism underlying the augmented capacity of MoO 2 as an anode material in Li-ion batteries

Transition-metal oxide anode materials have been observed to possess an intriguing surplus of capacity beyond the expected values based on conversion reaction. However, the mechanisms behind this phenomenon have remained contentious and elusive. Here, this study focuses on synthesized nanosized molybdenum dioxide and its electrochemical performance as an anode material for Li-ion batteries. Our findings reveal a substantial increase in capacity upon cycling, achieving approximately 1688 mA h g -1 , nearly double the theoretical capacity, after 700 cycles at a 1C rate. To elucidate the mechanisms underlying this augmented capacity, a comprehensive analysis employing in situ and ex situ X-ray diffraction, X-ray absorption spectroscopy, scanning electron microscopy, and transmission electron microscopy was conducted at various stages of the Li-ion cell cycling. Our results indicate that no conversion reaction occurs during the initial discharge phase, with Li 2 O and Mo remaining undetected. Instead, Li 0.98 MoO 2 is generated upon lithiation. Further materials characterization employing electron energy loss spectroscopy and energy-dispersive X-ray spectroscopy on the cycled electrode suggests the potential formation of a metallic Li-rich layer at the interface of the Li-ion intercalated phase subsequent to the formation of Li 0.98 MoO 2 , contributing to the surplus Li storage. Moreover, electrochemical impedance spectroscopy coupled with ex situ SEM and TEM analyses reveals that alterations in particle size and morphology, along with changes in the solid electrolyte interphase (SEI) resistance, are instrumental in the capacity variation observed upon cycling.

25 ENERGY STORAGE↗

Impact of Synthetic Parameters on Structure and Electrochemistry of High-Entropy Layered Oxide LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2

Here, this study explored a high-entropy layered oxide (HELO), LiNi 0.2 Co 0.2 Mn 0.2 Al 0.2 Fe 0.2 O 2 , prepared by coprecipitation followed by heat treatment. Coprecipitation yielded a kinetically favored product, and the subsequent heat treatment under various temperatures and times allowed tuning the material toward more thermodynamically favored structures. Refinement of X-ray powder diffraction (XRD) revealed that after 450 °C treatment, ~12% of the Ni 2+ in the structure was located within the lithium cation layer. After heat treatment at 600, 700, and 800 °C, there was a continued decrease of Ni 2+ in the lithium cation layer to 9.3, 6.3, and 3.7%, respectively. Longer heat treatment times at 800 °C decreased the level to 2.5%. Electrochemical behavior was evaluated by cyclic voltammetry, galvanostatic cycling, rate capability testing, and electrochemical impedance spectroscopy, where increased loaded voltage, functional capacity, rate capability, and decreased impedance were observed for samples treated at higher temperatures with lower cation mixing. X-ray absorption near edge spectroscopy (XANES) data indicated that the redox activity of Ni and Co was dominant in the electrochemistry, while the participation of Mn or Fe was minimal. The level of Ni oxidation state change between charge and discharge related to the heat treatment temperature where the samples with high cation mixing showed lower capacity consistent with some Ni 3+ in the transition metal layer inaccessible for electron transfer. Longer heat treatment times at 800 °C did not continue to provide a benefit in electrochemical function even with some additional reduction in cation mixing.

25 ENERGY STORAGE↗

Capacity Fade of Graphite/NMC811: Influence of Particle Morphology, Electrolyte, and Charge Voltage

LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is an important Li-ion battery cathode material; however, there is a tradeoff between delivered capacity and capacity retention. As the charge potential increases the capacity rises but at the expense of capacity retention. The decrease in capacity retention has been ascribed to several factors including particle cracking, surface reconstruction, transition metal dissolution, and electrolyte reactivity. The present study compares 4.1 and 4.3 V charging limits in commercially relevant graphite/NMC811 pouch cells for single crystal (SC) and polycrystalline (PC) NMC811 with ethylene carbonate (EC)-containing or EC-free electrolytes. The electrochemistry is rationalized through analysis of electrochemical impedance spectroscopy, positive electrode X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, X-ray diffraction, and negative electrode mapping by X-ray fluorescence. Graphite/SC-NMC811 cells show high-capacity retention at 4.1 V but exhibit degradation at 4.3 V charging potentials. The EC-free electrolyte cells led to higher capacity fade, especially when charged to 4.3 V. Cathode dissolution and deposition on the negative electrode from PC-NMC811 cells was higher than for samples from SC-NMC811 cells. This study reveals the impact of material type, charge voltage, and electrolyte composition on the reactions at the positive electrode, their influence on the negative electrode, and evolution with cycle number.

36 MATERIALS SCIENCE↗

Carbon decorated Li 3 V 2 (PO 4 ) 3 for high-rate lithium-ion batteries: Electrochemical performance and charge compensation mechanism

Fast charging and high-power delivering batteries are highly demanded in mobile electronics, electric vehicles and grid energy storage, but there are full of challenges. The star-material Li 3 V 2 (PO 4 ) 3 is demonstrated as a promising high-rate cathode material meeting the above requirements. Herein, we report the carbon decorated Li 3 V 2 (PO 4 ) 3 (LVP/C) cathode prepared via a facile method, which displays a remarkable high-rate capability and long-term cycling performance. Briefly, the prepared LVP/C delivers a high discharge capacity of 122 mAh g -1 (~93% of the theoretical capacity) at a high rate up to 20 C and a superior capacity retention of 87.1% after 1000 cycles. Importantly, by applying a combination of X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering, we clearly elucidate the structural and chemical evolutions of LVP upon various potentials and cycle numbers. Furthermore, we show unambiguous spectroscopic evidences that the evolution of the hybridization strength between V and O in LVP/C as a consequence of lithiation/delithiation is highly reversible both in the bulk and on the surface during the discharge-charge processes even over extended cycles, which should be responsible for the remarkable electrochemical performance of LVP/C. Our present study provides not only an effective synthesis strategy but also deeper insights into the surface and bulk electrochemical reaction mechanism of LVP, which should be beneficial for the further design of high-performance LVP electrode materials.

25 ENERGY STORAGE↗

Compositionally Complex Spinel Oxides as Conversion Anodes for Lithium-Ion Batteries

Four different compositionally complex multicomponent M 3 O 4 spinels containing 5–8 distinct metals were prepared by a rapid combustion synthesis method or solvothermal synthesis. High resolution synchrotron X-ray diffraction patterns show that the materials consist primarily of spinel phases with small amounts of rock salt impurities, and, in several samples, a minor amount of contracted spinel phase. Materials were investigated as conversion anodes in lithium half-cells and delivered significantly higher capacities than two-component MgFe 2 O 4 made by combustion synthesis. X-ray absorption near-edge structure (XANES) was used to estimate the oxidation states of the metals in the pristine, lithiated (discharged) and delithiated (charged) materials to better understand the redox processes in half cells that led to the improvement. Co, Ni, and Zn are reduced to low oxidation states during lithiation (cell discharge) but are only partially oxidized. The presence of a conductive metallic network that forms after lithiation is thought to account for the improved electrochemical characteristics. Interestingly, in most of the samples, iron is not fully reduced during initial lithiation unlike what happens with a set of related high entropy spinel ferrites studied previously. Finally, the improved electrochemical properties of these materials illustrates both the advantages of complexity and the difficulties in predicting their behavior.

25 ENERGY STORAGE↗

All-Solid-State Lithium–Sulfur Batteries Enhanced by Redox Mediators

We report redox mediators (RMs) play a vital role in some liquid electrolyte-based electrochemical energy storage systems. However, the concept of redox mediator in solid-state batteries remains unexplored. Here, we selected a group of RM candidates and investigated their behaviors and roles in all-solid-state lithium-sulfur batteries (ASSLSBs). The soluble-type quinone-based RM (AQT) shows the most favorable redox potential and the best redox reversibility that functions well for lithium sulfide (Li 2 S) oxidation in solid polymer electrolytes. Accordingly, Li 2 S cathodes with AQT RMs present a significantly reduced energy barrier (average oxidation potential of 2.4 V) during initial charging at 0.1 C at 60 °C and the following discharge capacity of 1133 mAh g s -1 . Using operando sulfur K-edge X-ray absorption spectroscopy, we directly tracked the sulfur speciation in ASSLSBs and proved that the solid-polysulfide-solid reaction of Li 2 S cathodes with RMs facilitated Li 2 S oxidation. In contrast, for bare Li 2 S cathodes, the solid-solid Li 2 S-sulfur direct conversion in the first charge cycle results in a high energy barrier for activation (charge to ~4 V) and low sulfur utilization. The Li 2 S@AQT cell demonstrates superior cycling stability (average Coulombic efficiency 98.9% for 150 cycles) and rate capability owing to the effective AQT-enhanced Li-S reaction kinetics. This work reveals the evolution of sulfur species in ASSLSBs and realizes the fast Li-S reaction kinetics by designing an effective sulfur speciation pathway

25 ENERGY STORAGE↗

Continued Advancement of Supported Liquid Membranes for Carbon Dioxide Control in Extravehicular Activity Applications

The development of a new, robust, portable life support system (PLSS) is a high priority for NASA in order to support longer and safer extravehicular activity (EVA) missions. One of the critical PLSS functions is maintaining the carbon dioxide (CO2) concentration in the suit at acceptable levels. Although the Metal Oxide (MetOx) canister has historically performed very well, it has a finite CO2 adsorption capacity. Therefore, the size and weight of the unit would have to be increased to extend EVA times. Consequently, new CO2 control technologies must be developed in order to meet mission objectives without increasing the size of the PLSS. Recent work has centered on sorbents that can be regenerated during the EVA; however, this strategy increases the system complexity and power consumption. A much simpler approach is to employ a membrane that vents CO2 to space and retains oxygen (O2). A membrane has many advantages over current technology: it is a continuous system with no limit on capacity, it requires no consumables, and it does not need any hardware to switch beds between absorption and regeneration. Unfortunately, conventional gas separation membranes do not have the needed selectivity for use in the PLSS. However, the required performance could be obtained with a supported liquid membrane (SLM), which consists of a microporous material filled with a liquid that selectively reacts with CO2 over O2. In a recently completed Phase II SBIR project, Reaction Systems, Inc. achieved the required CO2 permeance and selectivity with an SLM in a flat sheet configuration. This paper describes work to convert the SLM into a more compact form and to scale it up to handle more representative process flow rates.

Wickham, David T.↗

Magnesium Todorokite: Influence of Morphology on Electrochemistry in Lithium, Sodium and Magnesium Based Batteries

Samples of Mg-todorokite with mixed nanosheet & nanowire (referred to as nanosheets for the sake of simplicity) and pure nanowire morphology were prepared to probe the morphological impact on battery relevant electrochemistry. The samples had similar physicochemical properties where the Mg-todorokite nanosheets had a composition of Mg 0.20 MnO 2 with a crystallite size of 9 nm and water content of 0.29 moles of H 2 O per formula unit, while the nanowires had a composition of Mg 0.19 MnO 2 with a crystallite size of 14 nm and water content of 0.28. The electrochemistry of the Mg-todorokite materials was evaluated using cyclic voltammetry, galvanostatic cycling, and rate capability testing. The Mg-todorokite nanosheets showed higher discharge capacity than the nanowires in lithium, sodium and magnesium-based electrolytes. Notably, the nanowire materials exhibited excellent cycling stability compared to the nanosheets in lithium and sodium-based batteries. Finally, x-ray absorption spectroscopy (XAS) of lithiated samples suggests that Mn in the nanosheet containing material was more highly reduced to Mn 3+ after the 1st full discharge explaining the higher initial capacities observed. However, a MnO-like structural distortion was observed after extended cycling in the nanosheet material consistent with its poorer capacity retention.

25 ENERGY STORAGE↗

Elucidating Primary Degradation Mechanisms in High-Cycling-Capacity, Compositionally Tunable High-Entropy Hydrides

The hydrogen sorption properties of single-phase bcc (TiVNb) 100–x Cr x alloys (x = 0–35) are reported. All alloys absorb hydrogen quickly at 25 °C, forming fcc hydrides with storage capacity depending on the Cr content. Here, a thermodynamic destabilization of the fcc hydride is observed with increasing Cr concentration, which agrees well with previous compositional machine learning models for metal hydride thermodynamics. The steric effect or repulsive interactions between Cr–H might be responsible for this behavior. The cycling performances of the TiVNbCr alloy show an initial decrease in capacity, which cannot be explained by a structural change. Pair distribution function analysis of the total X-ray scattering on the first and last cycled hydrides demonstrated an average random fcc structure without lattice distortion at short-range order. If the as-cast alloy contains a very low density of defects, the first hydrogen absorption introduces dislocations and vacancies that cumulate into small vacancy clusters, as revealed by positron annihilation spectroscopy. Finally, the main reason for the capacity drop seems to be due to dislocations formed during cycling, while the presence of vacancy clusters might be related to the lattice relaxation. Having identified the major contribution to the capacity loss, compositional modifications to the TiVNbCr system can now be explored that minimize defect formation and maximize material cycling performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗