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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 523 records · Page 29

Microclusters of Kinked Silicon Nanowires Synthesized by a Recyclable Iodide Process for High-Performance Lithium-Ion Battery Anodes

Silicon shows great promise as a high-capacity anode material for lithium-ion batteries. Nanostructuring silicon minimizes the impact of fracturing during charging and discharging. However, synthesizing nanostructured silicon typically requires complicated procedures with high manufacturing costs. Additionally, these complicated procedures typically have poor secondary particle formation, a requirement to achieve a high tap density. Here, a cost-effective synthesis procedure which generates nearly ideal secondary particle clusters of nanostructured silicon is developed. The cost-effectiveness is a result of the in operando generation of silicon iodide from iodine gas and low-grade silicon microparticle. Decomposition of silicon iodide into crystalline silicon and iodine gas enables recycling of the iodine gas, allowing for near full reutilization of iodine in the following cycles. Additionally, the optimal nanostructures and microstructures of silicon synthesized by the recyclable iodide decomposition reaction enables 83.6% capacity retention over 1000 cycles. The good performance is a result of well-maintained morphology during cycling, enabling reutilization of the solid electrolyte interphase.

25 ENERGY STORAGE↗

A Study of Model-Based Protective Fast-Charging and Associated Degradation in Commercial Smartphone Cells: Insights on Cathode Degradation as a Result of Lithium Depositions on the Anode

The ever expanding mobile consumer electronic market has accelerated the need for safe and efficient fast-charging approaches that improve the overall speed of battery charging without hastened deterioration of the battery performance. Herein, the impact of a resource inexpensive, physics-based, electrochemically optimized fast-charging algorithm (charging time < 2 h) for mobile devices is investigated. A critical difference in the amount and morphology of lithium deposits on the anode for cells fast-charged without an optimized algorithm is observed and found to be the main cause of capacity decay. Furthermore, an in-depth study of the LiCoO 2 cathode regions opposite to pronounced lithium deposits on the anode reveals a “mirroring” phenomenon, i.e., a frozen monoclinic phase, and inactivity to relithiation. In operando hard X-ray absorption spectroscopy reveals that degraded spots on harvested cathodes seem to be activated again and participate in the intercalation process when lithiated at low rates from lithium foil counter electrodes. On the other hand, tests at higher C-rates, closer to the actual fast-charging rate, reveal only negligible oxidation state changes and therefore poor performance.

25 ENERGY STORAGE↗

Modification of the Coordination Environment of Active Sites on MoC for High-Efficiency CH 4 Production

Modulating the coordination environment of active sites on catalyst surfaces is crucial to developing effective catalysts and controlling catalysis, but it is highly challenging. Guided by our first-principles calculations, we experimentally accomplish the modification of the coordination environment of active sites on MoC nanoparticle surfaces by anchoring pyridinic N atom rings of holey graphene on Mo atoms. The rings produce electrostatic forces that enable the tuning of the Mo sites' affinity to reaction intermediates, which passivates Mo hollow sites, activates Mo top sites and reduces the over-adsorption of OH on the Mo active sites, as predicted by the calculations. The atomic-level modification is well confirmed by atomic-resolution imaging, high-resolution electron tomography, synchrotron soft X-ray spectroscopy and operando electrochemical infrared spectroscopy. Consequently, the Faradaic efficiency for CO 2 reduction to CH 4 is enhanced from 16% to 89%, a record high efficiency so far, in aqueous electrolyte. Meantime, it also exhibits a negligible activity loss over 50 h.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The Importance of Surface Oxygen for Lithiation and Morphology Evolution during Calcination of High-Nickel NMC Cathodes

Nanoscale morphology has a direct impact on the performance of materials for electrochemical energy storage. Despite this importance, little is known about the evolution of primary particle morphology nor its effect on chemical pathways during synthesis. In this work, operando characterization is combined with atomic-scale and continuum simulations to clarify the relationship between morphology of cathode primary particles and their lithiation during calcination of LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC-811). This combined approach reveals a key role for surface oxygen adsorption in facilitating the lithiation reaction by promoting metal diffusion and oxidation, and simultaneously providing surface sites for lithium insertion. Furthermore, oxygen surface termination is shown to increase the activation energy for sintering, leading to smaller primary particle sizes at intermediate temperatures. Smaller particles provide both shorter diffusion lengths for lithium incorporation and increased surface site density for lithium insertion. These insights provide a foundation for more tailored syntheses of cathode materials with optimized performance characteristics.

25 ENERGY STORAGE↗

Structural, Dynamic, and Chemical Complexities in Zinc Anode of an Operating Aqueous Zn-Ion Battery

Aqueous Zn-ion battery is a promising technology for electrochemical energy storage. The formation of Zn dendrites, however, can jeopardize the cell cycle life and thus, hinders the industrial adoption of this technology. A fundamental understanding of the kinetic mechanisms is crucial for improving the Zn-ion battery. Here, in situ and operando X-ray microscopy methods are utilized to visualize the Zn plating and stripping behaviors under different electrochemical conditions. It is demonstrated that the substrate curvature, local morphology, electrochemical protocols, and the surface chemistry can collectively affect the Zn plating behavior. Furthermore, these results provide new insights for developing the next-generation dendrite-free and long-span aqueous Zn-ion battery.

25 ENERGY STORAGE↗

Insight into the Fast-Rechargeability of a Novel Mo 1.5 W 1.5 Nb 14 O 44 Anode Material for High-Performance Lithium-Ion Batteries

Wadsley–Roth phased niobates are promising anode materials for lithium-ion batteries, while their inherently low electrical conductivity still limits their rate-capability. Herein, a novel doped Mo 1.5 W 1.5 Nb 14 O 44 (MWNO) material is facilely prepared via an ionothermal-synthesis-assisted doping strategy. The detailed crystal structure of MWNO is characterized by neutron powder diffraction and aberration corrected scanning transmission electron microscope, unveiling the full occupation of Mo 6+ -dopant at the t1 tetrahedral site. In half-cells, MWNO exhibits enhanced fast-rechargeability. In this work, the origin of the improved performance is investigated by ultraviolet–visible diffuse reflectance spectroscopy, density functional theory (DFT) computation, and electrochemical impedance spectroscopy, revealing that bandgap narrowing improves the electrical conductivity of MWNO. Furthermore, operando X-ray diffraction elucidates that MWNO exhibits a typical solid-solution phase conversion-based lithium-ion insertion/extraction mechanism with reversible structural evolution during the electrochemical reaction. The boosted lithium-ion diffusivity of MWNO, due to the Mo 6+ /W 6+ doping effect, is confirmed by a galvanostatic intermittent titration technique and DFT. With the simultaneously enhanced electrical conductivity and lithium-ion diffusivity, MWNO successfully demonstrates its fast-rechargeability and practicality in the LiNi 0.5 Mn 1.5 O 4 -coupled full-cells. Therefore, this work illustrates the potential of ionothermal synthesis in energy storage materials and provides a mechanistic understanding of the doping effect on improving material's electrochemical performance.

25 ENERGY STORAGE↗

How to GIWAXS: Grazing Incidence Wide Angle X‐Ray Scattering Applied to Metal Halide Perovskite Thin Films

Abstract The frequency of reports utilizing synchrotron‐based grazing incident wide angle X‐ray scattering (GIWAXS) to study metal halide perovskite thin films has exploded recently, as this technique has proven invaluable for understanding several structure‐property relationships that fundamentally limit optoelectronic performance. The GIWAXS geometry and temporal resolution are also inherently compatible with in situ and operando setups (including ISOS protocols), and a relatively large halide perovskite research community has deployed GIWAXS to unravel important kinetic and dynamic features in these materials. Considering its rising popularity, the aim here is to accelerate the required learning curve for new experimentalists by clearly detailing the underlying analytical concepts which can be leveraged to maximize GIWAXS studies of polycrystalline thin films and devices. Motivated by the vast range of measurement conditions offered, together with the wide variety of compositions and structural motifs available (i.e., from single‐crystal and polycrystalline systems, to quantum dots and layered superlatices), a comprehensive framework for conducting effective GIWAXS experiments is outlined for different purposes. It is anticipated that providing a clear perspective for this topic will help elevate the quality of future GIWAXS studies—which have become routine—and provide the impetus required to develop novel GIWAXS approaches to resolve unsettled scientific questions.

36 MATERIALS SCIENCE↗

Revealing the Sodium Storage Mechanisms in Hard Carbon Pores

Abstract Hard carbon (HC) is the most promising anode for the commercialization of sodium‐ion batteries (NIBs); however, a general mechanism for sodium storage in HC remains unclear, obstructing the development of highly efficient anodes for NIBs. To elucidate the mechanism of sodium storage in the pores, operando synchrotron small‐angle X‐ray scattering, wide‐angle X‐ray scattering, X‐ray absorption near edge structure, Raman spectroscopy, and galvanostatic measurements are combined. The multimodal approach provides mechanistic insights into the sodium pore‐filling process for different HC microstructures including the pore sizes that are preferentially filled, the extent to which different pore sizes are filled, and how the defect concentration influences pore filling. It is observed that sodium in the larger pores has an increased pseudo‐metallic sodium character consistent with larger sodium clusters. Furthermore, it is shown that the HCs prepared at higher pyrolysis temperatures have a larger capacity from sodium stored in the pores and that sodium intercalation between graphene layers occurs simultaneously with the pore filling in the plateau region. Opportunities are outlined to improve the performance of HC anodes by fully utilizing the pores for sodium storage, helping to pave the way for the commercialization of sodium ion batteries.

Kitsu Iglesias, Luis↗

Synergistic Co-Ir/Ru Composite Electrocatalysts Impart Efficient and Durable Oxygen Evolution Catalysis in Acid

Exploring highly active and robust catalysts, which have low precious metal content, to boost the kinetically sluggish oxygen evolution reaction (OER) is a key concern for hydrogen production via proton exchange membrane water electrolysis (PEMWE). Here, in this work, rational engineering of the morphology and the local geometric ligand environment of Ir and Ru catalysts are presented by using defect-rich, lanthanum- and lithium-doped Co 3 O 4 nanofiber (LLCF) as substrate that promotes the electrocatalytic OER. Two catalysts, IrCoOx@LLCF and RuCoOx@LLCF, achieve mass activities of 1013.5 A g Ir –1 and 1911.4 A g Ru –1 in 0.1 M HClO 4 at 300 mV overpotential, respectively, which are 26 and 50 times higher than that of commercial IrO 2 and RuO 2 . Operando X-ray absorption spectroscopy unveils the reversible structure of IrCoOx during the OER and the suppression of over-oxidation of Co and Ir, giving rise to high stability. Density functional theory calculations reveal that the local geometric ligand engineering optimizes the binding of oxygenated species to the active sites, resulting in strongly enhanced catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strategically Modified Ligand Incorporating Mixed Phosphonate and Carboxylate Groups to Enhance Performance in All-Iron Redox Flow Batteries

Iron redox flow batteries (Fe-RFBs) hold significant promise for achieving cost-effectiveness and utilizing abundant materials for stationary energy storage applications. Here, a design of a novel Fe complex utilizing a nitrogenous phosphonate/carboxylate mixed ligand, N,N-Bis(phosphonomethyl)glycine (BMPG), is presented to achieve high performance Fe anolyte. Compared to its all-phosphonate form, nitrilotri(methylphosphonic acid) (NTMPA), the new complex Fe(BPMG) 2 demonstrates a negatively shifted redox potential, resulting in ≈0.07 V (≈10%) increase in battery output voltage. Full battery testing paired with ferrocyanide catholyte demonstrates stable cycling (capacity degradation <0.0001%/cycle) over 730 consecutive charge/discharge cycles with Coulombic Efficiency of 100% at a current density of 20 mA cm -2 under near neutral pH (≈8). Of particular interest, density functional theory (DFT) studies and operando Raman measurements provide strong evidence supporting a molecular structure in BPMG, which reveals the mixed phosphonate/carboxylate groups in BPMG maintain the octahedral coordination of the Fe ion center with phosphonates exclusively, while leaving the carboxylate unbound for both Fe(II) and Fe(III) complexes. This structural similarity between BPMG-based Fe(II) and Fe(III) complexes effectively mitigates the slow redox reaction kinetics observed in Fe(NTMPA) 2 anolyte, where significant ligand reorientation occurs between Fe(II) and Fe(III) complexes.

25 ENERGY STORAGE↗

Probing Electrode Transformation under Dynamic Operation for Alkaline Water Electrolysis

Alkaline water electrolyzers (AWEs) play a pivotal role in the realm of large-scale hydrogen production. However, AWEs face significant challenges in electrode degradation particularly under dynamic operating conditions, induced by reverse current phenomenon during frequent startup/shutdown. Herein, this study aims to rationalize the degradation mechanisms of AWEs under these conditions. A three-electrode membrane electrode assembly (MEA) setup is first utilized to decouple polarization behaviors of anode and cathode in AWEs. Following a proposed accelerated stress testing protocol, the setup allows for tracking individual electrode performance transformations during frequent reverse current operation. Integrating operando cell studies with in situ and post-mortem characterizations, it is showed that continuous formation of highly active species, nickel (oxy)hydroxides, improves the anode performance for oxygen evolution reaction. On the contrary, irreversible oxidation of nickel to β-nickel hydroxide results in a severe degradation of cathode, leading to material dissolution, poor electrical conductivity and loss of catalytic activity for hydrogen evolution reaction. These results provide insights in nickel-based electrode transformation mechanisms for alkaline water electrolysis and indicate that cathode with higher redox reversibility can potentially improve durability of AWEs under dynamic conditions.

08 HYDROGEN↗

In Situ Electrochemistry of Buried Interfaces in Metal Halide Perovskites: Probing Energy Bands, Halide Redox Activity, and Kinetics

Control over charge injection and extraction processes across buried interfaces is fundamental for all (opto)electronic multilayer device platforms, necessitating detailed understanding of local structural and chemical differences that promote defect formation, distort energetic band-edge alignments, and alter charge transport processes. Herein, the implementation of a low-cost electroanalytical methodologies’ tool suite is described to quantitatively characterize buried interfaces and redox reactions in printable, mixed electrical–ionic, and redox-active metal halide perovskites and a prototypical hole-transporting nickel oxide (NiO x ) thin film. The objective is to demonstrate the power of electrochemical methodologies to improve the nanoscale understanding of complex interfaces within optoelectronic devices by providing case studies on how to: i) differentiate between electronic and chemical properties in NiO x contacts; ii) measure changes in reversibility of halide redox reactions via NiO x surface states; iii) assess energy alignment and charge transport across (modified) buried interfaces; and iv) quantify defects at buried interfaces that change with modifiers and differences in perovskite processing, including increasing defect concentrations when films are slot-die-coated versus spin-cast. The collective approach addresses major challenges in understanding the precise energy landscape and interface reactivity under relevant electric fields that mimic operando conditions (away from equilibrium) and across length scales in thin film device formats.

(spectro)electrochemistry↗

Thermal Dynamics and Lithium Plating Detection in High‐Power Li‐Ion Batteries for eVTOL Applications

The rapid electrification of aerial transportation is driving the need for high‐performance Li‐ion batteries that can operate reliably under stringent thermal and safety constraints. The unique mission profile of electric Vertical Take‐off and Landing (eVTOL) aircraft necessitates a focused investigation into the thermal behavior and safety characteristics of these batteries. Here, in this study, operando isothermal microcalorimetry is employed to examine the thermal evolution of Li‐ion batteries under cycling conditions representative of eVTOL operations. These findings reveal that high‐power discharge events—such as those during take‐off and landing—shift the thermal response toward exothermic behavior, in contrast to the typically endothermic response expected under near‐equilibrium cycling conditions. Additionally, the results suggest that advanced electrolyte formulations may help suppress excess heat generation, thereby improving battery safety. Notably, the calorimetric results exhibit a distinct thermal signature associated with lithium plating, offering a potential diagnostic for detecting Li plating during eVTOL operation. Overall, this study demonstrates the utility of isothermal microcalorimetry as a valuable tool for assessing thermal risks in Li‐ion batteries for eVTOL applications, and highlights the importance of targeted design strategies to mitigate safety hazards during high‐power demand scenarios.

Li plating↗

Neutron Scattering in Sodium-Ion Battery Research: Progress and Prospects

Sodium-ion batteries have attracted renewed interest in recent years and are widely studied as a complementary power source to Li-ion batteries for large-scale stationary energy storage and small electric vehicles. Compared with Li-ion batteries, Na-ion batteries offer several advantages, including elemental abundance, lower cost, improved safety, and better low-temperature performance. An in-depth understanding of Na-ion batteries across multiple length and time scales has further accelerated the rapid development of this technology. Among the various advanced characterization techniques used to study Na-ion batteries, neutron scattering has gained significant traction in recent years. It has become a powerful and versatile tool for probing structure, morphology, and sodium-ion dynamics over a wide range of length and time scales. In this article, we will briefly review the development of neutron scattering technology and highlight recent advances in applying neutron-based techniques—including neutron diffraction, total scattering, small-angle scattering, quasi-elastic/inelastic scattering, and neutron imaging—to Na-ion battery materials. We also provide perspectives on future technique developments, particularly in the realm of in situ and operando neutron scattering characterization, and discuss how these approaches could further enhance our understanding of Na-ion battery systems.

Liu, Jue [ORNL] (ORCID:000000024453910X)↗

Unveiling the High‐Voltage Reactivity and Gas Evolution With Aluminum‐Based Chloride and Oxychloride Catholytes in Solid‐State Sodium Batteries

All-solid-state sodium batteries (ASSBs) employing halide solid electrolytes (SEs) offer a cost-effective and energy-dense alternative to conventional liquid electrolyte systems. However, their high voltage (>4 V vs. Na/Na + ) performance remains limited by interfacial instability between the cathode active material (CAM) and the SE. We present here the electrochemical and interfacial behaviors of crystalline NaAlCl 4 and amorphous sodium–aluminum–oxychloride (NACO) SEs when combined with NaNi 0.5 Mn 0.5 O 2 cathode. While oxygen incorporation in NACO enhances ionic conductivity by nearly three orders of magnitude relative to NaAlCl 4 , it does not improve high-voltage cycling stability. Cells employing NACO exhibit accelerated capacity fade, increased cell impedance growth, and intrinsic oxygen evolution above 4.5 V vs. Na 3 Sn, as revealed by operando electrochemical mass spectrometry. In contrast, the NaAlCl 4 -based cells show no detectable gas release, underscoring their superior high-voltage stability and safety. Time-of-flight secondary-ion mass spectrometry confirms the formation of Al─O and Ni/Mn─Cl species, respectively, in the SE and CAM, indicating redox-driven anion exchange that contributes to kinetic hindrance of high-voltage phase transitions. The findings establish that while oxygen incorporation enhances ionic transport, it can compromise interfacial stability, suggesting pure chloride SEs may offer a more robust and intrinsically safer pathway for developing high-energy ASSBs.

25 ENERGY STORAGE↗

Hypochlorite Redox Chemistry Enables High-Voltage and High-Power Saltwater Batteries

Saltwater batteries (SWBs) are promising alternatives to lithium-ion batteries for large-scale stationary energy storage. However, the performance of conventional oxygen redox-based saltwater battery systems is often constrained by sluggish oxygen evolution and reduction reactions (OER/ORR) at the cathode, leading to low voltage efficiency and limited power density. Here, OER and ORR are replaced by hypochlorite-based redox reactions through the introduction of sodium hypochlorite into saltwater. Operando pH and dissolved oxygen measurements confirm that OER and ORR are minimized and that hypochlorite redox reactions dominate the cathode behavior. Owing to the higher operating potential and faster reaction kinetics, the hypochlorite-redox-based SWBs delivers a higher discharge voltage of 3.3 V and reduced charge-discharge voltage polarization to 0.66 V. Further improvement is achieved by adjusting the saltwater pH to near-neutral conditions, increasing the discharge voltage to 3.5 V and more than doubling the peak power. The hypochlorite redox environment also exhibits chemical stability with key cell components, including the solid electrolyte and cathode current collectors. Operation of series-connected cells and cells employing hard carbon anodes demonstrates scalability and compatibility with alternative anode materials. These results provide a strong foundation for next-generation SWBs targeting large-scale stationary energy storage applications.

Go, Wooseok [ORNL]↗

Hybrid Ionomer-Free Porous Transport Electrodes With Catalyst Coated Membranes for Enhanced Water Electrolysis

To promote industrial uptake of clean hydrogen production technologies such as polymer electrolyte membrane (PEM) water electrolyzers, advancements in catalyst layer (CL) morphology are required. We demonstrate how improved electrochemical performance can be achieved when using an ionomer free porous transport electrode (PTE) coupled with a traditional catalyst coated membrane (CCM) assembly in PEM water electrolyzers. Notably, we reveal that the superior performance achieved when utilizing a hybrid PTE and CCM assembly is due to enhanced ohmic performance caused by optimal contact with both the porous transport layer (PTL) and PEM interfaces. Using operando neutron radiography, we demonstrate that configurations utilizing a CCM resulted in more rapid water replenishment to reaction sites, indicating enhanced membrane hydration beneficial for performance. This enhanced membrane hydration coupled with improved contact area at the PEM-catalyst layer (CL) and PTL-CL interfaces was revealed through the reduced ohmic overpotentials of the hybrid PTE-CCM design, which achieved the lowest ohmic overpotential of 431 mV at 2000 mA cm−2. While the average in-plane water distributions are generally similar between cell configurations, we reveal that utilizing a PTE configuration promotes a more homogenous water distribution near the CL-membrane interface due to enhanced catalyst utilization.

Seip, Tess [ORNL] (ORCID:0000000232740594)↗