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DOE OSTI2025

Ligand‐Directed Actinide Oxo‐Bond Manipulation in Actinyl Thiacalix[4]arene Complexes

Understanding the chemistry of the inert actinide oxo bond in actinyl ions AnO2 2+ is important for controlling actinide behavior in the environment, during separations, and in nuclear waste (An=U, Np, Pu). The thioether calixarene TC4A (4-tert-butyltetrathiacalix[4]arene) binds equatorially to the actinyl cation forming a conical pocket that differentiates the two trans-oxo groups. The 'ate' complexes, [A]2[UO2(TC4A)] (A=[Li(DME)2], HNEt3) and [HNEt3]2[AnO2(TC4A)] (An=U, Np, Pu), enable selective oxo chemistry. Silylation of the UVI oxo groups by bis(trimethylsilyl)pyrazine occurs first at only the unencapsulated exo oxo and only one silylation is needed to enable migration of the endo oxo out of the cone, whereupon a second silylation affords the stable UIV cis-bis(siloxide) [A]2[U(OSiMe3)2(TC4A)]. Calculations confirm that only one silylation event is needed to initiate oxo rearrangement, and that the putative cis dioxo isomer of [UO2(TC4A)]2- would be stable if it could be accessed synthetically, at only 23 kcal.mol-1 in energy above the classical trans dioxo. Calculations for the transuranic cis[AnO2(TC4A)]2- (An=Np, Pu) are at higher energies, 30-35 kcal.mol-1, retaining the U complexes as the more obvious target for a cis-dioxo actinyl ion. The aryloxide (OAr) groups of the macrocycle are essential in stabilizing this as-yet unseen uranyl geometry as further bonding in the TC4A U-OAr groups stabilizes the U=O 'yl' bonds, explaining the stability of the putative cis[UO2(TC4A)]2- in this ligand framework.

Pyrch, Mikaela M↗

DOE OSTI2025

Lithium‐Containing Hybrid SEI Layer Enabling High Mass Loading and Anode‐Less Sodium Metal Batteries

The continuous rupturing and rebuilding of unstable solid electrolyte interphase (SEI) layer during cycling would block Na + diffusion and induce Na dendrite formation, ultimately limiting the practical application of high-energy-density sodium metal batteries. Herein, a hybrid SEI layer containing Li-species is dexterously constructed on the surface of sodium metal anode. Li-containing inorganic components (Li 3 N, LiF, and Li 2 CO 3 ) are introduced to stabilize the Na/electrolyte interface and enhance the mechanical and diffusion kinetic properties of the SEI layer, which can reduce the side reactions and gas generation, regulate Na + flux during cycling and promote rapid Na + migration for uniform dendrite-free Na deposition. As a result, the constructed Na symmetric cells achieve low overpotential and long cycle life of 5900, 1800, and 500 h at current densities of 3, 10, and 30 mA cm −2 , respectively. Furthermore, the full cells paired with the Na₃V₂(PO₄)₃ cathode demonstrate high specific capacity and excellent cycle stability, even at an ultra-high cathode loading of 39.3 mg cm −2 and a low N/P ratio (negative/positive electrode capacity ratio of 1.21).

Diffusion kinetic↗

DOE OSTI2025

Flux Synthesis of Lattice‐Engineered Rutile Solid Solutions for Acidic Oxygen Evolution

Developing efficient and stable electrocatalysts for the acidic oxygen evolution reaction (OER) is vital for advancing proton exchange membrane water electrolysis (PEMWE) technologies. Here, in this study, we report a flux synthesis of nitrogen-doped Ti–Ru rutile-type solid-solution oxides (M-TiRu 4 ) using molten NaNO 3 as the flux medium. The flux medium promotes the low-temperature conversion of TiN to rutile TiO 2 , while in situ-formed RuO 2 nanoparticles facilitate lattice templating and couple with interfacial ion migration, enabling the formation of homogeneous solid solutions with abundant lattice heterogeneity. Simultaneously, nitrogen atoms are stably incorporated into the lattice of solid solutions, inducing bandgap narrowing, which enhances electronic conductivity. The developed M-TiRu 4 catalyst exhibits exceptional acidic OER performance, delivering a low overpotential of 194 mV at 10 mA cm −2 , superior durability over 600 h, and a Ru mass activity 7.8 times that of commercial RuO 2 . At the device level, M-TiRu 4 enables PEMWE operation at 1.64 V @ 2 A cm −2 and maintains stable performance at 500 mA cm −2 for 200 h with a minimal degradation rate of 20 µV h −1 . This work demonstrates a robust approach for designing high-performance, durable acidic OER catalysts via synergistic lattice and electronic structure engineering, paving the way for next-generation water-splitting technologies.

Wang, Fan [Univ. of Tennessee, Knoxville, TN (Unit↗

DOE OSTI2026

Operational stability of mixed Sn–Pb perovskite solar cells: Mechanisms, mitigation strategies, and perspectives

Mixed Sn–Pb perovskites provide the 1.2–1.3 eV narrow-bandgap absorber needed for high efficiency of all perovskite tandems, but their deployment is limited by operational instability under light. This review synthesizes mechanistic origins and recent mitigation strategies for mixed Sn–Pb perovskite solar cells. The oxidation of Sn 2+ to Sn 4+ , often driven by iodine formation under light and bias, is the primary failure pathway; it creates Sn vacancies, self-doping, and nonradiative loss. Surface/grain-boundary defects, halide migration, reactive oxygen species, and interfacial redox at charge-transport layers, along with hole accumulation from poor band alignment, further accelerate Sn–Pb perovskite degradation. Here we survey recent stability advances across additive chemistry, surface and grain-boundary passivation, buried-interface redesign with modified or alternative hole transport layers, and solvent systems that preserve Sn 2+ and correct Sn–Pb speciation for scalable coating. Together, these recent advances have enabled devices to retain 80%–90% output for hundreds to over a thousand hours. Lastly, we provide our perspectives on further improving the operational stability of Sn–Pb perovskite and solar cells.

14 SOLAR ENERGY↗

DOE OSTI2023

Transforming layered 2D mats into multiphasic 3D nanofiber scaffolds with tailored gradient features for tissue regeneration

Abstract Multiphasic scaffolds with tailored gradient features hold significant promise for tissue regeneration applications. Herein, this work reports the transformation of two‐dimensional (2D) layered fiber mats into three‐dimensional (3D) multiphasic scaffolds using a ‘solids‐of‐revolution’ inspired gas‐foaming expansion technology. These scaffolds feature precise control over fiber alignment, pore size, and regional structure. Manipulating nanofiber mat layers and Pluronic F127 concentrations allows further customization of pore size and fiber alignment within different scaffold regions. The cellular response to multiphasic scaffolds demonstrates that the number of cells migrated and proliferated onto the scaffolds is mainly dependent on the pore size rather than fiber alignment. In vivo subcutaneous implantation of multiphasic scaffolds to rats reveals substantial cell infiltration, neo tissue formation, collagen deposition, and new vessel formation within scaffolds, greatly surpassing the capabilities of traditional nanofiber mats. Histological examination indicates the importance of optimizing pore size and fiber alignment for the promotion of cell infiltration and tissue regeneration. Overall, these scaffolds have potential applications in tissue modeling, studying tissue‐tissue interactions, interface tissue engineering, and high‐throughput screening for optimized tissue regeneration.

Shahriar, S. M. Shatil↗

DOE OSTI2024

LncRNA ZFAS1 promotes invasion of medullary thyroid carcinoma by enhancing EPAS1 expression via miR‐214‐3p/UCHL1 axis

Abstract lncRNA ZFAS1 was identified to facilitate thyroid cancer, but its role in medullary thyroid carcinoma (MTC) remains unknown. This study aimed to unravel the potential function of this lncRNA in MTC by investigating the involvement of the lncRNA ZFAS1 in a ceRNA network that regulates MTC invasion. Proliferation, invasion, and migration of cells were evaluated using EdU staining and Transwell assays. Immunoprecipitation (IP) assays, dual‐fluorescence reporter, and RNA IP assays were employed to examine the binding interaction among genes. Nude mice were used to explore the role of lncRNA ZFAS1 in MTC in vivo. ZFAS1 and EPAS1 were upregulated in MTC. Silencing ZFAS1 inhibited MTC cell proliferation and invasion under hypoxic conditions, which reduced EPAS1 protein levels. UCHL1 knockdown increased EPAS1 ubiquitination. ZFAS1 positively regulated UCHL1 expression by binding to miR‐214‐3p. Finally, silencing ZFAS1 significantly repressed tumor formation and metastasis in MTC. LncRNA ZFAS1 promotes invasion of MTC by upregulating EPAS1 expression via the miR‐214‐3p/UCHL1 axis.

Chen, Wenjing↗

DOE OSTI2026

Distinct Melt Infusion Architectures of Antiperovskite Solid Electrolytes

Antiperovskite solid electrolytes are an emerging class of lithium‐ion conductors distinguished by their unusually low melting points, enabling scalable, low‐temperature processing routes not accessible to most solid electrolytes. In this work, we synthesize phase‐pure chloride (Cl), bromide (Br), and mixed halide (ClBr) variants of antiperovskites and investigate their ionic conductivities in both powder and hot‐pressed forms. Hot pressing significantly enhances conductivity across all compositions, while energy‐dispersive X‐ray spectroscopy (EDS) of the mixed halide system reveals halide surface migration during densification. We further investigate the melt‐infiltration behavior of these electrolytes into substrates relevant to solid‐state battery architectures, including Al and Cu current collectors, conventional NMC and LFP cathodes, and a foamed NMC cathode with a highly porous architecture. The foamed cathode enables deep and uniform electrolyte penetration, highlighting the role of electrode architecture in facilitating melt infiltration. Across all substrates, electrolyte halide chemistry strongly influences wetting behavior, penetration depth, and resulting microstructural morphology. Together, these results establish clear processing–structure relationships for melt‐infiltrated antiperovskite solid electrolytes and demonstrate how electrolyte chemistry and electrode architecture govern interfacial morphology during integration, providing practical guidelines for processing and structural design in solid‐state battery systems.

antiperovskite↗

DOE OSTI2020

Photoredox Organic Synthesis Employing Heterogeneous Photocatalysts with Emphasis on Halide Perovskite

Abstract Lately, heterogeneous semiconductor materials have been explored as an emerging type of efficient photocatalyst for photoredox organic synthesis. Among these semiconductors, lead halide perovskite materials demonstrate unique properties towards excellent charge separation and charge transfer, extremely long charge carrier migration, high efficiency in visible light absorption, and long excited states lifetimes, etc., as proved in ground‐breaking solar cell applications, garnering necessary merits for an efficient catalytic system for photoredox organic reactions. Here, the latest progress in heterogeneous semiconductor materials towards this endeavor is examined, with particular emphasis on lead halide perovskite nanocrystals (NCs) in photocatalytic organic synthesis.

Lin, Yixiong↗

DOE OSTI2020

Solution-Based, Anion-Doping of Li 4 Ti 5 O 12 Nanoflowers for Lithium-Ion Battery Applications

Solution–based, anionic doping represents a convenient strategy with which to improve upon the conductivity of candidate anode materials such as Li 4 Ti 5 O 12 (LTO). As such, novel synthetic hydrothermally–inspired protocols have primarily been devised herein, aimed at the large–scale production of unique halogen–doped, micron–scale, three–dimensional, hierarchical LTO flower–like motifs. Although fluorine (F) doping has been explored, the use of chlorine (Cl) dopants is the primary focus here. Several experimental variables, such as dopant amount, lithium hydroxide concentration, and titanium butoxide purity, were probed and perfected. Furthermore, the Cl doping process did not damage the intrinsic LTO morphology. The analysis, based on interpreting a compilation of SEM, XRD, XPS, and TEM–EDS results, was used to determine an optimized dopant concentration of Cl. Electrochemical tests demonstrated an increased capacity via cycling of 12 % for a Cl–doped sample as compared with pristine LTO. Moreover, the Cl–doped LTO sample described in this study exhibited the highest discharge capacity yet reported at an observed rate of 2C for this material at 143mAh g –1 . Overall, these data suggest that the Cl dopant likely enhances not only the ion transport capabilities, but also the overall electrical conductivity of our as–prepared structures. Furthermore, to help explain these favorable findings, theoretical DFT calculations were used to postulate that the electronic conductivity and Li diffusion were likely improved by the presence of increased Ti 3+ ion concentration coupled with widening of the Li migration channel.

25 ENERGY STORAGE↗

DOE OSTI2021

Accessing Lanthanide-to-Lanthanide Energy Transfer in a Family of Site-Resolved [Ln III Ln III '] Heterodimetallic Complexes

The ligand H 3 L (6-[3-oxo-3-(2-hydroxyphenyl)propionyl]pyridine-2-carboxylic acid), which exhibits two different coordination pockets, has been exploited to engender and study energy transfer (ET) in two dinuclear [Ln III Ln III '] analogues of interest, [EuYb] and [NdYb]. Their structural and physical properties have been compared with newly synthesised analogues featuring no possible ET ([EuLu], [NdLu], and [GdYb]) and with the corresponding homometallic [EuEu] and [NdNd] analogues, which have been previously reported. Photophysical data suggest that ET between Eu III and Yb III does not occur to a significant extent, whereas emission from Yb III originates from sensitisation of the ligand. In contrast, energy migration seems to be occurring between the two Nd III centres in [NdNd], as well as in [NdYb], in which Yb III luminescence is thus, in part, sensitised by ET from Nd. This study shows the versatility of this molecular platform to further the investigation of lanthanide-to-lanthanide ET phenomena in defined molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Oxidative Dehydrogenation of N ‐Heteroaromatic Alkyl Alcohols and Amines Facilitated by Dearomative Tautomerization

The oxidation of alcohols, amines, and halides is a fundamental transformation in organic chemistry with significant applications in the synthesis of fine chemicals, pharmaceuticals, and natural products. Here we show that a broad variety of N-heteroarenes bearing hydroxymethyl, aminomethyl, or halomethyl groups are oxidatively dehydrogenated to their respective aldehydes by simply heating them in acidic or basic aqueous solution under ambient atmosphere. The quantitative oxidation of 9-acridinemethanol to 9-acridinecarboxaldehyde serves as an illustrative example, proceeding to completion within 3 hours in refluxing 5% aqueous acetic acid or even household vinegar. Quinoline derivatives may be similarly oxidized but require higher temperatures and longer reaction times, while indole derivatives are oxidized under basic conditions. Based on comprehensive regioselectivity screens, internal kinetic isotope competition, and density functional theory (DFT) calculations, we propose a mechanism in which migration of a methylene hydrogen to the pyridinic nitrogen by acid-catalyzed dearomative tautomerization yields an unstable enol or enamine intermediate that then irreversibly loses two hydrogen atoms to atmospheric oxygen. In addition to the simplicity and environmentally benign nature of our method, we observe no indication of any over-oxidation to carboxylic acids. Finally, we demonstrate the synthetic utility of this reaction through two different one-pot formylations of acridine.

Chemistry↗

DOE OSTI2020

Experiences in porting mini-applications to OpenACC and OpenMP on heterogeneous systems

This article studies mini-applications—Minisweep, GenASiS , GPP, and FF—that use computational methods commonly encountered in HPC. We have ported these applications to develop OpenACC and OpenMP versions, and evaluated their performance on Titan (Cray XK7 with K20x GPUs), Cori (Cray XC40 with Intel KNL), Summit (IBM AC922 with Volta GPUs), and Cori-GPU (Cray CS-Storm 500NX with Intel Skylake and Volta GPUs). Our goals are for these new ports to be useful to both application and compiler developers, to document and describe the lessons learned and the methodology to create optimized OpenMP and OpenACC versions, and to provide a description of possible migration paths between the two specifications. Cases where specific directives or code patterns result in improved performance for a given architecture are highlighted. Here, we also include discussions of the functionality and maturity of the latest compilers available on the above platforms with respect to OpenACC or OpenMP implementations.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2020

Recent Progress in Engineering Metal Halide Perovskites for Efficient Visible‐Light‐Driven Photocatalysis

Abstract Artificial photosynthesis has attracted increasing attention due to recent environmental and energy concerns. Metal halide perovskites (MHPs) demonstrating excellent optoelectronic properties have currently emerged as novel and efficient photocatalytic materials. Herein, the structural features of MHPs that are responsible for the photoinduced charge separation and charge migration properties are briefly introduced, and then important and necessary photophysical and photochemical aspects of MHPs related to photoredox catalysis are summarized. Subsequently, the applications of MHPs for solar energy harvesting and photocatalytic conversion, including H 2 evolution, CO 2 reduction, degradation of organic pollutants, and photoredox organic synthesis, are extensively demonstrated, with a focus on strategies for improving the performance (e.g., selectivity, activity, stability, recyclability, and environmental compatibility) of these MHP‐based photocatalytic systems. To conclude, existing challenges and prospects on the future development of MHP‐based materials towards photoredox catalysis applications are detailed.

Han, Chuang↗

DOE OSTI2021

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li 7‐3 x Ga x La 3 Zr 2 O 12 Garnet‐Type Electrolytes

Abstract One of the most promising electrolytes for all‐solid‐state lithium batteries is Li 7 La 3 Zr 2 O 12 . Previously, their thermodynamic stability, Li‐ion conductivity, and structural features induced by Ga‐doping have not been empirically determined or correlated. Here, their interplay was examined for Li 7−3 x Ga x La 3 Zr 2 O 12 with target x Ga=0, 0.25, 0.50, 0.75, and 1.00 atoms per formula unit (apfu). Formation enthalpies, obtained with calorimetry and found to be exothermic at all compositions, linearly decreased in stability with increased x Ga. At dilute x Ga substitution, the formation enthalpy curve shifted stepwise endothermically, and the conductivity increased to a maximum, coinciding with 0.529 Ga apfu. This correlated with percolation threshold analysis (0.558 Ga apfu). Further substitution (0.787 Ga apfu) produced a large decrease in the stability and conductivity due to a large increase in point defects and blocked Li‐migration pathways. At x Ga=1.140 apfu, a small exothermic shift was related to defect cluster organization extending the Li hopping distance and decreased Li‐ion conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Investigation of Drift Effects in UEDGE Simulations of NSTX-U Edge Plasma With Lithium Divertors

Lithium is a low-Z material, and lithium-based plasma-facing components (PFCs) are planned for the National Spherical Torus Experiment Upgrade (NSTX-U) to explore potential benefits for divertor power exhaust and core plasma management. NSTX-U is a medium-sized spherical tokamak with up to 12 MW of auxiliary heating, capable of generating reactor-relevant plasma conditions. This work presents boundary plasma simulations for NSTX-U with lithium PFCs using the UEDGE code, incorporating full magnetic and 𝐄 ×𝐁 drift physics. The simulations show that drifts strongly influence heat and particle transport: they enhance convective transport, broaden the scrape-off layer heat-flux width 𝜆 𝑞 , and reduce the anomalous heat diffusivity 𝜒 required to reproduce predicted SOL heat-flux width. 𝐄 ×𝐁 drifts provide poloidal transport, while ∇𝐵 (which includes both gradB and curvature) drifts provide radial heat and particle transport. Lithium transport is also affected by drifts, with lithium ions migrating from the outer divertor to the inner divertor through the private flux region (PFR) following the 𝐄 ×𝐁 drifts flow, lowering upstream impurity lithium densities. UEDGE is self-consistently coupled with the Wall-Li model to study plasma lithium PFC interactions depending on the local lithium sourcing based on local plasma conditions and lithium surface temperature. In these simulations, lithium evaporation shows a vapor-shielding effect that reduces divertor heat flux and increases radiative losses once surface temperatures exceed 450°C. This research work provides a first step toward self-consistent modeling of lithium PFCs in NSTX-U, demonstrating the impact of drift-driven plasma transport in SOL and divertor regions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2022

Predation probabilities and functional responses: How piscivorous waterbirds respond to pulses in fish abundance

Abstract How predators respond to changes in prey abundance (i.e., functional responses) is foundational to consumer–resource interactions, predator–prey dynamics, and the stability of predator–prey systems. Predation by piscivorous waterbirds on out‐migrating juvenile steelhead trout ( Oncorhynchus mykiss ) is considered a factor affecting the recovery of multiple Endangered Species Act‐listed steelhead populations in the Columbia River basin. Waterbird functional responses, however, may vary by predator species and location, with important implications to predator management strategies. We used a 13‐year dataset on waterbird abundance across seven breeding colonies (three Caspian tern [ Hydroprogne caspia ], two double‐crested cormorant [ Nannopterum auritum ], and two California and ring‐billed gull [ Larus californicus and Larus delawarensis ] colonies) and steelhead tag‐recovery data (>645,000 tagged and >32,000 recovered steelhead) to quantify weekly predation probabilities and functional responses across waterbird species, colonies, and years. Weekly predation probabilities were highly variable, ranging from 0.01 to 0.30 at tern colonies, 0.01 to 0.20 at cormorant colonies, and 0.03 to 0.13 at gull colonies. Per capita predation probabilities were an order of magnitude higher at inland tern and cormorant colonies relative to estuary colonies of the same species. Terns displayed Type II functional responses across colonies and years, where predation probabilities peaked at low steelhead abundances and declined as steelhead abundance increased (i.e., predator swamping). Cormorants nesting at the large estuary colony (several thousand birds) displayed a Type III functional response, but cormorants nesting at the smaller inland colony (several hundred birds) displayed a Type II response. Consumption probabilities of steelhead by gulls remained consistent across a large range of steelhead availability, suggesting a Type I or a Type III functional response, but a lack of colony abundance data prevented quantifying functional responses. The level of tern predation combined with Type II functional responses indicate possible population‐level impacts that could destabilize small or declining prey populations. Conversely, the apparent Type III functional responses of gulls and estuary nesting cormorants are indicative of prey switching behaviors targeted at periods of high steelhead abundance. Our results illustrate the complexity of predator–prey interactions and the importance of quantifying predator‐ and location‐specific functional responses when predicting the efficacy of management strategies to enhance prey populations.

Hostetter, Nathan J.↗

DOE OSTI2024

Restoring freshwater habitat mosaics to promote resilience of vulnerable salmon populations

Phenotypic diversity and abundance drive salmon resilience in the face of increasing environmental variability. But what happens when human activities fundamentally alter the habitat complexity that drives this diversity? And how can we restore habitats to recover both diversity and abundance to support salmon persistence in a warming climate? Here, we looked at the impact of a large watershed restoration effort on the abundance and climate resilience of the three remaining core natural spring-run Chinook Salmon populations in the California Central Valley (Butte, Mill, and Deer Creek). Butte Creek fish, which have floodplain access, had higher overall productivity and faster juvenile growth compared with Mill and Deer Creek populations, and the proportion of floodplain inundation was positively correlated with Butte Creek adult abundance two years later. While Butte Creek exhibited significant increases in abundance post-restoration (~2000%), it generally exhibited lower phenotypic diversity and only a marginal increase in population stability after restoration based on the coefficient of variation (CV). In particular, Butte Creek salmon tended to exhibit larger drops in escapement following dry years (e.g., return years 2010, 2017) compared with Mill and Deer Creek populations, presumably due to limited inundation of its downstream floodplain. The late-migrating juvenile strategy (i.e., yearling), which disproportionately supported Mill and Deer Creek populations during droughts, was uncommon among Butte Creek adults (averaging 60% of returns for Mill and Deer Creek vs. 0.3% for Butte Creek). Increased spring-run stock complex stability was found, post-restoration, when combining the three spring-run populations (i.e., lower aggregate CV). However, among-river pairwise correlations also suggested increased synchronization in population abundances post-restoration, potentially due to increasing frequency and severity of extreme climatic events (e.g., droughts and ocean warming). This study underscores the importance of restoring a connected mosaic of aquatic habitats across modified landscapes, such as cold water refugia and floodplains, to preserve multiple (across-population) life history pathways for increasing salmon stock complex stability and abundance. These landscape-scale process-based habitat restoration efforts are likely to be crucial for the successful long-term recovery of vulnerable species in a rapidly changing climate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X-ray Absorption Spectroscopic Characterization

The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur (Li/S) cells. A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue. Herein, we employed in situ/operando X-ray absorption spectroscopy (XAS) to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces, respectively, in a real-time condition. After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix (BSOC), we found the Li/S cell showed greatly improved sulfur utilization and longer life span. The operando S K-edge XAS results revealed that the BSOC modification was bi-functional: trapping polysulfides and catalyzing conversion of sulfur species simultaneously. We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection. Finally, our results could offer potential stratagem for designing more advanced Li/S cells.

25 ENERGY STORAGE↗