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At least 289 records · Page 16

Triggering Anionic Redox Activity in Li 3 NbS 4 Through Cationic Disordering or Substitution

Extensive utilization of Li-ion batteries for varieties of applications necessitates ceaseless improvements of electrode materials for achieving higher energy density. Towards this goal, Li-rich layered oxides exhibiting high capacity due to cumulated cationic and anionic redox activities are under study for nearly a decade. Still, several unanswered questions remain with respect to these Li-driven anionic redox reactions in terms of the activation process and long-term consequences upon cycling. Here, the Li-rich Li 3 NbS 4 phase is focused, and synthesized as two different polymorphs, namely ordered and disordered phases. From analyses of their chemical and electrochemical properties, a crystal-electronic structure relationship is unraveled that triggers the anionic redox activity in these compounds. Moreover, through complementary theoretical calculations, the capability of cationic disorder to trigger anionic redox activity via the hybridization of cationic and non-bonding anionic energy levels is shown. This finding is further supported by the appearance of anionic redox activity by introducing the disorder through cationic substitution. Altogether, the insights derived here can help in designing new anionic redox materials with optimum performances for practical applications.

25 ENERGY STORAGE↗

Exceptional Thermochemical Stability of Graphene on N-Polar GaN for Remote Epitaxy

In this study, we investigate the thermochemical stability of graphene on the GaN substrate for metal–organic chemical vapor deposition (MOCVD)-based remote epitaxy. Despite excellent physical properties of GaN, making it a compelling choice for high-performance electronic and light-emitting device applications, the challenge of thermochemical decomposition of graphene on a GaN substrate at high temperatures has obstructed the achievement of remote homoepitaxy via MOCVD. Our research uncovers an unexpected stability of graphene on N-polar GaN, thereby enabling the MOCVD-based remote homoepitaxy of N-polar GaN. Our comparative analysis of N- and Ga-polar GaN substrates reveals markedly different outcomes: while a graphene/N-polar GaN substrate produces releasable microcrystals (μCs), a graphene/Ga-polar GaN substrate yields nonreleasable thin films. We attribute this discrepancy to the polarity-dependent thermochemical stability of graphene on the GaN substrate and its subsequent reaction with hydrogen. Evidence obtained from Raman spectroscopy, electron microscopic analyses, and overlayer delamination points to a pronounced thermochemical stability of graphene on N-polar GaN during MOCVD-based remote homoepitaxy. Molecular dynamics simulations, corroborated by experimental data, further substantiate that the thermochemical stability of graphene is reliant on the polarity of GaN, due to different reactions with hydrogen at high temperatures. In conclusion, based on the N-polar remote homoepitaxy of μCs, the practical application of our findings was demonstrated in fabrication of flexible light-emitting diodes composed of p–n junction μCs with InGaN heterostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

cuAlign: Scalable Network Alignment on GPU Accelerators

Given two graphs, the objective of network alignment is to find the best one-to-one mapping of vertices in one graph (??) to vertices in the other (??), such that the number of overlaps is maximized. We say that edges(??, ??) ???and(??', ??') ??? are overlapped if ?? is mapped to ??' and ?? is mapped to??'. Network alignment is an important optimization problem with several applications in bioinformatics, computer vision and ontology matching. Since it is an NP-hard problem, efficient heuristics and scalable implementations are necessary. In this work, we introduce a new framework that combines the concepts of intra-network proximity using vertex embedding,Belief Propagation (BP) and approximate weighted matching, and provides qualitative improvements up to22%over state-of-the-art approaches. We also provide scalable implementations on GPU accelerators, demonstrating up to19×speedup for Belief Propagation and 3× speedup for approximate weighted matching relative to previous multithreaded implementation. A combination of combinatorial and algebraic kernels within the network alignment algorithm poses significant hurdles for parallelization. Load imbalance and irregular DRAM traffic limit achievable performance on GPUs. Our novel approach identifies and exploits unique structural proper-ties of the BP-based algorithm and employs code fusion to reduce data movement between different steps of the algorithm. Using a diverse set of inputs, we demonstrate qualitative improvements of our algorithms, and performance gains of our GPU-accelerated implementation. We believe that our work will enable algorithmic improvements and practical applications of network alignment.

Xiang, Lizhi↗

Advancing representations of equity and justice in climate mitigation futures

THIS PAPER WAS PRIMARILY COMPLETED PRIOR TO THE AUTHOR JOINING PNNL AND NO DOE FUNDING WAS USED FOR THIS PAPER. In this work, we review how equity and justice issues in global climate mitigation scenarios are addressed within Integrated Assessment Models (IAMs) and propose a new research agenda to strengthen their integration in model development and application. We begin by examining prominent concerns at the science-policy interface. We introduce a typology of equity and justice limitations in climate mitigation scenarios, distinguishing among structural, methodological, and epistemological biases that shape what integrated assessment models can reveal at policy-relevant scales. Reflecting on these concerns, we propose a research agenda that describes new avenues of work and draws together distinct emerging initiatives. This agenda is based on the feasibility and depth of required interventions, from incremental improvements to structural reforms and alternative participatory approaches. Drawing on reflexive insights from integrated assessment practitioners, it addresses the operational challenges of translating justice concepts into metrics, including risks of reductionism, tokenism, and narrow definitions. Underlying this research agenda is a recognition that modeling communities must engage more critically with implicit assumptions in model design and use that have equity and justice implications. Achieving equitable climate futures will require transformative actions that integrate diverse justice concerns, advance sustainable development goals, and confront systemic inequities across both human and ecological dimensions. Although models will never capture all these aspects, they can be significantly enhanced to support more informed discussion and practical application. Our contribution proposes a way forward to achieving this goal.

Pachauri, Shonali↗

Potassium Prussian blue-coated Li-rich cathode with enhanced lithium ion storage property

With high specific capacity, the layered Li-rich Mn-based oxide (LRMO) is a promising candidate cathode material for Li-ion batteries. However, the irreversible release of Li-ions during the first charging process, instability of LRMO/electrolyte interface and relatively low ion conductivity of LRMO result in low initial Coulombic efficiency (ICE), poor cycle stability and rate performance, which prohibit its further application. Furthermore, interface engineering via additive coating is expected to effectively address these issues. Herein, we rely on potassium Prussian blue (KPB), a Li + acceptor with good ion conductivity, as a new coating material on LRMO particles. The KPB coating not only forms a protective layer on the surface of LRMO against electrolyte corrosion, but also functions as a host for Li + transport and accommodation, leading to enhanced ion conductivity and ICE of LRMO cathode. Consequently, 2 wt% KPB coated LRMO cathode achieved an initial discharge capacity of up to 281.7 mA h g -1 with an ICE of 85.69% compared to an ICE of 79.52% for the LRMO cathode without coating. The cycling and rate performance are also greatly improved as evidenced by the well maintained capacity of up to 176.8 mA h g -1 after 100 cycles at a current density of 0.5 C, compared to the limited capacity of only 135.3 mA h g -1 for the LRMO cathode without coating. Overall, this work pioneers the use of potassium Prussian blue as additive coating material to enhance performance of LRMO cathode, and we expect it to inspire the battery community with new strategies of material engineering/design toward practical application in high-energy lithium-ion batteries.

25 ENERGY STORAGE↗

Out-of-equilibrium dynamics of a grid-like Fe( II ) spin crossover dimer triggered by a two-photon excitation

The application of two-photon excitation (TPE) in the study of light-responsive materials holds immense potential due to its deeper penetration and reduced photodamage. Despite these benefits, TPE has been underutilised in the investigation of the photoinduced spin crossover (SCO) phenomenon. Here, we employ TPE to delve into the out-of-equilibrium dynamics of a SCO Fe II dimer of the form [Fe II (HL) 2 ] 2 (BF 4 ) 4 ·2MeCN (HL = 3,5-bis{6-(2,2'-bipyridyl)}pyrazole). Optical transient absorption (OTA) spectroscopy in solution proves that the same dynamics take place under both one-photon excitation (OPE) and TPE. The results show the emergence of the photoinduced high spin state in less than 2 ps and with a lifetime of 147 ns. Time-resolved photocrystallography (TRXRD) reveals a single molecular reorganisation within the first 500 ps following TPE. Additionally, variable temperature single crystal X-ray diffraction (VTSCXRD) and magnetic susceptibility measurements confirm that the thermal transition is silenced by the solvent. While the results of the OTA and TRXRD utilising TPE are intriguing, the high pump fluencies required to excite enough metal centres to the high spin state may impair its practical application. Nonetheless, this study sheds light on the potential of TPE for the investigation of the out-of-equilibrium dynamics of SCO complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithium superoxide-based high rate Li-Air batteries enabled by Di-iridium sulfur bridge active sites

Li-oxygen (Li-O 2 ) batteries can potentially provide much higher energy density than Li-ion batteries; however, the practical application of these batteries is hindered due to several drawbacks such as low current rates and high overpotential for the charging process. Here, in this paper, we report a novel Li-Air battery system that operates under high current rates (up to 1mAcm -2 ) with LiO 2 as the primary discharge product instead of the commonly reported Li 2 O 2 . This LiO 2 based battery at high rates is through a combination of an as-synthesized new one-dimensional (1D) transition metal trichalcogenide mid-entropy alloy of SnIrS 3.6 as a cathode catalyst and an electrolyte blend with a SnI 2 bi-functional additive. It is revealed that SnIrS 3.6 has a microporous structure composed of six- and five-coordinated metal atoms, forming octahedral and triangular bipyramids which has not been observed in other layered chalcogeide materials. DFT calculations reveal that the SnIrS 3.6 structure can result in LiO 2 formation through di-iridium sulfur bridge active sites that results in strong binding of O 2 and LiO 2 preventing disproportionation to Li 2 O 2 and enabling high rates. This finding will open a new perspective in designing advanced LiO 2 -based Li-O 2 batteries for real practices.

25 ENERGY STORAGE↗

The role of quantum computing in advancing scientific high-performance computing: A perspective from the ADAC institute

Quantum computing (QC) has gained significant attention over the past two decades due to its potential for speeding up classically demanding tasks. This transition from an academic focus to a thriving commercial sector is reflected in substantial global investments. While advancements in qubit counts and functionalities continue at a rapid pace, current quantum systems still lack the scalability for practical applications, facing challenges such as too high error rates and limited coherence times. Here, this perspective paper examines the relationship between QC and high-performance computing (HPC), highlighting their complementary roles in enhancing computational efficiency. It is widely acknowledged that even fully error-corrected QC will not be suited for all computational tasks. Rather, future compute infrastructures are anticipated to employ quantum acceleration within hybrid systems that integrate HPC and QC. While QC can enhance classical computing, traditional HPC remains essential for maximizing quantum acceleration. This integration is a priority for supercomputing centers and companies, sparking innovation to address the challenges of merging these technologies. The novelty of this work lies in its unique perspective, reflecting the collective insights of the Accelerated Data Analytics and Computing (ADAC) Institute, a global consortium of over 20 leading HPC centers. Recognizing the growing importance of QC, ADAC established a Quantum Computing Working Group in 2023 to foster collaboration and knowledge-sharing among its members. This paper synthesizes insights from the group’s collaborative efforts and incorporates findings from a member survey that captures shared experiences, ongoing projects, and strategic directions. By outlining the current landscape and challenges of QC integration into HPC ecosystems, this work offers HPC specialists practical and forward-looking guidance on the opportunities and implications of QC in computationally intensive endeavors.

Accelerated Data Analytics and↗

Optimization of catalyst-coated membranes for enhancing performance in proton exchange membrane electrolyzer cells

To achieve large-scale application of proton exchange membrane electrolyzer cells (PEMECs) for hydrogen production, it is highly desirable to reduce the manufacturing cost while enhancing cell performance. In the PEMPECs, a catalyst-coated membrane (CCM) is the vital component where electrochemical reactions and mass transport mainly occur. The fabrication methods and catalyst layer (CL) structure can significantly affect the cell performance. Herein, for the first time, a comparative study of CCM fabrications with decal transfer and direct spray deposition methods have been conducted by both ex-situ materials characterization and in-situ performance testing in PEMECs. It is found CCMs that are fabricated with a direct spray deposition method display enhanced cell performance compared to CCMs fabricated with a decal transfer method, mainly due to the largely reduced ohmic resistance and improved mass transport. More importantly, cell performance can be greatly enhanced by simply regulating the Nafion ionomer content at the anode CL. The optimal Nafion ionomer content of 10 wt% gives the best cell performance at 80 °C with a low cell voltage of 1.887 V at 2 A cm -2 , outperforming the commercial CCM and most other previous publications. Our study provides a valuable guidance for fabrication and optimization of CCMs with significantly enhanced performance and reduced cost for practical application of the PEMECs.

08 HYDROGEN↗

Integrable symplectic maps with a polygon tessellation

Identifying integrable dynamics remains a formidable challenge, and despite centuries of research, only a handful of examples are known to date. In this article, we explore a distinct form of area-preserving (symplectic) mappings derived from the stroboscopic Poincaré cross section of a kicked rotator—an oscillator subjected to an external force periodically switched on in short pulses. The significance of this class of problems extends to various applications in physics and mathematics, including particle accelerators, crystallography, and studies of chaos. Notably, Suris's theorem constrains the integrability within this category of mappings, outlining potential scenarios with analytic invariants of motion. In this paper, we challenge the assumption of the analyticity of the invariant by exploring piecewise linear transformations on a torus ( T 2 ) and associated systems on the plane ( R 2 ), incorporating arithmetic quasiperiodicity and discontinuities. Introducing a new automated technique, we discovered previously unknown scenarios featuring polygonal invariants that form perfect tessellations and, moreover, fibrations of the plane or torus. This work reveals a novel category of planar tilings characterized by discrete symmetries that emerge from the invertibility of transformations and are intrinsically linked to the presence of integrability. Our algorithm relies on the analysis of the Poincaré rotation number and its piecewise monotonic nature for integrable cases, contrasting with the noisy behavior in the case of chaos, thereby allowing for clear separation. Some of the newly discovered systems exhibit the peculiar behavior of “integrable diffusion,” characterized by infinite and quasirandom hopping between tiles while being confined to a set of invariant segments. Finally, through the implementation of a smoothening procedure, all mappings can be generalized to quasi-integrable scenarios with suppressed volume occupied by chaotic trajectories, thereby opening doors to potential practical applications. Published by the American Physical Society 2024

43 PARTICLE ACCELERATORS↗

Investigation of the Solution Chemistry of Hybrid Organic–Inorganic Indium Halides for New Material Discovery

Recently, metal halide perovskites (MHPs) have emerged as a new class of materials for optical and electronic applications such as solar cells and ionizing radiation detectors. Although the solution-processability of MHPs is among their greatest advantages, the solution chemistries of most metal halide systems and their relationship with the observed structural and chemical diversity are poorly understood. In this work, we study the solution chemistry of a model indium halide system, methylammonium (MA)–In–Br, using a combination of the UV–vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS) measurements, small-angle X-ray scattering (SAXS), and density functional theory (DFT) calculations. Our results show that indium could form either octahedral [InBr 6 3– ] or tetrahedral [InBr 4 – ] anions in solution or a combination of both, depending on the loading ratios of MABr and InBr 3 reactants. Understanding the solution chemistry of this system and recognizing the optical fingerprints of these polyanions allow for targeted crystallization of two novel compounds: MAInBr 4 featuring tetrahedral [InBr 4 – ] anions and MA 2 InBr 5 containing both octahedral [InBr 6 3– ] and tetrahedral [InBr 4 – ] anions. Further increase of the MABr content leads to the formation of previously reported MA 4 InBr 7 , containing only octahedral [InBr 6 3– ] anions separated by Br – anions. Furthermore, our results suggest that understanding the solution chemistry of multinary metal halide systems could be a valuable tool for discovering functional materials for practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stretching of immersed polyelectrolyte brushes in shear flow

In this article, the way that polymer brushes respond to shear flow has important implications in various applications, including antifouling, corrosion protection, and stimuli-responsive materials. However, there is still much to learn about the behaviours and mechanisms that govern these responses. To address this gap in knowledge, our study uses in situ X-ray reflectivity to investigate how poly(styrene sulfonate) (PSS) brushes stretch and change in different environments, such as isopropanol (a poor solvent), water (a good solvent), and aqueous solutions containing various cations (Cs + , Ba 2+ , La 3+ , and Y 3+ ). We have designed a custom apparatus that exposes the PSS brushes to both tangential shear forces from the primary flow and upward drag forces from a secondary flow. Our experimental findings clearly show that shear forces have a significant impact on how the chains in PSS brushes are arranged. At low shear rates, the tangential shear force causes the chains to tilt, leading to brush contraction. In contrast, higher shear rates generate an upward shear force that stretches and expands the chains. By analysing electron density profiles obtained from X-ray reflectivity, we gain valuable insights into how the PSS brushes respond structurally, especially the role of the diffuse layer in this dynamic behaviour. Our results highlight the importance of the initial chain configuration, which is influenced by the solvent and cations present, in shaping how polymer brushes respond to shear flow. The strength of the salt bridge network also plays a crucial role in determining how easily the brushes can stretch, with stronger networks offering more resistance to stretching. Ultimately, our study aims to enhance our understanding of polymer physics at interfaces, with a particular focus on practical applications involving polymer brushes.

36 MATERIALS SCIENCE↗

Accommodation of Silicon in an Interconnected Copper Network for Robust Li-Ion Storage

Silicon (Si)-based materials are one of the most promising anodes to be applied in rechargeable lithium ion batteries. However, the active Si/electrolyte interface causes continuous side reactions and poor conductivity, which significantly decreases the cycling stability. Cu is the only metallic current collector that has been known to promote electron conduction and lithium-ion transfer without alloying reaction occurrence. However, to the best current knowledge, scalable interface engineering incorporating Cu has not been reported. In this study, this conductive Cu interface (CCI) is constructed through a self-assembly carbothermic reduction method to achieve efficient protection of Si/electrolyte interfaces while allowing for fast Li + diffusion. The energy barrier of lithium-ion diffusion through Cu is calculated to be 0.1965 eV, which is much lower than that through Au, Fe, and Ni films. Benefiting from the enhanced interfacial protection and kinetics of Si with CCI, a fading rate of only 0.068% is maintained for 1000 cycles and an aerial capacity of 4.78 mAh cm -2 is achieved after 280 cycles, which is comparable to the industry standards required for practical application.

36 MATERIALS SCIENCE↗

Negative Charge Confined Amine Carriers within the Nanowire Network for Stable and Efficient Membrane Carbon Capture

Membrane-based carbon dioxide (CO 2 ) capture has attracted great research interest owing to its potential for higher separation efficiency and lower energy consumption. However, it is still a challenging task to capture CO 2 with membrane from flue gas, especially under moderate-temperature and high-humidity conditions. Here, a stable CO 2 -selective membrane that can operate at temperatures up to 90 °C and under high humidity is reported. The positively charged amine carriers for CO 2 are confined within the negatively charged polymer modified carbon nanotube (CNT) network. In this structure, interconnected CNTs act as the framework for the selective layer and provide numerous nanochannels for gas transport. The negatively charged polymer ensures the carrier stability and further regulates the size of nanochannels in the CNT network. By virtue of carrier-facilitated transport, high CO 2 permeance (up to 3300 gas permeation units) and high CO 2 /N 2 selectivity (400) are achieved under simulated flue gas conditions. Moreover, theoretical calculations verify that the stable separation performance is due to the strong electrostatic interaction between the amine carriers and polymer matrix. The high performance and good stability indicate the great potential of this novel membrane structure for practical application in CO 2 capture.

36 MATERIALS SCIENCE↗

Effects of Fluorinated Diluents in Localized High‐Concentration Electrolytes for Lithium–Oxygen Batteries

Abstract A stable electrolyte is critical for practical application of lithium–oxygen batteries (LOBs). Although the ionic conductivity and electrochemical stability of the electrolytes have been extensively investigated before, their oxygen solubility, viscosity, volatility, and the stability against singlet oxygen ( 1 O 2 ) still need to be comprehensively investigated to provide a full picture of the electrolytes, especially for an open system such as LOBs. Herein, a systematic investigation is reported on the localized high‐concentration electrolytes (LHCEs) using different fluorinated diluents in comparison with those of conventional electrolytes. The physical properties and activation energies for reactions with singlet oxygen ( 1 O 2 ) of these electrolytes are calculated by density functional theory. The electrochemical performances of LOBs using these electrolytes are compared. This study reveals that the correlation between the stability of the electrolytes and their physical and electrochemical properties depends strongly on the diluents in LHCEs. Therefore, it shines light on the rational design of new electrolytes for LOBs.

Kwak, Won‐Jin↗

Enabling Stable High‐Voltage LiCoO 2 Operation by Using Synergetic Interfacial Modification Strategy

Abstract Structural and interfacial instability of the LiCoO 2 cathode under a voltage exceeding 4.5 V (vs Li/Li + ) severely hinders its practical applications for high‐energy‐density lithium batteries. Herein, a modified electrolyte with nitriles (suberonitrile or 1,3,6‐hexanetricarbonitrile) and fluoroethylene carbonate (FEC) coadditives is demonstrated to form an ultrathin and uniform interface layer on LiCoO 2 cathode under a synergetic effect. As such, LiCoO 2 /Li cells display excellent cyclability at a cutoff voltage of 4.6 V with a capacity retention over 72% after 300 cycles and 60% after 200 cycles at 30 and 55 °C, respectively, even achieving operation at a high current rate (10 C) upon 500 cycles as compared to the controls with fast‐falling capacity to zero. Furthermore, an adsorption‐coordination mechanism between nitriles and cobalt and synergetic effect of coadditives are explored by the alliance of spectroscopic analysis and theoretical calculations. The contributed lone‐pairs on the N 2p orbital of nitriles in coordination lowers the real oxidation state of Co 3+/4+ so that it decreases its catalysis on electrolytes, and the synergy from nitrile‐derived species regulates FEC to form an LiF‐containing electron‐insulated interface layer. This work shares a new insight to nitriles with the synergy of coadditives and paves a way to refine (ultra)high‐voltage LiCoO 2 cathode for high‐energy‐density energy storages.

Yang, Xuerui↗

Decreasing the Overpotential of Aprotic Li-CO 2 Batteries with the In-Plane Alloy Structure in Ultrathin 2D Ru-Based Nanosheets

We report the aprotic Li-CO 2 battery is emerging as a promising energy storage technology with the capability of CO 2 fixation and conversion. However, its practical applications are still impeded by the large overpotential. Herein, the general synthesis of a series of ultrathin 2D Ru-M (M = Co, Ni, and Cu) nanosheets by a facile one-pot solvothermal method is reported. As a proof-of-concept application, the representative RuCo nanosheets are used as the cathode catalysts for Li-CO 2 batteries, which demonstrate a low charge voltage of 3.74 V, a small overpotential of 0.94 V, and hence a high energy efficiency of 75%. Ex/in situ studies and density functional theory calculations reveal that the excellent catalytic performance of RuCo nanosheets originates from the enhanced adsorption toward Li and CO 2 during discharge as well as the elevated electron interaction with Li 2 CO 3 during charge by the in-plane RuCo alloy structure. This work indicates the feasibility of boosting the electrochemical performance of Li-CO 2 batteries by in-plane metal alloy sites of ultrathin 2D alloy nanomaterials.

25 ENERGY STORAGE↗

Enabling Conversion-Type Iron Fluoride Cathode by Halide-Based Solid Electrolyte

The practical application of low-cost and energy-dense iron fluoride cathodes has been hindered by the first cycle electrochemical irreversibility, cycling instability, and large voltage hysteresis. Here, we report that these challenges may be overcome by the utilization of halide-based solid electrolytes (SEs). The excellent electrochemical stability of halide-based SEs enables a complete conversion and deconversion of FeF 2 which cannot be achieved with sulfide-based SEs. Due to restricted and reversible decomposition of SE, prevention of Fe dissolution, mechanical confinement of active material, as well as improved electrode kinetics, solid-state FeF 2 cathode with halide-based SE demonstrated superior electrochemical performance compared with FeF 2 electrodes in liquid electrolytes, with a high 1st cycle coulombic efficiency (~100 %), high specific capacity (~600 mAh/g), long cycle life (>100 cycles) and high-rate performance (up to 2C). In conclusion, our results suggest solidifying the batteries may be a viable approach to addressing the long-standing key challenges of iron fluoride cathodes.

25 ENERGY STORAGE↗