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At least 325 records · Page 18

Aqueous vs. nonaqueous Zn-ion batteries: consequences of the desolvation penalty at the interface

Zinc ion batteries using metallic zinc as the negative electrode have gained considerable interest for electrochemical energy storage, whose development is crucial for the adoption of renewable energy technologies, as zinc has a very high volumetric capacity (5845 mA h cm -3 ), is inexpensive and compatible with aqueous electrolytes. However, the divalent charge of zinc ions, which restricts the choice of host material due to hindered solid-state diffusion, can also pose a problem for interfacial charge transfer. We report our findings on reversible intercalation of up to two Zn 2+ ions in layered V 3 O 7 ·H 2 O. This material exhibits very high capacity and power (375 mA h g -1 at a 1C rate, and 275 mA h g -1 at an 8C rate) in an aqueous electrolyte compared to a very low capacity and slow rate capabilities in a nonaqueous medium. Operando XRD studies, together with impedance analysis, reveal solid solution behavior associated with Zn 2+ -ion diffusion within a water monolayer in the interlayer gap in both systems, but very sluggish interfacial charge transfer in the nonaqueous electrolyte. This points to desolvation at the interface as a major factor in dictating the kinetics. Temperature dependent impedance studies show high activation energies associated with the nonaqueous charge transfer process, identifying the origin of poor electrochemical performance.

25 ENERGY STORAGE↗

High rate lithium-sulfur batteries enabled by mesoporous TiO{sub 2} nanotubes prepared by electrospinning

Graphical abstract: Mesoporous titanium dioxide nanotubes (MTDNTs) used as host for sulfur was prepared by electrospinning technique and subsequent thermal treatment. The nanotube walls of MTDNTs act as a host for sulfur and the hollow structure is favorable for the fast transmission of Li{sup +} ions. After sulfur was encapsulated into the pores of nanotube walls of MTDNTs, the MTDNTs/S composite electrode displays a relatively good cycling performance and especially excellent rate performance (about 610 mAh g-1 at 8 C). - Highlights: • Mesoporous titanium dioxide nanotubes (MTDNTs) were fabricated by electrospinning and subsequent thermal treatment. • MTDNTs was used as host for sulfur, TEM and SEM analysis showed that sulfur distributed in the meso pores of MTDNTs walls. • MTDNTs/S composite cathode delivers a reversible discharge capacity of 610 mAh g{sup −1} at a high current rate of 8 C. - Abstract: Mesoporous titanium dioxide nanotubes (MTDNTs) were prepared by electrospinning and subsequent thermal treatment. The as-synthesized MTDNTs possess anatase mischcrystal structure, hollow texture morphology, and a relatively high specific surface area of 93.6 m{sup 2} g{sup −1} with a pore volume of 0.2190 cm{sup −3} g{sup −1}. The nanotube walls of MTDNTs act as a host for sulfur and the hollow structure is favorable for the fast transmission of Li{sup +} ions. After sulfur was encapsulated into the pores of nanotube walls of MTDNTs, the MTDNTs/S composite electrode displays a relatively good cycling performance and especially excellent rate performance (about 610 mAh g{sup −1} at 8 C). The retention capacity can be up to 74.2% when the discharge rate increases from 0.5C to 8.0 C.

36 MATERIALS SCIENCE↗

Exploring the All-to-All Collective Optimization Space with ConnectX CORE-Direct

The all-to-all collective communication operation is used by many scientific applications, and is one of the most time consuming and challenging collective operation to optimize. The algorithms for all-to-all operations typically fall into two classes, logarithmic and linear scaling algorithms, with Bruck's algorithm, a logarithmic scaling algorithm, used in many small-data all-to-all implementations. The recent addition of InfiniBand CORE-Direct support for network management of collective communications offers new opportunities for optimizing all-to-all operation as well as supporting truly asynchronous implementations of these operations. This paper presents several new enhancements to the Bruck small-data algorithm that leverage CORE-Direct and other InfiniBand network capabilities to produce efficient implementations of this collective operation. These include RDMA, SR-RNR, and SR-RTR algorithms. In addition, nonblocking implementations of these collective operations are also presented. Benchmark results show that the RDMA algorithm, which uses CORE-Direct capabilities to offload collective communication management to the Host Channel Adapter (HCA), hardware gather support for sending non-continuous data, and low-latency RDMA semantics, performs the best. For a 64 processes and 128 byte-per-process all-to-all, the RDMA algorithm performs 27% better than Bruck's algorithm implementation in Open MPI and 136% better than the SR-RTR algorithm. In addition, the nonblocking versions of these algorithms have the same performance characteristics as the blocking algorithms. Finally, measurements of computation/communication overlap capacity show that all offloaded algorithms achieve about 98% overlap for large data all-to-all, whereas implementations using host-based progress achieve only about 9.5% overlap.

Venkata, Manjunath Gorentla↗

Insight into the Capacity Fading Mechanism of Amorphous Se 2 S 5 Confined in Micro/Mesoporous Carbon Matrix in Ether-Based Electrolytes

In contrast to the stable cycle performance of space confined Se-based cathodes for lithium batteries in carbonate-based electrolytes, their common capacity fading in ether-based electrolytes has been paid less attention and not yet well-addressed so far. In this work, the lithiation/delithiation of amorphous Se2S5 confined in micro/mesoporous carbon (Se2S5/MPC) cathode was investigated by in situ X-ray near edge absorption spectroscopy (XANES) and theoretical calculations. The Se2S5/MPC composite was synthesized by a modified vaporization-condensation method to ensure a good encapsulation of Se2S5 into the pores of MPC host. In situ XANES results illustrated that the lithiation/delithiation reversibility of Se component was gradually decreased in ether-based electrolytes, leading to an aggravated formation of long-chain polyselenides during cycling and further capacity decay. Moreover, ab initio calculations revealed that the binding energy of polyselenides (Li2Sen) with carbon host is in an order of Li2Se6 > Li2Se4 > Li2Se. The insights into the failure mechanism of Se-based cathode gain in this work are expected to serve as a guide for future design on high performance Se-based cathodes.

ab initio calculations↗

Structural characterization of layered Na 0.5 Co 0.5 Mn 0.5 O 2 material as a promising cathode for sodium-ion batteries

Layered Na0.5Co0.5Mn0.5O2 material is synthesized through a facile mixed hydroxy-carbonate route using (Co0.5Mn0.5)2(OH)2CO3 precursor and well characterized as a hexagonal layered structure under P63/mmc space group. The lattice parameters and unit cell volume (a ¼ 2.8363 Å, c ¼ 11.3152 Å and V ¼ 78.83 Å3 ) are calculated by Rietveld refinement analysis. A flaky-bundle morphology is obtained to the layered Na0.5Co0.5Mn0.5O2 material with the hexagonal flake size ~30 nm. Advanced transmission electron microscopic images are revealed the local structure of the layered Na0.5Co0.5Mn0.5O2 material with contrasting bright dots and faint dark dots corresponding to the Co/Mn and Na atoms. Two oxidation and reduction peaks are occurred in a cyclic voltammetric analysis corresponding to Co3þ/Co4þ and Mn3þ/Mn4þ redox processes. These reversible processes are attributed to the intercalation/de-intercalation of Naþ ions into the host structure of layered Na0.5Co0.5Mn0.5O2 material. Accordingly, the sodium cell is delivered the initial charge-discharge capacity 53/144 mAh g1 at 0.5 C, which cycling studies are extended to rate capability test at 1 C, 3 C and 5C. Eventually, the Na-ion full-cell is yielded cathode charge-discharge capacity 55/52 mAh g1 at 0.212 mA and exhibited as a high voltage cathode for Na-ion batteries.

Cathode performance↗

Influence of surface chemistry on Li nucleation energetics on graphene-based surfaces

Lithium metal is a promising high-capacity anode material for solid-state batteries, but it typically suffers from poor cyclability. Carbon scaffold hosts have the potential to improve this performance due to their high electronic conductivity and large surface area, which facilitates lithium-ion adsorption and desorption. Scaffold surface chemistry is known to significantly influence performance outcomes, but the details of these interactions are not fully understood. Here, this study employs first-principles simulations to explore lithium transport and nucleation on graphene anodes with various surface chemistries. Using enhanced sampling techniques, ab initio molecular dynamics, and density functional theory calculations, we find that although surface chemistry has a minimal impact on lithium interfacial transport, it influences surface nucleation significantly. Both heteroatom dopants and intrinsic defects lower the nucleation barrier, creating a more favorable environment for lithium nucleation compared to pristine graphene. In addition, our results reveal a complex interplay between surface lithium concentration, lithium transport, and nucleation kinetics. These findings highlight the potential of surface modifications to precisely control nucleation processes on carbon-based anodes and provide design guidance for reducing dendrite formation and improving the cycle life of solid-state batteries.

36 MATERIALS SCIENCE↗

A Systems Engineering Analysis of National Ignition Facility Industrial Controls Systems and Safety Interlock Systems Remote Input/Output Networking Migration from ControlNet to EtherNet/IP

The ControlNet industrial communications protocol and modules used in the Industrial Control System (ICS) and Safety Interlock System (SIS) at the National Ignition Facility (NIF) are no longer necessary and the ICS and SIS would be better served by migrating the communications structure to use EtherNet/Industrial Protocol (IP) and EtherNet bridge modules instead. By the admission of the vendor of ControlNet hardware, Rockwell Automation, in literature by Bill Petro [1], “Moving forward, customers will be able to optimize their asset utilization better using EtherNet/IP protocol than with ControlNet.” The NIF is one of the key elements of the Inertial Confinement Fusion (ICF) program at Lawrence Livermore National Laboratory (LLNL), a federally funded research and development center (FFRDC). The NIF contains the systems and provides the operational capacity to perform ICF, high energy density (HED), and discovery science experiments utilizing 192 individual beamlines, a host of diagnostics, and all the industrial systems required to facilitate these beamlines and diagnostics. The industrial systems are governed by the ICS and SIS, with the ICS providing control and the SIS providing monitoring and permissives. Construction on the NIF began in 1997 and was certified complete in 2009 and, as a result, the ICS and SIS were developed during this time using the tools that were available then. This includes the communications structure and protocols for these systems, much of which was, and still is, ControlNet. ControlNet, particularly during the time that the ICS and SIS were being built, has several attractive features. ControlNet hardware is exclusive to Rockwell Automation, which was the automation hardware chosen for the ICS and SIS. One feature that could be considered an advantage or a disadvantage depending on the communication needs of the system is that ControlNet also utilizes no active network components, excluding repeaters which are not always necessary. According to the architect of the ICS system at the NIF, Gordon Lau, one of the most attractive features of the ControlNet protocol during development of the ICS and SIS was that it is deterministic, providing timing of data transfer that is executed exactly as it is defined by the developer.

42 ENGINEERING↗

Advanced strategies for the development of porous carbon as a Li host/current collector for lithium metal batteries

Lithium metal is considered a promising anode material for high-energy-density rechargeable batteries because of its high specific theoretical capacity (3860 mAh g -1 , low mass density (0.534 g cm -3 ), and low electrochemical redox potential (-3.04 V vs. the standard hydrogen electrode). However, the high reactivity of Li with the electrolyte leads to the formation of an unstable solid electrolyte interphase (SEI) and continuous side reactions. Also, the non-uniform lithium-ion flux and infinite volume expansion of Li metal cause the growth of Li dendrites. These pose significant safety challenges and cause rapid capacity fading of the lithium metal batteries (LiMBs). To resolve these issues, a low-cost, easily processed, lightweight, high-performance carbon-based porous matrix is considered promising to host Li metal deposition. The three-dimensional (3D) porous nano/microstructured carbon provides sufficient space for Li accommodation during Li plating, buffers the volume changes during Li plating/stripping, and lowers the effective current density contributing to dendrite-free Li deposition. Besides, the outstanding electrochemical and mechanical stability, flexibility and the high electronic conductivity enable the nano/microstructured carbon to serve as both Li host and current collector. The development of 3D carbon/Li composite by mechanical roll-press techniques not only eliminates the complex and risky procedure of making carbon/Li composite based on Li plating or molten Li infusion but also stabilizes the capacity at higher Li plating/stripping rates. Recently, there is an advancement in the lithiophilic decorations of 3D structure to introduce sufficient nucleation sites and the development of artificial SEI on top of the 3D matrix to suppress Li dendrite formation. Such 3D structural modifications create a uniform electric field, lower the Li nucleation overpotential, provide strong mechanical and chemical stability, and stabilize the interface thereby inhibiting the degradation of lithium and the electrolyte. Here we summarize the research progress on porous carbon/Li composites in terms of materials type, structure, fabrication technique, their electrochemical battery performance, and identify the critical challenges that need to be addressed for high-energy-density practical LiMBs.

25 ENERGY STORAGE↗

An Electron/Ion Dual‐Conductive Alloy Framework for High‐Rate and High‐Capacity Solid‐State Lithium‐Metal Batteries

Abstract The solid‐state Li battery is a promising energy‐storage system that is both safe and features a high energy density. A main obstacle to its application is the poor interface contact between the solid electrodes and the ceramic electrolyte. Surface treatment methods have been proposed to improve the interface of the ceramic electrolytes, but they are generally limited to low‐capacity or short‐term cycling. Herein, an electron/ion dual‐conductive solid framework is proposed by partially dealloying the Li–Mg alloy anode on a garnet‐type solid‐state electrolyte. The Li–Mg alloy framework serves as a solid electron/ion dual‐conductive Li host during cell cycling, in which the Li metal can cycle as a Li‐rich or Li‐deficient alloy anode, free from interface deterioration or volume collapse. Thus, the capacity, current density, and cycle life of the solid Li anode are improved. The cycle capability of this solid anode is demonstrated by cycling for 500 h at 1 mA cm −2 , followed by another 500 h at 2 mA cm −2 without short‐circuiting, realizing a record high cumulative capacity of 750 mA h cm −2 for garnet‐type all‐solid‐state Li batteries. This alloy framework with electron/ion dual‐conductive pathways creates the possibility to realize high‐energy solid‐state Li batteries with extended lifespans.

Yang, Chunpeng↗

Efficient sulfur host based on NiCo{sub 2}O{sub 4} hollow microtubes for advanced Li-S batteries

High energy density and cost effectiveness make lithium-sulfur battery a promising candidate for next-generation electrochemical energy storage technology. Here, we have synthesized a highly efficient sulfur host namely NiCo{sub 2}O{sub 4} hollow microtubes/sulfur composite (NiCo{sub 2}O{sub 4}/S). The hollow interior cavity providing structural integrity while sufficient self-functionalized surfaces of NiCo{sub 2}O{sub 4} chemically bind polysulfides to prevent their dissolution in the organic electrolyte. When used in lithium-sulfur batteries, the synthesized NiCo{sub 2}O{sub 4}/S cathode delivers high specific capacity (1274 mAh g{sup −1} at 0.2 C), long cycling performance at 0.5 C, and good rate capability at high current rates. - Highlights: • Hollow NiCo{sub 2}O{sub 4}/S microtubes were evaluated as an efficient sulfur host. • The designed 1D hollow architecture resulted in better cycling performance. • NiCo{sub 2}O{sub 4}/S delivered high capacity, long cycle life and good rate capability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reversing the Irreversible: Thermodynamic Stabilization of LiAlH 4 Nanoconfined Within a Nitrogen-Doped Carbon Host

A general problem when designing functional nanomaterials for energy storage is the lack of control over the stability and reactivity of metastable phases. Using the high-capacity hydrogen storage candidate LiAlH4 as an exemplar, we demonstrate an alternative approach to the thermodynamic stabilization of metastable metal hydrides by coordination to nitrogen binding sites within the nanopores of N-doped CMK-3 carbon (NCMK-3). The resulting LiAlH 4 @NCMK-3 material releases H 2 at temperatures as low as 126 °C with full decomposition below 240 °C, bypassing the usual Li 3 AlH 6 intermediate observed in bulk. Moreover, >80% of LiAlH 4 can be regenerated under 100 MPa H 2 , a feat previously thought to be impossible. Nitrogen sites are critical to these improvements, as no reversibility is observed with undoped CMK-3. Density functional theory predicts a drastically reduced Al–H bond dissociation energy and supports the observed change in the reaction pathway. Finally, the calculations also provide a rationale for the solid-state reversibility, which derives from the combined effects of nanoconfinement, Li adatom formation, and charge redistribution between the metal hydride and the host.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A 3D Lithiophilic Mo 2 N–Modified Carbon Nanofiber Architecture for Dendrite–Free Lithium–Metal Anodes in a Full Cell

The pursuit for high-energy-density batteries has inspired the resurgence of metallic lithium (Li) as a promising anode, yet its practical viability is restricted by the uncontrollable Li dendrite growth and huge volume changes during repeated cycling. Herein, a new 3D framework configured with Mo 2 N-mofidied carbon nanofiber (CNF) architecture is established as a Li host via a facile fabrication method. The lithiophilic Mo 2 N acts as a homogeneously pre-planted seed with ultralow Li nucleation overpotential, thus spatially guiding a uniform Li nucleation and deposition in the matrix. The conductive CNF skeleton effectively homogenizes the current distribution and Li-ion flux, further suppressing Li-dendrite formation. As a result, the 3D hybrid Mo 2 N@CNF structure facilitates a dendrite-free morphology with greatly alleviated volume expansion, delivering a significantly improved Coulombic efficiency of ≈99.2% over 150 cycles at 4 mA cm –2 . Symmetric cells with Mo 2 N@CNF substrates stably operate over 1500 h at 6 mA cm –2 for 6 mA h cm –2 . Furthermore, full cells paired with LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) cathodes in conventional carbonate electrolytes achieve a remarkable capacity retention of 90% over 150 cycles. Finally, this work sheds new light on the facile design of 3D lithiophilic hosts for dendrite-free lithium-metal anodes.

25 ENERGY STORAGE↗

THE HUNT FOR EXOMOONS WITH KEPLER (HEK). II. ANALYSIS OF SEVEN VIABLE SATELLITE-HOSTING PLANET CANDIDATES

From the list of 2321 transiting planet candidates announced by the Kepler Mission, we select seven targets with favorable properties for the capacity to dynamically maintain an exomoon and present a detectable signal. These seven candidates were identified through our automatic target selection (TSA) algorithm and target selection prioritization (TSP) filtering, whereby we excluded systems exhibiting significant time-correlated noise and focused on those with a single transiting planet candidate of radius less than 6 R{sub Circled-Plus }. We find no compelling evidence for an exomoon around any of the seven Kepler Objects of Interest (KOIs) but constrain the satellite-to-planet mass ratios for each. For four of the seven KOIs, we estimate a 95% upper quantile of M{sub S} /M{sub P} < 0.04, which given the radii of the candidates, likely probes down to sub-Earth masses. We also derive precise transit times and durations for each candidate and find no evidence for dynamical variations in any of the KOIs. With just a few systems analyzed thus far in the ongoing ''Hunt for Exomoons with Kepler'' (HEK) project, projections on eta-moon would be premature, but a high frequency of large moons around Super-Earths/Mini-Neptunes would be premature, but a high frequency of large moons around Super-Earths/Mini-Neptunes would appear to be incommensurable with our results so far.

79 ASTRONOMY AND ASTROPHYSICS↗

A Study Of Geological Disposal Facility (GDF) Ageing Phenomena In Bentonite - 17605

Since the 1950's, the UK's nuclear activity in energy, defence and medicine has led to the accumulation of a large amount of higher activity radioactive waste (HAW). Most of nuclear waste arises in a wide variety of physical and chemical forms with different radioisotopes and loadings. Due to complexity in HAW, it is imperative that there be a rigorous management system that ensures population and environmental safety over extended periods. The concept of Deep Geological Disposal of waste in a stable geological formation is, nowadays, an internationally accepted solution as the surest and the most viable long term method for management. Any future Geological Disposal Facility (GDF) will comprise, among other artificial and natural engineered barriers, a barrier immediately around the waste containers compounded by a sealing material. The long-term stability of a GDF will be determined by the design and construction of the engineered barriers, and the mechanical, hydraulic and geochemical interactions that may happen between the different engineered components as a result of combined processes such as the heat produced by radioactive decay and the ion water composition of the surrounding host rock. Bentonite clay has been selected as the most promising buffer and backfill material in many disposal programmes because of its swelling capacity, low permeability, plasticity and cation exchange capacity. In the nuclear scope, bentonite testing at different scale-lengths (laboratory and field scale) has been performed and implemented in order to examine the thermo-hydro-mechanical (THM) and thermo-hydro-geochemical (THG) processes that may happen in the engineered barriers and geological settings associated with a GDF. Two major European field scale tests have been performed to better understand bentonite performance and behaviour immediately after HAW emplacements. The Full-Scale Engineered Barriers Experiment (FEBEX) at the Grimsel Test Sit (Switzerland) and the Alternative Buffer Material (ABM) Project at the Aespoe Hard Rock Laboratory (Sweden). The Febex Experiment was a pilot project designed for 'field research' of HAW repository hosted in crystalline rock where surrogate HAW canisters were placed horizontally in drifts, surrounded by compacted blocks of bentonite, sealed by a concrete plug and maintaining a constant canister surface temperature of 100 deg. C. After five years of operation, a partial dismantling was carried out in 2002. Heater processes occurring in the surrounding bentonite. The dismantling of the heater no. 2 (after 18 years of operation) started in late 2014 and is planned to be finished at the end of 2016 (termed FEBEX-DP). The FEBEX Project utilised bentonite from the Cortijo de Archidona deposit (Almeria, Spain). This 'Febex' bentonite is sourced from calcium-magnesium montmorillonite with good properties in relation to swelling capacity, permeability, adsorption capacity, and thermal conductivity. The ABM Project is a large-scale programme that has been running since 2006. The programme is designed to study a suite of possible buffer materials and correlate the physical and chemical properties of eleven different types of bentonites to their fundamental mineralogical properties. The ABM test consists in three 'packages' containing a central heater tube surrounded by different pre-compacted bentonite blocks and instrumentation. Each 'package' was installed in separate boreholes. The target temperature for the surface of the heated tubes in contact with the bentonite was 130 deg. C. Both FEBEX and ABM test the bentonite was saturated with water percolating from surrounding host rock (FEBEX and ABM) and also via artificial supply systems (ABM), being the water itself acting as a long term corrosion agent. For both experiments and emerging interest is in the interaction of bentonite with metallic components, under geological disposal conditions are not considered to be thermodynamically stable and hence arising corrosion products could interact with the buffer. These interactions depend on various factors such as the redox potential, temperature, pH, solute concentration and buffer material characteristics. During the operational phases of the FEBEX and ABM and after its 'closure' a significant volume of air was found to be retained in the bentonite. Under these conditions a period of initial aerobic corrosion by the air in the bentonite barrier would have occurred followed by establishment of anaerobic corrosion would be the dominant process ongoing. The anaerobic corrosion began when the bentonite became water saturated. Under these conditions, the water acted as the major oxidant. The present project focuses on the characterization of samples arising from the FEBEX and ABM Projects as well as performing additional independent experiments designed to complement these prior studies. Characterization will focus mainly on corrosion related alteration combined with thermal effects. Through detailed sample characterization, the intention is to achieve a greater knowledge regarding the changes to the bentonite under the experimental conditions to which it was exposed, and plausible alterations in its THM and THG properties occurring during the experiment due to blended effects of temperature,water content, engineering structural components and solutes are also to be measured. The fulfilment of a large-scale 'in-situ' test is intricate, time-consuming and with an abundance of external variables that are not always well controlled. For this reason, the University of Bristol is performing a series of well constrained time-resolved laboratory tests which bentonite is being subjected to different possible scenarios that may happen whilst in a HAW repository. In virtue of this experiment, the UoB aims to understand the illitisation and cementation process and their effects on bentonite safety properties. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Molecular Mechanisms of Innate Immune Inhibition by Non-Segmented Negative-Sense RNA Viruses

The host innate immune system serves as the first line of defense against viral infections. Germline-encoded pattern recognition receptors detect molecular patterns associated with pathogens and activate innate immune responses. Of particular relevance to viral infections are those pattern recognition receptors that activate type I interferon responses, which establish an antiviral state. The order Mononegavirales is composed of viruses that possess single-stranded, non-segmented negative-sense (NNS) RNA genomes and are important human pathogens that consistently antagonize signaling related to type I interferon responses. NNS viruses have limited encoding capacity compared to many DNA viruses, and as a likely consequence, most open reading frames encode multifunctional viral proteins that interact with host factors in order to evade host cell defenses while promoting viral replication. In this review, we will discuss the molecular mechanisms of innate immune evasion by select NNS viruses. Furthermore, a greater understanding of these interactions will be critical in facilitating the development of effective therapeutics and viral countermeasures.

59 BASIC BIOLOGICAL SCIENCES↗

Polymer Binders Constructed through Dynamic Noncovalent Bonds for High-Capacity Silicon-Based Anodes

Silicon (Si) is a promising candidate for high-capacity anode materials owing to its high theoretical capacity (3579 mAh g -1 ), low working voltage, and wide natural abundance, although its huge volume variation during charge/discharge processes always results in a short cycling life. Polymer binders play a vital role in improving the cycling performance of Si-based anodes, although traditional polyvinylidene difluoride cannot fulfill the requirements owing to its weak van der Waals forces with the Si surface. Recently, polymer binders constructed by dynamic bonds have been developed, which are reported to allow high-energy-density electrodes with improved electrochemical performance. With dynamic bonds including hydrogen bonding, ionic bonding, and host–guest interactions, these polymer binders possess self-healing capabilities and enhanced mechanical performance, achieving a tremendous advance in addressing the capacity fading of Si-based anodes. In this study, we will summarize the research progress of polymer binders constructed with dynamic bonds, and the challenges for their real applications in advanced Li-ion batteries will also be discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithiophilic V 2 O 5 nanobelt arrays decorated 3D framework hosts for highly stable composite lithium metal anodes

The lithium metal anode has been considered to be an optimal anode material for high-energy-density battery system due to its ultrahigh specific capacity. However, the sharp dendrite growth and infinite volume expansion have significantly impeded its commercial application. In this paper, we propose that V 2 O 5 as the lithiophilic substance can be decorated onto 3D stable frameworks to fabricate dendrite-suppressed composite Li metal anodes via a molten Li infusion method. It is demonstrated that the energetic chemical reaction between V 2 O 5 and molten Li together with the capillary effect based on the nanostructure of interconnected V 2 O 5 nanobelt arrays contributes synergistically to the great Li affinity of the V 2 O 5 -Ni foam (V 2 O 5 -NF) host and facilitate the efficient and uniform intake of molten Li into the 3D framework. Benefitting from the homogeneous Li distribution in the framework, the decreased local current density of the electrode and the stable property of the host, dendrite-free Li stripping/plating behavior and alleviated volume fluctuation have been achieved for the Li-V 2 O 5 -NF composite anode. Compared with the bare Li anode, the as-obtained Li-V 2 O 5 -NF composite anode exhibits much stable stripping/plating profiles with low overpotential (~18 mV) for ultralong lifespan (1600 h) at a current density of 1 mA cm -2 in symmetric Li/Li cell. Furthermore, outstanding rate capability and long-term cycling performance (78.8% capacity retention after 500 cycles under 2 C) are obtained in full cells when coupled with Li 4 Ti 5 O 12 (LTO) cathodes, indicating a promising potential for practical application. Moreover, this work demonstrates that using a new lithiophilic material, V 2 O 5 , should be an effective method to construct high stable 3D Li metal anode for Li metal battery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Mg 2+ deintercalation in manganese spinel nanocrystals

Transition metal oxides are promising materials as cathodes for divalent batteries with high capacity under high voltage. A major challenge is the sluggish kinetics of intercalation of divalent cations into the oxide host. Tailoring of the size, composition and crystal structure of oxides is a necessary strategy to alleviate these barriers, which challenges our control of their synthesis. In this work, we selectively synthesize spinel-type Mg x Mn 3-x O 4 nanocrystals with different Mg/Mn ratios and investigate their ability to electrochemically shuttle Mg 2+ ions. Crystal-chemical characterization of the reaction outcomes was conducted with X-ray diffraction, X-ray absorption spectroscopy, electron microscopy, and elemental analysis. Both 5 nm thick MgMn 2 O 4 nanosheets and 10 nm Mg 0.41 Mn 2.59 O 4 nanocubes underwent reversible Mg 2+ deintercalation, yet no obvious reaction was observed in 60 nm Mg 1.2 Mn 1.8 O 4 nanocubes. Our results suggest that both the size of the spinel nanocrystals and the Mg/Mn ratios play a role in the observed behaviour. The advances in the synthesis of spinel oxide nanocrystals achieved, and their correlation with Mg 2+ deintercalation, pave the way toward the precise synthesis of multivalent cathode materials that fundamentally overcome barriers to practical application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗