First-Principles Calculations of TiB4 and TiB5 as Anodes with High Capacity for Na-Ion Batteries.

The electrochemical properties of TiB4 and TiB5 monolayers in Na-ion batteries (NIBs) were studied by using the first-principles calculation method based on density functional theory. The TiB4/TiB5 monolayer showed excellent Na storage capacity, capable of adsorbing two layers of Na with theoretical capacities of 1176.77 and 1052.05 mA g-1, respectively. The average operating voltages of the TiB4 and TiB5 monolayers are 0.073 and 0.042 eV, respectively, indicating that they can be used as anode materials for NIBs. More interestingly, the exposed B surface not only brings a high theoretical capacity but also provides a relatively small diffusion barrier of 0.16 (for TiB4) and 0.33 eV (for TiB5), enhancing their rate capability in NIBs.

Unlocking the Power of Magnesium Batteries: Synergistic Effect of InSb-C Composites to Achieve Superior Electrochemical Performance.

Pure magnesium anode used in rechargeable magnesium batteries (RMB) exhibits high theoretical capacity but has been challenged by the passivation issue with conventional electrolytes. Alloy-type anodes have the potential to surpass this issue and have attracted increasing attention. However, the kinetic performance and stabilities of conventional alloy anodes are still constrained. In this study, the InSb-10%C anode is synthesized by a two-step high-energy ball milling process. The InSb-10%C anode exhibits a remarkably high capacity of up to 448 mA h g-1, significantly improved cycle performance (234 mA h g-1 at 100 cycles) and rate performance (168 mA h g-1 at 500 mA g-1). The above-mentioned superior performance of the InSb-10%C anode for RMBs is attributed to the cellular graphitized amorphous carbon composite structure (CGA) which effectively refines the particle size and restricts the volume expansion. Additionally, the reduced surface electron density of InSb combined with the high conductivity resulting from graphitization enhances the Mg2+ diffusion performance. Notably, the InSb-10%C anode demonstrates good compatibility with conventional halogen-free salt ether-based electrolytes in the full battery configuration.

H2O-Mg2+ Waltz-Like Shuttle Enables High-Capacity and Ultralong-Life Magnesium-Ion Batteries.

Mg-ion batteries (MIBs) are promising next-generation secondary batteries, but suffer from sluggish Mg2+ migration kinetics and structural collapse of the cathode materials. Here, an H2O-Mg2+ waltz-like shuttle mechanism in the lamellar cathode, which is realized by the coordination, adaptive rotation and flipping, and co-migration of lattice H2O molecules with inserted Mg2+, leading to the fast Mg2+ migration kinetics, is reported; after Mg2+ extraction, the lattice H2O molecules rearrange to stabilize the lamellar structure, eliminating structural collapse of the cathode. Consequently, the demo cathode of Mg0.75V10O24·nH2O (MVOH) exhibits a high capacity of 350 mAh g-1 at a current density of 50 mA g-1 and maintains a capacity of 70 mAh g-1 at 4 A g-1. The full aqueous MIB based on MVOH delivers an ultralong lifespan of 5000 cycles The reported waltz-like shuttle mechanism of lattice H2O provides a novel strategy to develop high-performance cathodes for MIBs as well as other multivalent-ion batteries.

Large-Scale Integration of the Ion-Reinforced Phytic Acid Layer Stabilizing Magnesium Metal Anode.

Rechargeable magnesium batteries (RMBs) have garnered significant attention for their potential in large-scale energy storage applications. However, the commercial development of RMBs has been severely hampered by the rapid failure of large-sized Mg metal anodes, especially under fast and deep cycling conditions. Herein, a concept proof involving a large-scale ion-reinforced phytic acid (PA) layer (100 cm × 7.5 cm) with an excellent water-oxygen tolerance, high Mg2+ conductivity, and favorable electrochemical stability is proposed to enable rapid and uniform plating/stripping of Mg metal anode. Guided by even distributions of Mg2+ flux and electric field, the as-prepared large-sized PA-Al@Mg electrode (5.8 cm × 4.5 cm) exhibits no perforation and uniform Mg plating/stripping after cycling. Consequently, an ultralong lifespan (2400 h at 3 mA cm-2 with 1 mAh cm-2) and high current tolerance (300 h at 9 mA cm-2 with 1 mAh cm-2) of the symmetric cell using the PA-Al@Mg anode could be achieved. Notably, the PA-Al@Mg//Mo6S8 full cell demonstrates exceptional stability, operating for 8000 cycles at 5 C with a capacity retention of 99.8%, surpassing that of bare Mg (3000 cycles, 74.7%). Moreover, a large-sized PA-Al@Mg anode successfully contributes to the stable pouch cell (200 and 750 cycles at 0.1 and 1 C), further confirming its significant potential for practical utilization. This work provides valuable theoretical insights and technological support for the practical implementation of RMBs.

Dual-Defect Engineering Strategy Enables High-Durability Rechargeable Magnesium-Metal Batteries.

Rechargeable magnesium-metal batteries (RMMBs) are promising next-generation secondary batteries; however, their development is inhibited by the low capacity and short cycle lifespan of cathodes. Although various strategies have been devised to enhance the Mg2+ migration kinetics and structural stability of cathodes, they fail to improve electronic conductivity, rendering the cathodes incompatible with magnesium-metal anodes. Herein, we propose a dual-defect engineering strategy, namely, the incorporation of Mg2+ pre-intercalation defect (P-Mgd) and oxygen defect (Od), to simultaneously improve the Mg2+ migration kinetics, structural stability, and electronic conductivity of the cathodes of RMMBs. Using lamellar V2O5·nH2O as a demo cathode material, we prepare a cathode comprising Mg0.07V2O5·1.4H2O nanobelts composited with reduced graphene oxide (MVOH/rGO) with P-Mgd and Od. The Od enlarges interlayer spacing, accelerates Mg2+ migration kinetics, and prevents structural collapse, while the P-Mgd stabilizes the lamellar structure and increases electronic conductivity. Consequently, the MVOH/rGO cathode exhibits a high capacity of 197 mAh g-1, and the developed Mg foil//MVOH/rGO full cell demonstrates an incredible lifespan of 850 cycles at 0.1 A g-1, capable of powering a light-emitting diode. The proposed dual-defect engineering strategy provides new insights into developing high-durability, high-capacity cathodes, advancing the practical application of RMMBs, and other new secondary batteries.

Study on Plastic Constitutive Relation and Ductile Fracture Criterion of AM60B Magnesium Alloy.

It is currently a challenge to accurately predict the deformation and fracture behavior of metal parts in automobile crashes. Many studies have shown that the deformation and fracture behavior of materials are significantly affected by the stress state during automobile crashes with complex stress state characteristics. In order to further promote the application of die-cast magnesium alloys in automobiles, it is particularly important to study the material deformation and fracture behavior of die-cast magnesium alloys. In this paper, the mechanical properties of the AM60B die-cast magnesium alloy sheet under four stress states (shear, tension, R10 notch tension, and cupping) were designed and tested. Based on the von Mises isotropic constitutive model and Swift weighted Hockett-Sherby hardening model, the plastic constitutive model of die-cast magnesium alloy was established. Based on the plastic model and the fracture model (JC, MMC, and DIEM) considering the influence of three stress states, the deformation and fracture behavior of the AM60B die-cast magnesium alloy front-end members in three-point bending were predicted by experiments and finite element simulation. The experimental results show that the deformation mode and loading-displacement curve trend of the AM60B die-cast magnesium alloy front members are the same, the crack initiation point and crack initiation time are the same, and the crack shape is similar. The results show that the complex stress state constitutive model parameters and the DIEM fracture model obtained in this paper can accurately predict the deformation and fracture failure behavior of the AM60B die-cast magnesium alloy sheet.

Covalent Organic Framework Membranes from Oppositely Charged Nanosheets toward Efficient Desalination.

Fabricating covalent organic framework (COF) membranes through the pre-assembly of nanosheets with different properties may open a novel avenue to the fabrication of advanced 2D membranes. Herein, COF membranes are fabricated using oppositely-charged COF nanosheets (CONs). Negatively-charged CONs and positively-charged CONs are pre-assembled through simple physical mixing, yielding the CONs with an aspect ratio of exceeding 10 000, which are assembled into three kinds of COF membranes. The optimal membranes exhibit the highest desalination performance with permeation flux of 132.66 kg m-2 h-1, salt rejection of 99.99%, and superior long-term operation stability.

Research Progress and the Prospect of Damping Magnesium Alloys.

As the lightest structural metal material, magnesium alloys possess good casting properties, high electrical and thermal conductivity, high electromagnetic shielding, and excellent damping properties. With the increasing demand for lightweight, high-strength, and high-damping structural materials in aviation, automobiles, rail transit, and other industries with serious vibration and noise, damping magnesium alloy materials are becoming one of the important development directions of magnesium alloys. A comprehensive review of the progress in this field is conducive to the development of damping magnesium alloys. This review not only looks back on the traditional damping magnesium alloys represented by Mg-Zr alloys, Mg-Cu-Mn alloys, etc. but also introduces the new damping magnesium materials, such as magnesium matrix composites and porous magnesium. But up to now, there have still been some problems in the research of damping magnesium materials. The effect of spiral dislocation on damping is still unknown and needs to be studied; the contradiction between damping performance and mechanical properties still lacks a good balance method. In the future, the introduction of more diversified damping regulating methods, such as adding other elements and reinforcements, optimizing the manufacturing method of damping magnesium alloy, etc., to solve these issues, will be the development trend of damping magnesium materials.

Catalyzing Desolvation at Cathode-Electrolyte Interface Enabling High-Performance Magnesium-Ion Batteries.

Magnesium ion batteries (MIBs) are expected to be the promising candidates in the post-lithium-ion era with high safety, low cost and almost dendrite-free nature. However, the sluggish diffusion kinetics and strong solvation capability of the strongly polarized Mg2+ are seriously limiting the specific capacity and lifespan of MIBs. In this work, catalytic desolvation is introduced into MIBs for the first time by modifying vanadium pentoxide (V2 O5 ) with molybdenum disulfide quantum dots (MQDs), and it is demonstrated via density function theory (DFT) calculations that MQDs can effectively lower the desolvation energy barrier of Mg2+ , and therefore catalyze the dissociation of Mg2+ -1,2-Dimethoxyethane (Mg2+ -DME) bonds and release free electrolyte cations, finally contributing to a fast diffusion kinetics within the cathode. Meanwhile, the local interlayer expansion can also increase the layer spacing of V2 O5 and speed up the magnesiation/demagnesiation kinetics. Benefiting from the structural configuration, MIBs exhibit superb reversible capacity (≈300 mAh g-1 at 50 mA g-1 ) and unparalleled cycling stability (15 000 cycles at 2 A g-1 with a capacity of ≈70 mAh g-1 ). This approach based on catalytic reactions to regulate the desolvation behavior of the whole interface provides a new idea and reference for the development of high-performance MIBs.

Theoretical insights into the intercalation mechanism of Li, Na, and Mg ions in a metallic BN/VS2 heterostructure.

Layered VS2 has been widely used as a battery anode material owing to its large specific surface area and controllable ion-transport channel. However, its semiconductor properties and poor cycling stability seriously limit its further applications. Herein, a two-dimensional BN/VS2 heterostructure (BVH) was constructed as an anode material for rechargeable metal-ion batteries (RMIBs). Demonstrated using first principles calculations, BVH exhibits a metallic property due to lattice stress between monolayer BN and VS2. BVH displays low ion diffusion energy barriers (0.13, 0.43, and 0.56 eV) and high theoretical capacities (447, 553.5, and 340.7 mA h g-1) for Li+, Na+, and Mg2+ storage. In BVH, the VS2 layer as the main redox center supports charge transfer, while the inactive BN layer enables high structural stability. This synergistic effect is expected to simultaneously achieve a high rate, high capacity, and long life. This design provides an important insight into developing new anode materials for RMIBs.

Biomineralization-Inspired Synthesis of Hybrid COF Nanosheets toward Efficient Desalination Membranes.

Synthesis of covalent organic framework nanosheets (CONs) with high aspect ratio is crucial to their assembly into advanced membranes. Nonetheless, the π-π stacking between covalent organic framework (COF) layers often leads to thick CONs. Herein, inspired by biomineralization process, a series of aspect ratio CONs >15 000 is synthesized by multifunctional polyelectrolytes which not only provide the nucleation sites for pre-assembly with COF monomer, but also suppress π-π interaction for anisotropic growth through protonation. The membrane assembled from CONs exhibited water permeance of 341 kg m-2 h-1 and salt rejection of 99.5% in desalination, outperforming ever-reported membranes. This method establishes a platform for the synthesis of crystalline nanosheets.

Dipole Coupling Accelerated H2 O Dissociation by Magnesium-Based Intermetallic Catalysts.

The water (H2 O) dissociation is critical for various H2 O-associated reactions, including water gas shift, hydrogen evolution reaction and hydrolysis corrosion. While the d-band center concept offers a catalyst design guideline for H2 O activation, it cannot be applied to intermetallic or main group elements-based systems because Coulomb interaction was not considered. Herein, using hydrolysis corrosion of Mg as an example, we illustrate the critical role of the dipole of the intermetallic catalysts for H2 O dissociation. The H2 O dissociation kinetics can be enhanced using Mgx Mey (Me=Co, Ni, Cu, Si and Al) as catalysts, and the hydrogen generation rate of Mg2 Ni-loaded Mg reached 80 times as high as Ni-loaded Mg. The adsorbed H2 O molecules strongly couple with the Mg-Me dipole of Mgx Mey , lowering the H2 O dissociation barrier. The dipole-based H2 O dissociation mechanism is applicable to non-transition metal-based systems, such as Mg2 Si and Mg17 Al12 , offering a flexible catalyst design strategy for controllable H2 O dissociation.

Organic Molecular Intercalation Enabled Anionic Redox Chemistry with Fast Kinetics for High Performance Magnesium Storage.

Rechargeable magnesium-ion batteries possess desirable characteristics in large-scale energy storage applications. However, severe polarization, sluggish kinetics and structural instability caused by high charge density Mg2+ hinder the development of high-performance cathode materials. Herein, the anionic redox chemistry in VS4 is successfully activated by inducing cations reduction and introducing anionic vacancies via polyacrylonitrile (PAN) intercalation. Increased interlayer spacing and structural vacancies can promote the electrolyte ions migration and accelerate the reaction kinetics. Thanks to this "three birds with one stone" strategy, PAN intercalated VS4 exhibits an outstanding electrochemical performance: high discharge specific capacity of 187.2 mAh g-1 at 200 mA g-1 after stabilization and a long lifespan of 5000 cycles at 2 A g-1 are achieved, outperforming other reported VS4-based materials to date for magnesium storage under the APC electrolyte. Theoretical calculations confirm that the intercalated PAN can indeed induce cations reduction and generate anionic vacancies by promoting electron transfer, which can accelerate the electrochemical reaction kinetics and activate the anionic redox chemistry, thus improving the magnesium storage performance. This approach of organic molecular intercalation represents a promising guideline for electrode material design on the development of advanced multivalent-ion batteries.

Binary Mg-1†at%Gd alloy anode for high-performance rechargeable magnesium batteries.

Rechargeable magnesium batteries (RMBs) become a highly promising candidate for the large-scale energy storage system by right of the high volumetric capacity, intrinsic safety and abundant resources of Mg anode. However, the uneven Mg stripping and large overpotential will cause a severe pitting perforation and the followed failure of Mg anode. Herein, we proposed a high-performance binary Mg-1 at% Gd alloy anode prepared by the melting and hot extrusion. The introduction of 1 at% Gd element can effectively reduce the Mg2+ diffusion energy barrier (0.34 eV) on alloy surface and induces the formation of a robust and low-resistance electrolyte/anode interphase, thus enabling a uniform and fast Mg plating/stripping. As a result, the Mg-1 at.% Gd anode displays a largely enhanced life of 220 h and a low overpotential of 213 mV at a high current density of 5.0 mA cm-2 with 2.5 mAh cm-2 . Moreover, the assembled Mg-1 at.% Gd//Mo6 S8 full cell delivers a high rate performance (73.5 mAh g-1 at 5 C) and ultralong cycling stability of 8000 cycles at 5 C. This work brings new insights to design the new-type and practical Mg alloy anodes for commercial RMBs.

Research Progress on the Damping Mechanism of Magnesium Alloys.

Magnesium alloys with high damping, high specific strength and low density have attracted great attention in recent years. However, the application of magnesium alloys is limited by the balance between their mechanical and damping properties. The strength and plasticity of magnesium alloys with high damping performance often cannot meet the industrial requirements. Understanding the damping mechanism of magnesium alloys is significant for developing new materials with high damping and mechanical properties. In this paper, the damping mechanisms and internal factors of the damping properties of magnesium alloys are comprehensively reviewed. Some damping mechanisms have been studied by many scholars, and it has been found that they can be used to explain damping performance. Among existing damping mechanisms, the G-L dislocation theory, twin damping mechanism and interface damping mechanism are considered common. In addition, some specific long-period stacking ordered (LPSO) phases' crystal structures are conducive to dislocation movement, which is good for improving damping performance. Usually, the damping properties of magnesium alloys are affected by some internal factors directly, such as dislocation density, solute atoms, grain texture and boundaries, etc. These internal factors affect damping performance by influencing the dissipation of energy within the crystal. Scholars are working to find novel damping mechanisms and suitable solute atoms that can improve damping performance. It is important to understand the main damping mechanisms and the internal factors for guiding the development of novel high-damping magnesium alloys.

Zwitterionic Covalent Organic Framework Based Electrostatic Field Electrocatalysts for Durable Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are one of the most promising candidates for next-generation energy storage systems. To develop long-life LSBs, there is an urgent need to develop functional materials with higher catalytic activity toward polysulfides and reduced dendritic lithium growth. Herein, an electrostatic field electrocatalyst is designed in a zwitterionic covalent organic framework (COF) with a "two birds with one stone" ability for simultaneously overcoming obstacles in the lithium metal anode and sulfur cathode. The synergism between cationic and anionic moieties in the zwitterionic COF creates an electrostatic field for bidirectionally catalyzing S cathode conversion. Besides, the rational design of zwitterionic COF as a separator modification layer allows lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) dissociation and fast lithium-ion conduction, which alleviates lithium dendrite growth and thus improves the cycling life of LSBs. This contribution not only pioneers the application of zwitterionic COF in the field of LSBs but also highlights the potential of electrostatic field electrocatalysts.

A two-dimensional VO2/VS2 heterostructure as a promising cathode material for rechargeable Mg batteries: a first principles study.

Rechargeable magnesium batteries (RMBs) are considered as highly promising energy storage systems. However, the lack of cathode materials with fast Mg2+ diffusion kinetics and high energy density severely hinders the development of RMBs. Herein, a two-dimensional (2D) VO2/VS2 heterostructure as a RMB cathode material is proposed by introducing an O-V-O layer in VS2 to improve the discharge voltage and specific capacity while keeping the fast Mg2+ diffusion kinetics. Based on first principle calculations, the geometric structures, electronic characteristics of the VO2/VS2 heterostructure, and the adsorption properties and diffusion behaviors of Mg2+ in VO2/VS2 are systematically studied. The metallic properties of VO2/VS2 and a relatively low diffusion barrier of Mg2+ (0.6 eV) in VO2/VS2 enable a large potential in delivering high rate performance in actual RMBs. Compared with traditional VS2 materials (1.25 V), the average discharge platform of VO2/VS2 could be increased to 1.7 V. The theoretical capacities of the layered VS2 and VO2/VS2 are calculated as 233 and 301 mA h g-1, respectively. Thus, the VO2/VS2 heterostructure exhibits a high theoretical energy density of 511.7 W h kg-1, significantly surpassing that of VS2 (291.3 W h kg-1). This work provides important guidance for designing high-energy and high-rate 2D heterostructure cathode materials for RMBs and other multivalent ion batteries.

Two-step fabrication of COF membranes for efficient carbon capture.

Covalent organic framework (COF) materials have been considered as disruptive membrane materials for gas separation. The dominant one-step method for COF nanosheet synthesis often suffers from coupling among polymerization, assembly and crystallization processes. Herein, we propose a two-step method comprising a framework assembly step and functional group switching step to synthesize COF nanosheets and the corresponding COF membranes. In the first step, the pristine COF-316 nanosheets bearing cyano groups are prepared via interfacial polymerization. In the second step, the cyano groups in COF-316 nanosheets were switched into amidoxime groups or carboxyl groups. Through the vacuum-assisted self-assembly method, the COF nanosheets were fabricated into membranes with a thickness below 100 nm. Featuring numerous mass transport channels and homogeneous distribution of functional groups, the amidoxime-modified COF-316 membrane demonstrated excellent separation performance, with a permeance above 500 GPU and a CO2/N2 selectivity above 50. The two-step method may inspire the rational design and fabrication of organic framework membranes.

Asymmetric Extrusion Technology of Mg Alloy: A Review.

Magnesium (Mg) alloy is a widely used lightweight metal structural material due to its high specific strength and stiffness, excellent damping performance, and recyclability. Wrought Mg alloys are particularly favored in fields such as aerospace, transportation, and biomedical stents. However, most wrought Mg alloys with a hexagonal close-packed (HCP) crystal structure lack sufficient independent slip systems to meet the von Mises criterion for uniform plastic deformation at room temperature. This can result in the formation of a strong basal texture during plastic deformation and poor room temperature plastic formability. Enhancing the room temperature forming performance is therefore a crucial challenge that needs to be addressed in order to expand the application of Mg alloy sheets. Our research group has comprehensively summarized significant work and the latest research progress in improving the room temperature forming of Mg alloy sheets via extrusion technology in recent years. Specifically, we have developed a new type of asymmetric extrusion technology that combines material structure evolution, mechanical properties, and forming behavior analysis. We have elucidated the extrusion process characteristics, texture control mechanism, and forming properties of Mg alloy sheets through plastic deformation mechanisms, mold design, and finite element numerical simulation. The findings of our study present an innovative extrusion technology for the fabrication of highly formable Mg alloy sheets, which can be utilized in various applications.

Enabling Ultrafast Single Mg2+ Insertion Kinetics of Magnesium-Ion Batteries via In Situ Dynamic Catalysis and Re-equilibration Effects.

Magnesium-ion batteries (MIBs) have great potential in large-scale energy storage field with high capacity, excellent safety, and low cost. However, the strong solvation effect of Mg2+ will lead to the formation of solvated ions in electrolytes with larger size and sluggish diffusion/reaction kinetics. Here, the concept of interfacial catalytic bond breaking is first introduced into the cathode design of MIBs by hybriding MoS2 quantum dots with VS4 (VS4@MQDs) as the cathode. The "in situ dynamic catalysis and re-equilibration" effects can catalyze the Cl-Mg bond breaking and trigger single Mg2+ insertion/extraction chemistries, which can significantly accelerate the diffusion and reaction kinetics, as verified by the decreased diffusion energy barriers (0.26 eV for Mg2+ vs 2.47 eV for MgCl+) and fast diffusion coefficient. Benefitting from these dynamic catalysis effects, the constructed VS4@MQD-based MIBs deliver a high discharge capacity of ∼120 mA h g-1 at 200 mA g-1 and a long-term cyclic stability of 1000 cycles at 1 A g-1. The improved performance and detailed characterizations well prove that the active ions in MIBs change from MgCl+/Mg2Cl3+ to Mg2+ with fast kinetics.