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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.
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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.
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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.
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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.
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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 (V2O5) 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 V2O5 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.
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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.
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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.
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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 80â 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.
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Using N2O as a universal reaction gas, a new strategy was proposed for the highly sensitive interference-free simultaneous determination of nonmetallic impurity elements in high-purity magnesium (Mg) alloys by ICP-MS/MS. In the MS/MS mode, through O-atom and N-atom transfer reactions, 28Si+ and 31P+ were converted to the oxide ions 28Si16O2+ and 31P16O+, respectively, while 32S+ and 35Cl+ were converted to the nitride ions 32S14N+ and 14N35Cl+, respectively. The ion pairs formed via the 28Si+ â 28Si16O2+, 31P+ â 31P16O+, 32S+ â 32S14N+, and 35Cl+ â 14N35Cl+ reactions by the mass shift method could eliminate spectral interferences. Compared with the O2 and H2 reaction modes, the present approach delivered much higher sensitivity and lower limit of detection (LOD) of the analytes. The accuracy of the developed method was evaluated via standard addition method and comparative analysis by sector field ICP-MS (SF-ICP-MS). The study indicates that in the MS/MS mode, use of N2O as reaction gas can provide interference-free conditions and sufficiently low LODs for analytes. The LODs of Si, P, S, and Cl could reach down to 17.2, 4.43, 10.8, and 31.9 ng L-1, respectively, and the recoveries were in the range of 94.0-106%. The determination results of the analytes were consistent with those obtained by SF-ICP-MS. This study presents a systematic method for the precise and accurate quantification of Si, P, S, and Cl in high-purity Mg alloys by ICP-MS/MS. The developed method provides valuable reference that can be expanded and applied to other fields.
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With the pursuit of high-energy-density for lithium-ion batteries (LIBs), the hidden safety problems of batteries have gradually emerged. LiNix Coy Mn1- x - y O2 (NCM) is considered as an ideal cathode material to meet the urgent needs of high-energy-density batteries. However, the oxygen precipitation reaction of NCM cathode at high temperature brings serious safety concerns. In order to promote high-safety lithium-ion batteries, herein, a new type of flame-retardant separator is prepared using flame-retardant (melamine pyrophosphate, MPP) and thermal stable Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). MPP takes the advantage of nitrogen-phosphorus synergistic effect upon the increased internal temperature of LIBs, including the dilution effect of noncombustible gas and the rapidly suppression of undesirable thermal runaway. The developed flame-retardant separators show negligible shrinkage over 200 °C and it takes only 0.54 s to extinguish the flame in the ignition test, which are much superior to commercial polyolefin separators. Moreover, pouch cells are assembled to demonstrate the application potential of PVDF-HFP/MPP separators and further verify the safety performance. It is anticipated that the separator with nitrogen-phosphorus flame-retardant can be extensively applied to various high-energy-density devices owing to simplicity and cost-effectiveness.
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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.
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Ultrathin covalent organic framework (COF) membranes are urgently demanded in molecular/ionic separations. Herein, we reported an electrochemical interfacial polymerization strategy to fabricate ultrathin COF membranes with thickness of 85â nm, by actively manipulate self-healing effect and self-inhibiting effect. The resulting COF membrane exhibited superior performance in brine desalination with the permeation flux of 92â kg m-2 h-1 and the rejection of 99.96 %. Our electrochemical interfacial polymerization strategy enriches the fabrication approach of COF membranes and facilitates the rational design of ultrathin membranes.
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A new strategy for the determination of metal impurities in magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) electrolytes for rechargeable magnesium batteries using inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) was proposed. Mg(TFSI)2 was dissolved in 1,2-dimethoxyethane (DME), and 13 metal impurity elements were directly determined. Since N2 has a lower O atom affinity (1.6 eV) than the O atom (5.2 eV), N2O was a more effective O atom transfer gas than O2. In the MS/MS mode, N2O was selected as the reaction gas, and high sensitivities and low limits of detection (LODs) of analytes were obtained by mass shift methods. The accuracy of proposed analytical methods was assessed by the spike recovery experiments and comparative analyses using sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). LODs were in the range of 0.18-26.6 ng kg-1, the recoveries were 92.5%-107%, and the relative standard deviation (RSD) was 2.0%-5.3%. No significant difference was observed between the ICP-MS/MS and SF-ICP-MS results at a 95% confidence level. The measurement realized the rapid determination of 13 metal impurity elements in Mg(TFSI)2 using N2O as a reaction gas with high sensitivity, accuracy, and precision. The method was applied for the analysis of Mg(TFSI)2 products with satisfactory results.
Assuntos
Magnésio , Espectrometria de Massas em Tandem , Eletrólitos , Limite de Detecção , Análise Espectral , Espectrometria de Massas em Tandem/métodosRESUMO
Rechargeable magnesium batteries (RMBs) suffer from low capacity and poor cyclability of cathode materials, which is due to the sluggish Mg2+ diffusion kinetics and large lattice strain. Here, a layer-interweaving mechanism in lamellar cathode to simultaneously facilitate Mg2+ diffusion and release Mg2+ -insertion strain is reported. In the Cu3 V2 O7 (OH)2 ·2H2 O (CVOH) cathode, Mg2+ diffusion highways are generated by the vertical interweaving of CVOH layers and V6 O13 layers that nucleate in CVOH during discharging, which are switchable by Mg2+ insertion/extraction. These highways enhance the Mg2+ diffusion coefficient by three orders of magnitude and release 50% Mg2+ -insertion strain. This enables CVOH to exhibit a high capacity of 262 mAh g-1 at high current density of 250 mA g-1 in aqua, and extremely low capacity loss of 0.0004% per cycle in the activated carbon//CVOH cell. This work inspires designing the magnesiation phase transformation of electrodes to resolve both kinetic and strain issues for high-performance RMBs.
Assuntos
Fontes de Energia Elétrica , Magnésio , EletrodosRESUMO
A composite coating with good load-carrying and controlled release capabilities for the corrosion inhibitor benzotriazole (BTA) was prepared while providing active and passive corrosion protection for magnesium alloy systems. In this paper, the organic corrosion inhibitor BTA was loaded into the ZIF-8/GO hybrid (GZB), and then, the GZB composite was coated with hexadecyltrimethoxysilane (HDTMS). Then, the GZB composites carried by HDTMS were made to adhere a ternary MgAlY layered double hydroxide (LDH) coating based on microarc oxidation (MAO) coating by electrophoresis (Si-MgAlY LDH coating). The successful loading of BTA by GZB composites was verified by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Meanwhile, the Si-MgAlY LDH coating was characterized by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The potentiodynamic polarization curves show that the corrosion current density of the Si-MgAlY LDH coating reaches (2.08 ± 0.49) × 10-9 A/cm2, which means that the Si-MgAlY LDH coating greatly improves the corrosion resistance of magnesium alloy AZ31. The Si-MgAlY LDH coating can also achieve self-healing function in harsh environments, which is attributed to the synergistic effect of passive and active protection. The composite coating is of great significance to expand the potential applications of magnesium alloys.
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Although magnesium rechargeable batteries (MRBs) have gained considerable attention, research relating to MRBs is still in its infancy. One issue is that magnesium ions are difficult to reversibly (de)intercalate in most electrode materials. Among various available cathodes, VO2(B) is a promising layered cathode material for use in MRBs. Totally different from monolayer VO2, the magnesiation mechanism in monoclinic bulk VO2(B) has not been clearly clarified to this day. For the first time, we systematically investigated the influence of magnetism and van der Waals (vdW) forces on the electronic structure and diffusion kinetics of magnesium in bulk VO2(B) using a series of DFT+U calculations. The Mg diffusivity can reach a high value of 1.62 × 10-7 cm2 s-1 at 300 K, which is comparable to Li+. These results demonstrate that VO2(B) is a potential host material with high mobility and fast kinetics.
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Molecular separations that enable selective transport of target molecules from gas and liquid molecular mixtures, such as CO2 capture, olefin/paraffin separations, and organic solvent nanofiltration, represent the most energy sensitive and significant demands. Membranes are favored for molecular separations owing to the advantages of energy efficiency, simplicity, scalability, and small environmental footprint. A number of emerging microporous organic materials have displayed great potential as building blocks of molecular separation membranes, which not only integrate the rigid, engineered pore structures and desirable stability of inorganic molecular sieve membranes, but also exhibit a high degree of freedom to create chemically rich combinations/sequences. To gain a deep insight into the intrinsic connections and characteristics of these microporous organic material-based membranes, in this review, for the first time, we propose the concept of organic molecular sieve membranes (OMSMs) with a focus on the precise construction of membrane structures and efficient intensification of membrane processes. The platform chemistries, designing principles, and assembly methods for the precise construction of OMSMs are elaborated. Conventional mass transport mechanisms are analyzed based on the interactions between OMSMs and penetrate(s). Particularly, the 'STEM' guidelines of OMSMs are highlighted to guide the precise construction of OMSM structures and efficient intensification of OMSM processes. Emerging mass transport mechanisms are elucidated inspired by the phenomena and principles of the mass transport processes in the biological realm. The representative applications of OMSMs in gas and liquid molecular mixture separations are highlighted. The major challenges and brief perspectives for the fundamental science and practical applications of OMSMs are tentatively identified.
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Ion selective separators with the capability of conducting lithium ion and blocking polysulfides are critical and highly desired for high-performance lithium-sulfur (Li-S) batteries. Herein, we fabricate an ion selective film of covalent organic framework (denoted as TpPa-SO3Li) onto the commercial Celgard separator. The aligned nanochannels and continuous negatively charged sites in the TpPa-SO3Li layer can effectively facilitate the lithium ion conduction and meanwhile significantly suppress the diffusion of polysulfides via the electrostatic interaction. Consequently, the TpPa-SO3Li layer exhibits excellent ion selectivity with an extremely high lithium ion transference number of 0.88. When using this novel functional layer, the Li-S batteries with a high sulfur loading of 5.4 mg cm-2 can acquire a high initial capacity of 822.9 mA h g-1 and high retention rate of 78% after 100 cycles at 0.2 C. This work provides new insights into developing high-performance Li-S batteries via ion selective separator strategy.
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Rechargeable magnesium batteries (RMBs) have been considered a promising energy-storage device due to their high energy density and high safety, but they still suffer from a lack of high-rate performance and cycle performance of the cathode. Nanosized CuCo2 S4 /Cu7.2 S4 composites have been synthesized for the first time by a facile solvothermal method. Herein, the magnesium ion storage behavior when applied in the cathode for RMBs is discussed. Electrochemical results demonstrated that the CuCo2 S4 /Cu7.2 S4 composites exhibit a high initial discharge capacity of 256â mAh g-1 at 10â mA g-1 and 123â mAh g-1 at 300â mA g-1 at room temperature and an outstanding long-term cyclic stability over 300â cycles at 300â mA g-1 . Furthermore, the electrochemical storage mechanism demonstrated that the storage process of magnesium ion in the CuCo2 S4 /Cu7.2 S4 cathode is mainly driven by strong pseudocapacitive effects.
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The application of magnesium alloys is seriously limited by their poor environmental adaptability. In this work, we report a robust superamphiphobic coating, which endows magnesium alloys with extraordinary environmental adaptability. The coating was fabricated on magnesium alloys by a facile, cost-effective, and scalable method, one-step particle-free spraying. The as-treated magnesium alloys show excellent superamphiphobicity with the static contact angles (CAs) of water, ethylene glycol, benzyl alcohol, and cyclohexanol droplets of 157.5°, 155.1°, 151.7°, and 151.3°, respectively. These samples also display small dynamic CAs (0° for water and 10° for ethylene glycol) and water super-repellency, which endow magnesium surfaces with droplet impact resistance, self-cleaning, and oil-resistance functions. The simulating environmental-adaptability tests demonstrate that the as-treated magnesium alloys can remain superamphiphobic under various mechanical, chemical, and physical damages including sand impact (⩾10 cycles), water impact (v = 4.5 m·s-1, 2 impacts·s-1, 20 h), abrasion (1.0 kPa, 50 cycles), strong acid/alkaline solution (pH = 1-14), organic solvents immersion (ethylene glycol, n-hexane, ≥48 h), high temperature (200 °C, 72 h), and ultraviolet irradiation (λ = 254 nm, 672 h). The natural environmental-adaptability tests in the acidic industrial atmosphere for 40 days further confirm the robustness of the as-treated magnesium alloys under harsh environments. This work not only provides a promising method for industrially fabricating environmental-adaptable coatings on metallic materials but also paves the way for the much wider applications of magnesium alloys.