Unraveling Energy Storage Performance and Mechanism of Metal-Organic Framework-Derived Copper Vanadium Oxides with Tunable Composition for Aqueous Zinc-Ion Batteries.

Achieving high-performance aqueous zinc (Zn)-ion batteries (AZIBs) requires stable and efficient cathode materials capable of reversible Zn-ion intercalation. Although layered vanadium oxides possess high Zn-ion storage capacity, their sluggish kinetics and poor conductivity present significant hurdles for further enhancing the performance of AZIBs. In response to this challenge, a dissolution-regrowth and conversion approach is formulated using metal-organic frameworks (MOFs) as a sacrificial template, which enables the in situ creation of copper vanadium oxides (CuVOx) with porous 1D channels and distinctive nanoarchitectures. Owing to their distinctive structure, the optimized CuVOx cathode experiences a reaction involving the synergistic insertion/extraction of Zn2+, resulting in rapid Zn2+ diffusion kinetics and enhanced electrochemical activity postactivation. Specifically, the activated electrode delivers a reversible capacity of 519 mAh g-1 at 0.5 A g-1 for AZIBs. It is noteworthy that the electrode exhibits a remarkable reversible rate capacity of 220 mAh g-1 at 5 A g-1 with excellent durable cycleability, retaining 88% of its capacity even after 3000 cycles. Various ex situ testing methods endorse the reversible insertion/extraction of Zn2+ in the CuVOx cathode. This study provides a novel insight into high-performance MOF-derived unique structure designs for AZIB electrodes.

Hydrogen Peroxide Tuned Morphology and Crystal Structure of Barium Vanadate-Based Nanostructures for Aqueous Zinc-Ion Storage Properties.

Improving the layered-structure stability and suppressing vanadium (V) dissolution during repeated Zn2+ insertion/extraction processes are key to promoting the electrochemical stability of V-based cathodes for aqueous zinc (Zn)-ion batteries (AZIBs). In this study, barium vanadate (Ba2V2O7, BVO) nanostructures (NSs) are synthesized using a facile hydrothermal method. The formation process of the BVO NSs is controlled by adjusting the concentration of hydrogen peroxide (H2O2), and these NSs are employed as potential cathode materials for AZIBs. As the H2O2 content increases, the corresponding electrochemical properties demonstrate a discernible parabolic trend, with an initial increase, followed by a subsequent decrease. Benefiting from the effect of H2O2 concentration, the optimized BVO electrode with 20 mL H2O2 delivers a specific capacity of 180.15 mA h g-1 at 1 A g-1 with good rate capability and a long-term cyclability of 158.34 mA h g-1 at 3 A g-1 over 2000 cycles. Thus, this study provides a method for designing cathode materials with robust structures to boost the electrochemical performance of AZIBs.

Oxygenated copper vanadium selenide composite nanostructures as a cathode material for zinc-ion batteries with high stability up to 10 000 cycles.

The development of aqueous zinc-ion batteries (AZiBs) towards practical implementations is hampered by unsuitable host cathode materials. Herein, we reported a high-capacity, stable, and long-cycle-life (10 000 cycles) oxygenated copper vanadium selenide composite material (Cu0.59V2O5/Cu0.828V2O5@Cu1.8Se1/Cu3Se2, denoted as O-CuVSe) as a cathode for AZiBs. The newly constructed O-CuVSe composite cathode can be operated in the wide potential window of 0.4-2.0 V, exhibiting a high specific capacity of 154 mA h g-1 at 0.2 A g-1 over 100 cycles. Interestingly, the O-CuVSe composite cathode delivered excellent specific capacities of 117 and 101.4 mA h g-1 over 1000 cycles at 1 and 2 A g-1, respectively. Even at a high current density of 5 A g-1, the cathode delivered a high reversible capacity of 74.5 mA h g-1 over an ultra-long cycling life of 10 000 cycles with no obvious capacity fading. Apart from this, the cathode exhibited excellent rate capability at different current densities. The superior electrochemical properties originate from the synergistic effects between the oxygen vacancy engineering and interlayer doping of Cu ions to increase the structural stability during the cycling, enhancing the electron/ion transport kinetics. Moreover, the Zn2+ storage mechanism in the Zn/O-CuVSe aqueous rechargeable battery was explored. This study provides a new opportunity for the fabrication of different kinds of a new class of cathode materials for high-voltage and high-capacity AZiBs and other energy storage devices.

Metal-Organic Framework-Derived Co3 V2 O8 @CuV2 O6 Hybrid Architecture as a Multifunctional Binder-Free Electrode for Li-Ion Batteries and Hybrid Supercapacitors.

Metal-organic frameworks (MOFs) are promising materials in diverse fields because of their constructive traits of varied structural topologies, high porosity, and high surface area. MOFs are also an ideal precursor/template to derive porous and functional morphologies. Herein, Co3 V2 O8 nanohexagonal prisms are grafted on CuV2 O6 nanorod arrays (CuV-CoV)-grown copper foam (CF) using solution-processing methods, followed by thermal treatment. Direct preparation of active material on CF can potentially eliminate electrochemically inactive and non-conductive binders, leading to improved charge-transfer rate. Furthermore, solution-processing methods are simple and cost-effective. Owing to versatile valence states and good redox activity, the vanadium-incorporated mixed metal oxides (CuV-CoV) exhibited superior electrochemical performance in lithium (Li)-ion battery and supercapacitor (SC) studies. Furthermore, hollow carbon particles (HCPs) derived from MOF particles (MOF-HCPs) are used as the anode material in SCs. A hybrid SC (HSC) fabricated with CuV-CoV and MOF-HCP materials exhibited noteworthy electrochemical properties. Moreover, a solid-state HSC (SSHSC) is constructed and its real-time feasibility is investigated by harvesting the dynamic energy of a bicycle with the help of a direct current generator. The charged SSHSCs potentially powered various electronic components.

Graphene Matrix Sheathed Metal Vanadate Porous Nanospheres for Enhanced Longevity and High-Rate Energy Storage Devices.

Rational design of anode materials comprising rich benefits of high capacity, superior rate capability, and exalted lifetime is of considerable significance in the progress of high-performance Li-ion batteries (LIBs) and supercapatteries. Herein, highly porous cobalt vanadate (Co2VO4) nanospheres encapsulated with reduced graphene oxide (rGO) nanosheets (rGO@CoV PNSs) were prepared by a facile hydrothermal method and employed as a hybrid composite-based anode material for energy storage devices. The nanocavities and porous features of CoV nanospheres, and the laminated rGO nanosheets over CoV PNSs can significantly surpass the volume changes and enhance the surface electrokinetics, respectively. With benefits of rich redox activity and constructive traits, the rGO@CoV PNSs as an electrode material in LIBs exhibited superior reversible capacity of 780.6 mAh/g after 100 cycles with remarkable rate performance. Moreover, the hybrid composite displayed an excellent reversible capacity of 531.8 mAh/g even after 1000 cycles performed at 1000 mA/g. Utilizing the synergistic features, the rGO@CoV PNSs composite was also explored as a battery-type electrode for supercapatteries. The fabricated supercapattery device with rGO@CoV PNSs and rGO demonstrated good rate performance including superior areal energy (0.048 mWh/cm2) and power (9.96 mW/cm2) densities. Therefore, the graphene sheathed metal vanadates would be an ultrahigh rate electrode candidates for energy storage devices.

Ternary MOF-Based Redox Active Sites Enabled 3D-on-2D Nanoarchitectured Battery-Type Electrodes for High-Energy-Density Supercapatteries.

Designing rationally combined metal-organic frameworks (MOFs) with multifunctional nanogeometries is of significant research interest to enable the electrochemical properties in advanced energy storage devices. Herein, we explored a new class of binder-free dual-layered Ni-Co-Mn-based MOFs (NCM-based MOFs) with three-dimensional (3D)-on-2D nanoarchitectures through a polarity-induced solution-phase method for high-performance supercapatteries. The hierarchical NCM-based MOFs having grown on nickel foam exhibit a battery-type charge storage mechanism with superior areal capacity (1311.4 µAh cm-2 at 5 mA cm-2), good rate capability (61.8%; 811.67 µAh cm-2 at 50 mA cm-2), and an excellent cycling durability. The superior charge storage properties are ascribed to the synergistic features, higher accessible active sites of dual-layered nanogeometries, and exalted redox chemistry of multi metallic guest species, respectively. The bilayered NCM-based MOFs are further employed as a battery-type electrode for the fabrication of supercapattery paradigm with biomass-derived nitrogen/oxygen doped porous carbon as a negative electrode, which demonstrates excellent capacity of 1.6 mAh cm-2 along with high energy and power densities of 1.21 mWh cm-2 and 32.49 mW cm-2, respectively. Following, the MOF-based supercapattery was further assembled with a renewable solar power harvester to use as a self-charging station for various portable electronic applications.

Synergistic Effects of Cobalt Molybdate@Phosphate Core-Shell Architectures with Ultrahigh Capacity for Rechargeable Hybrid Supercapacitors.

Designing binder-free and core-shell-like electrode materials with synergistic effects has attracted widespread attention for the development of high energy density hybrid supercapacitors (HSCs). Herein, binder-free cobalt molybdate nanosheet-laminated cobalt phosphate micropetals on nickel foam (CoM NS@CoP/NF) were facilely prepared for use as an effective battery-type electrode in HSCs. With the multifunctional features, the rationally combined core-shell-like CoM NS@CoP/NF electrode exhibited a maximum capacity of 886.8 µA h/cm2 at a current density of 5 mA/cm2 with a good rate capability of 64.2% and cycling stability of 87.4% (after 10 000 cycles). The high electrochemical performance of the hybrid composite could be attributed to the synergistic effects of hierarchical architectures and large accessible electroactive area, which facilitates the fast electron/transportation within the active material and accelerates the redox chemistry process. Utilizing the superior energy-storage properties, a pouch-type HSC was fabricated with core-shell-like CoM NS@CoP-6 h architectures as a battery-type electrode and activated carbon as a capacitive-type electrode in an aqueous alkaline electrolyte. The miniature hybrid device exhibited maximum energy and power densities of 0.44 mW h/cm2 and 40.35 mW/cm2, respectively, with good cycling stability. Moreover, the HSCs can energize various portable electronic equipments, which demonstrates their suitability for real-time applications.

Role of quercetin and caloric restriction on the biomolecular composition of aged rat cerebral cortex: An FTIR study.

Aging brain is characterized by a change in biomolecular composition leading to a diverse range of neurological diseases. Anti-aging research is of current interest, to lessen the burden of age-related macromolecular damage through antioxidant supplementation and caloric restriction. However, data concerning the effect of these anti-aging regimens on age-related biomolecular changes in rat brain is still lacking. In the present study, for the first time, we employed Fourier transform infrared (FTIR) spectroscopy, to investigate the effect of quercetin, caloric restriction (CR) and combination of both on alterations in the composition of lipids and proteins of aged rat brain cerebral cortex. Aged male Wistar rats (21 months old) were divided into four groups: Control (CONT), fed pellet diet; Quercetin (QUER), fed quercetin (50 mg/kg/day); CR (caloric restriction) (fed 40% reduced CONT), and CRQ (40% CR and 50 mg/kg/day QUER). Three-month-old rats served as young control (YOUNG). Our short-term study (45 days) shows decreased band area of unsaturated lipids, decreased area ratios of olefinic/lipid and CH2 antisymmetric stretching (2925 cm-1)/lipids in CONT group compared to young rats, suggesting age-associated lipid peroxidation in aged rats. A slight decrease in the frequency of CH2 antisymmetric mode of lipids (whereas no change in CH2 symmetric mode), but a decrease in bandwidths of both CH2 antisymmetric and symmetric modes of lipids was observed for CONT group compared to YOUNG. Further, a significant decrease in the peak area of infrared bands of proteins and an increase in the peak area of the CO band of lipids was observed in the CONT group. Our data also show that lower levels of α-helical structures and higher levels of random coils, representing altered protein secondary structure composition in the CONT group compared to YOUNG group. Reduction in neuronal cell density and shrinked nucleus was also observed in aged rats. Increase in the accumulation of oxidative mediated damage to macromolecules and diminished antioxidant levels, could be the possible reason for the age-related alterations in the composition of lipids and proteins. However, the combination of quercetin and CR, but not either treatment alone, significantly prevented the age associated alterations in the lipid and protein profiles in the rat cerebral cortex. Further, our results help to understand the mechanism of action of antioxidants under non-restriction and CR conditions, this might help in the development of novel anti-aging treatments to ameliorate oxidative stress in age-related disorders.