Synchronous organic-inorganic co-intercalated ammonium vanadate cathode for advanced aqueous zinc-ion batteries

Vanadium-based cathode materials are attractive for aqueous zinc-ion batteries(AZIBs)owing to the high capacity from their open frameworks and multiple valences.However,the cycle stability and rate capability are still restricted by the low electrical conductivity and trapped diffusion kinetics.Here,we propose an organic-inorganic co-intercalation strategy to regulate the structure of ammonium vanadate(NH_(4)V_(4)O_(10),NVO).The introduction of Al^(3+)and polyaniline(PANI)induces the optimized layered structure and generation of urchin-like hierarchical construction(AP-NVO),based on heterogeneous nucleation and dissolution-recrystallization growth mechanism.Owing to these favorable features,the AP-NVO electrode delivers a desirable discharge capacity of 386 mA h g^(-1) at 1.0 A g^(-1),high-rate capability of 263 mA h g^(-1 )at 5.0 A g^(-1) and excellent cycling stability with 80.4%capacity retention over 2000 cycles at 5.0 A g^(-1).Such satisfactory electrochemical performance is believed to result from the enhanced reaction kinetics provided by the stable layered structure and a high intercalation pseudo-capacitance reaction.These results could provide enlightening insights into the design of layered vanadium oxide cathodematerials.

Fast and Stable Zinc Anode‑Based Electrochromic Displays Enabled by Bimetallically Doped Vanadate and Aqueous Zn^(2+)/Na^(+)Hybrid Electrolytes

Vanadates are a class of the most promising electrochromic materials for displays as their multicolor characteristics.However,the slow switching times and vanadate dissolution issues of recently reported vanadates significantly hinder their diverse practical applications.Herein,novel strategies are developed to design electrochemically stable vanadates having rapid switching times.We show that the interlayer spacing is greatly broadened by introducing sodium and lanthanum ions into V_(3)O_(8)interlayers,which facilitates the transportation of cations and enhances the electrochemical kinetics.In addition,a hybrid Zn^(2+)/Na^(+)electrolyte is designed to inhibit vanadate dissolution while significantly accelerating electrochemical kinetics.As a result,our electrochromic displays yield the most rapid switching times in comparison with any reported Zn-vanadate electrochromic displays.It is envisioned that stable vanadate-based electrochromic displays having video speed switching are appearing on the near horizon.

Tailored BiVO_(4)/In_(2)O_(3)nanostructures with boosted charge separation ability toward unassisted water splitting

The development of new heterostructures with high photoactivity is a breakthrough for the limitation of solar-driven water splitting.Here,we first introduce indium oxide(In_(2)O_(3))nanorods(NRs)as a novel electron transport layer for bismuth vanadate(BiVO_(4))with a short charge diffusion length.In_(2)O_(3)NRs reinforce the electron transport and hole blocking of BiVO_(4),surpassing the state-of-the-art photoelectrochemical performances of BiVO_(4)-based photoanodes.Also,a tannin-nickel-iron complex(TANF)is used as an oxygen evolution catalyst to speed up the reaction kinetics.The final TANF/BiVO_(4)/In_(2)O_(3)NR photoanode generates photocurrent densities of 7.1 mAcm^(−2) in sulfite oxidation and 4.2 mA cm^(−2) in water oxidation at 1.23 V versus the reversible hydrogen electrode.Furthermore,the“artificial leaf,”which is a tandem cell with a perovskite/silicon solar cell,shows a solar-to-hydrogen conversion efficiency of 6.2%for unbiased solar water splitting.We reveal significant advances in the photoactivity of TANF/BiVO_(4)/In_(2)O_(3)NRs from the tailored nanostructure and band structure for charge dynamics.

Na2V6O16·2.14H2O nanobelts as a stable cathode for aqueous zinc-ion batteries with long-term cycling performance

Aqueous zinc-ion batteries(ZIBs) have been considered as one of the most promising electrochemical devices for large-scale energy storage system owing to their low cost and high safety. Herein, Na2V6O16·2.14H2O nanobelts are synthesized and applied as cathode material for ZIBs. The sample displays a high capacity of 466 m Ahg^-1 at 100 mAg^-1 and stable cycling performance with a capacity retention of 90% over 20 0 0 cycles at the 20 Ag^-1. Moreover, Na2V6O16·2.14H2O presents a capable rate ability and a high energy density of 312 Wh kg^-1 at a specific power of 70 Wkg^-1. The superior electrochemical performance is attributed to the large interlayer spacing and outstanding structure stability, which promise the highly reversible intercalation and extraction of zinc ion. The electrochemical kinetics and zinc ion storage mechanism are also investigated. This work demonstrates that nanoscale electrode materials with large interlayer spacing can effectively enhance the electrochemical performance of aqueous ZIBs, which can be extended to other metal ion batteries, such as magnesium ion batteries and aluminum ion batteries.

Rechargeable Aqueous Zinc-Ion Batteries in MgSO4/ZnSO4 Hybrid Electrolytes

MgSO4 is chosen as an additive to address the capacity fading issue in the rechargeable zinc-ion battery system of MgxV2O5·nH2O//ZnSO4//zinc.Electrolytes with different concentration ratios of ZnSO4 and MgSO4 are investigated.The batteries measured in the 1 M ZnSO4^-1 M MgSO4 electrolyte outplay other competitors,which deliver a high specific capacity of 374 mAh g^-1 at a current density of 100 mA g^-1 and exhibit a competitive rate performance with the reversible capacity of 175 mAh g^-1 at 5 A g^-1.This study provides a promising route to improve the performance of vanadium-based cathodes for aqueous zinc-ion batteries with electrolyte optimization in cost-effective electrolytes.

Ultra-High Mass-Loading Cathode for Aqueous Zinc-Ion Battery Based on Graphene-Wrapped Aluminum Vanadate Nanobelts

Rechargeable aqueous zinc-ion batteries(AZIBs)have their unique advantages of cost efficiency,high safety,and environmental friendliness.However,challenges facing the cathode materials include whether they can remain chemically stable in aqueous electrolyte and provide a robust structure for the storage of Zn2+.Here,we report on H11Al2V6O23.2@graphene(HAVO@G)with exceptionally large layer spacing of(001)plane(13.36?).The graphene-wrapped structure can keep the structure stable during discharge/charge process,thereby promoting the inhibition of the dissolution of elements in the aqueous electrolyte.While used as cathode for AZIBs,HAVO@G electrode delivers ideal rate performance(reversible capacity of 305.4,276.6,230.0,201.7,180.6 mAh g?1 at current densities between 1 and 10 A g?1).Remarkably,the electrode exhibits excellent and stable cycling stability even at a high loading mass of^15.7 mg cm?2,with an ideal reversible capacity of 131.7 mAh g?1 after 400 cycles at 2 A g?1.

Electro-deoxidation of V_2O_3 in molten CaCl_2-NaCl-CaO

The electro-deoxidation of V2O3 precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl2 and NaC1 with additions of CaO, a cathode of compact V2O3, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. 3 g of V2O3 could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V2O3 formed the intermediate product CaV2O4.

High‑Energy and High‑Power Pseudocapacitor–Battery Hybrid Sodium‑Ion Capacitor with Na^(+) Intercalation Pseudocapacitance Anode

High-performance and low-cost sodium-ion capacitors(SICs)show tremendous potential applications in public transport and grid energy storage.However,conventional SICs are limited by the low specific capacity,poor rate capability,and low initial coulombic efficiency(ICE)of anode materials.Herein,we report layered iron vanadate(Fe5V15O39(OH)9·9H2O)ultrathin nanosheets with a thickness of~2.2 nm(FeVO UNSs)as a novel anode for rapid and reversible sodium-ion storage.According to in situ synchrotron X-ray diffractions and electrochemical analysis,the storage mechanism of FeVO UNSs anode is Na+intercalation pseudocapacitance under a safe potential window.The FeVO UNSs anode delivers high ICE(93.86%),high reversible capacity(292 mAh g^−1),excellent cycling stability,and remarkable rate capability.Furthermore,a pseudocapacitor–battery hybrid SIC(PBH-SIC)consisting of pseudocapacitor-type FeVO UNSs anode and battery-type Na3(VO)2(PO4)2F cathode is assembled with the elimination of presodiation treatments.The PBH-SIC involves faradaic reaction on both cathode and anode materials,delivering a high energy density of 126 Wh kg^−1 at 91 W kg^−1,a high power density of 7.6 kW kg^−1 with an energy density of 43 Wh kg−1,and 9000 stable cycles.The tunable vanadate materials with high-performance Na+intercalation pseudocapacitance provide a direction for developing next-generation highenergy capacitors.

Optimizing the electrolyte salt of aqueous zinc-ion batteries based on a high-performance calcium vanadate hydrate cathode material

It is urgent to develop high-performance cathode materials for the emerging aqueous zinc-ion batteries with a facile strategy and optimize the related components.Herein,a Ca0.23V2O5·0.95 H2O nanobelt cathode material with a rather large interlayer spacing of 13.0 A is prepared via a one-step hydrothermal approach.The battery with this cathode material and 3 M Zn(CF3SO3)2 electrolyte displays high specific capacity(355.2 mAh g^(-1) at 0.2 A g^(-1)),great rate capability(240.8 mAh g^(-1) at 5 A g^(-1)),and excellent cyclability(97.7% capacity retention over 2000 cycles).Such superior performances are ascribed to fast electrochemical kinetics,outstanding electrode/electrolyte interface stability,and nearly dendrite-free characteristic.Instead,when ZnSO4 or Zn(ClO4)2 is used to replace Zn(CF3SO3)2,the electrochemical performances become much inferior,due to the slow electrochemical kinetics,inhomogeneous Zn stripping/plating process,and the formation of large dendrites and byproducts.This work not only discloses a high-performance cathode material for aqueous zinc-ion batteries but also offers a reference for the choice of electrolyte salt.

Layered barium vanadate nanobelts for high-performance aqueous zinc-ion batteries

Aqueous zinc-ion batteries(ZIBs)are deemed as the idea option for large-scale energy storage systems owing to many alluring merits including low manufacture cost,environmental friendliness,and high operations safety.However,to develop high-performance cathode is still significant for practical application of ZIBs.Herein,Ba_(0.23)V_(2)O_(5)·1.1H_(2)O(BaVO)nanobelts were fabricated as cathode materials of ZIBs by a typical hydrothermal synthesis method.Benefiting from the increased interlayer distance of 1.31 nm by Ba2+ and H2O pre-intercalated,the obtained BaVO nanobelts showed an excellent initial discharge capacity of 378 mAh·g^(-1) at 0.1 A·g^(-1),a great rate performance(e.g.,172 mAh·g^(-1) at 5 A·g^(-1)),and a superior capacity retention(93% after 2000 cycles at 5 A·g^(-1)).

Enhanced Reversible Zinc Ion Intercalation in Deficient Ammonium Vanadate for High-Performance Aqueous Zinc-Ion Battery

Ammonium vanadate with bronze structure(NH_(4)V_(4)O_(10))is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost.However,the extraction of NH^(+)_(4) at a high voltage during charge/discharge processes leads to irreversible reaction and structure degradation.In this work,partial NH^(+)_(4) ions were pre-removed from NH_(4)V_(4)O_(10) through heat treatment;NH_(4)V_(4)O_(10) nanosheets were directly grown on carbon cloth through hydrothermal method.Defi-cient NH_(4)V_(4)O_(10)(denoted as NVO),with enlarged interlayer spacing,facilitated fast zinc ions transport and high storage capacity and ensured the highly reversible electrochemical reaction and the good stability of layered structure.The NVO nanosheets delivered a high specific capac-ity of 457 mAh g^(−1) at a current density of 100 mA g^(−1) and a capacity retention of 81%over 1000 cycles at 2 A g^(−1).The initial Coulombic efficiency of NVO could reach up to 97%compared to 85%of NH_(4)V_(4)O_(10) and maintain almost 100%during cycling,indicating the high reaction reversibility in NVO electrode.

Crystal Facet Engineering of TiO_(2) Nanostructures for Enhancing Photoelectrochemical Water Splitting with BiVO_(4) Nanodots

Although bismuth vanadate(BiVO4)has been promising as photoanode material for photoelectrochemical water splitting,its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes.As a hole blocking layer of BiVO4,titanium dioxide(TiO_(2)) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity.Herein,a crystal facet engineering of TiO_(2) nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots.We design two types of TiO_(2) nanostructures,which are nanorods(NRs)and nanoflowers(NFs)with different(001)and(110)crystal facets,respectively,and fabricate BiVO4/TiO_(2) heterostructure photoanodes.The BiVO4/TiO_(2) NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO_(2) NRs.Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination,which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO_(2) NFs.This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes.

Porous Co_(2)VO_(4) Nanodisk as a High-Energy and Fast-Charging Anode for Lithium-Ion Batteries

High-energy–density lithium-ion batteries(LIBs)that can be safely fast-charged are desirable for electric vehicles.However,sub-optimal lithiation potential and low capacity of commonly used LIBs anode cause safety issues and low energy density.Here we hypothesize that a cobalt vanadate oxide,Co_(2)VO_(4),can be attractive anode material for fast-charging LIBs due to its high capacity(~1000 mAh g^(−1))and safe lithiation potential(~0.65 V vs.Li^(+)/Li).The Li+diffusion coefficient of Co2VO4 is evaluated by theoretical calculation to be as high as 3.15×10^(-10) cm^(2) s^(−1),proving Co_(2)VO_(4) a promising anode in fast-charging LIBs.A hexagonal porous Co2VO4 nanodisk(PCVO ND)structure is designed accordingly,featuring a high specific surface area of 74.57 m^(2) g^(−1) and numerous pores with a pore size of 14 nm.This unique structure succeeds in enhancing Li^(+) and electron transfer,leading to superior fast-charging performance than current commercial anodes.As a result,the PCVO ND shows a high initial reversible capacity of 911.0 mAh g^(−1) at 0.4 C,excellent fast-charging capacity(344.3 mAh g^(−1) at 10 C for 1000 cycles),outstanding long-term cycling stability(only 0.024% capacity loss per cycle at 10 C for 1000 cycles),confirming the commercial feasibility of PCVO ND in fast-charging LIBs.

Investigation of sodium vanadate as a high-performance aqueous zinc-ion battery cathode

Due to the intrinsic advantages of nontoxicity, low-cost, and abundant resource of metallic zinc, aqueous zinc-ion batteries (ZIBs) have attracted universal interest [1,2]. Tremendous cathode materials have been exploited in aqueous ZIBs, such as manganese-based materials [3-11], Co-based materials [12,13] and vanadium-based materials [14-21].

A High-Capacity Ammonium Vanadate Cathode for Zinc-Ion Battery

Given the advantages of being abundant in resources,environmental benign and highly safe,rechargeable zinc-ion batteries(ZIBs)enter the global spotlight for their potential utilization in large-scale energy storage.Despite their preliminary success,zinc-ion storage that is able to deliver capacity>400 mAh g^-1 remains a great challenge.Here,we demonstrate the viability of NH4V4O10(NVO)as high-capacity cathode that breaks through the bottleneck of ZIBs in limited capacity.The first-principles calculations reveal that layered NVO is a good host to provide fast Zn^2+ions diffusion channel along its[010]direction in the interlayer space.On the other hand,to further enhance Zn^2+ion intercalation kinetics and long-term cycling stability,a three-dimensional(3D)flower-like architecture that is self-assembled by NVO nanobelts(3D-NVO)is rationally designed and fabricated through a microwave-assisted hydrothermal method.As a result,such 3D-NVO cathode possesses high capacity(485 mAh g^-1)and superior long-term cycling performance(3000 times)at 10 A g^-1(~50 s to full discharge/charge).Additionally,based on the excellent 3D-NVO cathode,a quasi-solid-state ZIB with capacity of 378 mAh g^-1is developed.

Recent perspectives into biochemistry of decavanadate

The number of papers about decavanadate has doubled in the past decade. In the present review, new insights into decavanadate biochemistry, cell biology, and antidiabetic and antitumor activities are described. Decameric vanadate species (V10) clearly differs from monomeric vanadate (V1), and affects differently calcium pumps, and structure and function of myosin and actin. Only decavanadate inhibits calcium accumulation by calcium pump ATPase, and strongly inhibits actomyosin ATPase activity (IC50 = 1.4 μmol/L, V10), whereas no such ef- fects are detected with V1 up to 150 μmol/L; prevents actin polymerization (IC50 of 68 μmol/L, whereas no effects detected with up to 2 mmol/L V1); and interacts with actin in a way that induces cysteine oxidation and vanadate reduction to vanadyl. Moreover, in vivo decavanadate toxicity studies have revealed that acute exposure to polyoxovanadate induces different changes in antioxidant enzymes and oxidative stress parameters, in comparison with vanadate. In vitro studies have clearly demonstrated that mitochondrial oxygen consumption is strongly affected by decavanadate (IC50, 0.1 μmol/L); perhaps the most relevant biological effect. Finally, decavanadate (100 μmol/L) increases rat adipocyte glucose accumulation more potently than several vanadium complexes. Preliminary studies sug- gest that decavanadate does not have similar effects in human adipocytes. Although decavanadate can be a useful biochemical tool, further studies must be carried out before it can be conf irmed that decavanadate and its complexes can be used as anticancer or antidiabetic agents.

Construction of BiVO_(4)/BiOCl@C Z-scheme heterojunction for enhanced photoelectrochemical performance

A Z-scheme heterostructure of Mo,W co-doped BiVO_(4)(Mo,W:BVO/BiOCl@C)was fabricated by a simple solid solution drying and calcination(SSDC)method.The heterostructure was characterized by X-ray diffraction(XRD),Fourier transform infrared(FTIR),X-ray photoelectron spectroscopy(XPS),etc.Under visible light irradiation,Mo,W:BVO/BiOCl@C heterostructure exhibits excellent photoelectrochemical capability compared with other as-prepared samples.The photocurrent density and the incident photon-to-electron conversion efficiency(IPCE)are about 5.4 and 9.0 times higher than those of pure BiVO_(4),respectively.The enhancement of the photoelectrochemical performance can be attributed to the construct of Z-scheme system,which is deduced from the radical trapping experiments.The Mo,W:BVO/BiOCl@C Z-scheme heterojunction enhances the visible-light absorption and reduces the recombination rate of charge carriers.This work provides an effective strategy to construct Z-scheme photoelectrodes for the application of photoelectrochemical water splitting.

Solid-state reaction of a CaO−V_(2)O_(5)mixture:A fundamental study for the vanadium extraction process

The aim of this study was to investigate the phase transformation and kinetics of the solid-state reaction of CaO−V_(2)O_(5),which is the predominant binary mixture involved in the vanadium recovery process.Thermal analysis,X-ray diffraction spectroscopy,scanning electron microscopy,and energy dispersive spectrometry were used to characterize the solid-state reaction of the samples.The extent of the solid reac-tion was derived using the preliminary quantitative phase analysis of the X-ray patterns.The results indicate that the solid reaction of the CaO−V_(2)O_(5)mixture is strongly influenced by the reaction temperature and CaO/V_(2)O_(5)mole ratio.The transformation of calcium vanadate in-volves a step-by-step reaction of CaO−V_(2)O_(5),CaO−CaV_(2)O_(6),and CaO−Ca_(2)V_(2)O7 depending on the CaO/V_(2)O_(5)mole ratio.The kinetic data of the solid reaction of the CaO−V_(2)O_(5)(1:1)mixture followed a second-order reaction model.The activation energy(Ea)and preexponential factor(A)were determined to be 145.38 kJ/mol,and 3.67×10^(8)min^(−1),respectively.

A novel yellow emitting phosphor Dy^(3+),Bi^(3+) co-doped YVO_4 potentially for white light emitting diodes

Novel Y1-x-yVO4：xDy3＋, yBi3＋ （0.01 ≤ x ≤ 0.05,0 ≤ y ≤0.20） phosphors for light emitting diode （LED） were successfully synthesised by solid-state reaction. The calculation results of electronic structure show that YVO4 has a direct band gap with 3 eV at G. The top of the valence band is dominated by O 2p state and the bottom of the conduction band is mainly composed of O 2p and V 3d states. An efficient yellow emission under near-ultraviolet （365 nm） excitation is observed. Compared with the pure YVO4：Dy3＋ samples, the Dy3＋, Bi3＋ co-doped samples show a more intensive emission peak （at 574 nm） and a new broad emission band （450-770 nm）, due to the 4F9/2 - 6H13/2 transition of Dy3＋ and the emission of the VO43-Bi3＋ complex respectively. The optimum chromaticity index of Y1-x-yVO4：xDy3＋, yBi3＋ （0.01 ≤ x ≤0.05,0 ≤y ≤ 0.20） is （0.447, 0.497）, which indicates that YVO4：Dy3＋, Bi3＋ has higher colour saturation than the commercial phosphor YAG： Ce3＋. The effects of concentration of Dy3＋, Bi3＋, electric states and the photoluminescence properties are discussed in details.

Photoelectrochemical evaluation of SILAR-deposited nanoporous BiVO4 photoanodes for solar-driven water splitting

We report a photoelectrochemical investigation of BiVO4 photoanodes prepared by successive ionic layer adsorption and reaction(SILAR),a facile method that yields uniform nanoporous films.After characterization of the phase,morphology,composition,and optical properties of the prepared films,the efficiencies of charge separation(ηsep)and water oxidation(ηox)in solar water splitting cells employing these photoanodes were estimated following a previously reported procedure.Unexpected wavelength and illumination direction dependencies were discovered in the derived efficiencies,casting doubt on the validity of the analysis.An alternative approach using a diffusion–reaction model that explicitly considers the efficiency of electron collection resolved the discrepancies and explained the illumination direction dependence of the photocurrent.Electron diffusion lengths(Ln)of 0.45μm and 0.55μm were derived for pristine and cobalt phosphate(Co-Pi)modified BiVO4,respectively,which are much shorter than the film thickness of^2.1μm.The Co-Pi treatment also increasedηoxfrom 0.86 to^1,which is the main reason for the overall performance enhancement caused by adding Co-Pi.These findings suggest that there is little scope for improving the performance of SILAR-deposited BiVO4 photoanodes by further catalyzing water oxidation,but enhanced performance is achievable if electron transport can be improved.