Real-time monitoring of capacity loss for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wei, Zhongbao; Bhattarai, Arjun; Zou, Changfu; Meng, Shujuan; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2018-06-01

The long-term operation of the vanadium redox flow battery is accompanied by ion diffusion across the separator and side reactions, which can lead to electrolyte imbalance and capacity loss. The accurate online monitoring of capacity loss is therefore valuable for the reliable and efficient operation of vanadium redox flow battery system. In this paper, a model-based online monitoring method is proposed to detect capacity loss in the vanadium redox flow battery in real time. A first-order equivalent circuit model is built to capture the dynamics of the vanadium redox flow battery. The model parameters are online identified from the onboard measureable signals with the recursive least squares, in seeking to keep a high modeling accuracy and robustness under a wide range of working scenarios. Based on the online adapted model, an observer is designed with the extended Kalman Filter to keep tracking both the capacity and state of charge of the battery in real time. Experiments are conducted on a lab-scale battery system. Results suggest that the online adapted model is able to simulate the battery behavior with high accuracy. The capacity loss as well as the state of charge can be estimated accurately in a real-time manner.

Amphoteric Ion-Exchange Membranes with Significantly Improved Vanadium Barrier Properties for All-Vanadium Redox Flow Batteries.

PubMed

Nibel, Olga; Rojek, Tomasz; Schmidt, Thomas J; Gubler, Lorenz

2017-07-10

All-vanadium redox flow batteries (VRBs) have attracted considerable interest as promising energy-storage devices that can allow the efficient utilization of renewable energy sources. The membrane, which separates the porous electrodes in a redox flow cell, is one of the key components in VRBs. High rates of crossover of vanadium ions and water through the membrane impair the efficiency and capacity of a VRB. Thus, membranes with low permeation rate of vanadium species and water are required, also characterized by low resistance and stability in the VRB environment. Here, we present a new design concept for amphoteric ion-exchange membranes, based on radiation-induced grafting of vinylpyridine into an ethylene tetrafluoroethylene base film and a two-step functionalization to introduce cationic and anionic exchange sites, respectively. During long-term cycling, redox flow cells containing these membranes showed higher efficiency, less pronounced electrolyte imbalance, and significantly reduced capacity decay compared to the cells with the benchmark material Nafion 117. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance of a low cost interdigitated flow design on a 1 kW class all vanadium mixed acid redox flow battery

NASA Astrophysics Data System (ADS)

Reed, David; Thomsen, Edwin; Li, Bin; Wang, Wei; Nie, Zimin; Koeppel, Brian; Sprenkle, Vincent

2016-02-01

Three flow designs were operated in a 3-cell 1 kW class all vanadium mixed acid redox flow battery. The influence of electrode surface area and flow rate on the coulombic, voltage, and energy efficiency and the pressure drop in the flow circuit will be discussed and correlated to the flow design. Material cost associated with each flow design will also be discussed.

Hydrophilic Channel Alignment of Perfluoronated Sulfonic-Acid Ionomers for Vanadium Redox Flow Batteries.

PubMed

So, Soonyong; Cha, Min Suc; Jo, Sang-Woo; Kim, Tae-Ho; Lee, Jang Yong; Hong, Young Taik

2018-06-13

It is known that uniaxially drawn perfluoronated sulfonic-acid ionomers (PFSAs) show diffusion anisotropy because of the aligned water channels along the deformation direction. We apply the uniaxially stretched membranes to vanadium redox flow batteries (VRFBs) to suppress the permeation of active species, vanadium ions through the transverse directions. The aligned water channels render much lower vanadium permeability, resulting in higher Coulombic efficiency (>98%) and longer self-discharge time (>250 h). Similar to vanadium ions, proton conduction through the membranes also decreases as the stretching ratio increases, but the thinned membranes show the enhanced voltage and energy efficiencies over the range of current density, 50-100 mA/cm 2 . Hydrophilic channel alignment of PFSAs is also beneficial for long-term cycling of VRFBs in terms of capacity retention and cell performances. This simple pretreatment of membranes offers an effective and facile way to overcome high vanadium permeability of PFSAs for VRFBs.

Balancing Osmotic Pressure of Electrolytes for Nanoporous Membrane Vanadium Redox Flow Battery with a Draw Solute.

PubMed

Yan, Ligen; Li, Dan; Li, Shuaiqiang; Xu, Zhi; Dong, Junhang; Jing, Wenheng; Xing, Weihong

2016-12-28

Vanadium redox flow batteries with nanoporous membranes (VRFBNM) have been demonstrated to be good energy storage devices. Yet the capacity decay due to permeation of vanadium and water makes their commercialization very difficult. Inspired by the forward osmosis (FO) mechanism, the VRFBNM battery capacity decrease was alleviated by adding a soluble draw solute (e.g., 2-methylimidazole) into the catholyte, which can counterbalance the osmotic pressure between the positive and negative half-cell. No change of the electrolyte volume has been observed after VRFBNM being operated for 55 h, revealing that the permeation of water and vanadium ions was effectively limited. Consequently, the Coulombic efficiency (CE) of nanoporous TiO 2 vanadium redox flow battery (VRFB) was enhanced from 93.5% to 95.3%, meanwhile, its capacity decay was significantly suppressed from 60.7% to 27.5% upon the addition of soluble draw solute. Moreover, the energy capacity of the VRFBNM was noticeably improved from 297.0 to 406.4 mAh remarkably. These results indicate balancing the osmotic pressure via the addition of draw solute can restrict pressure-dependent vanadium permeation and it can be established as a promising method for up-scaling VRFBNM application.

The role of phosphate additive in stabilization of sulphuric-acid-based vanadium(V) electrolyte for all-vanadium redox-flow batteries

NASA Astrophysics Data System (ADS)

Roznyatovskaya, Nataliya V.; Roznyatovsky, Vitaly A.; Höhne, Carl-Christoph; Fühl, Matthias; Gerber, Tobias; Küttinger, Michael; Noack, Jens; Fischer, Peter; Pinkwart, Karsten; Tübke, Jens

2017-09-01

Catholyte in all-vanadium redox-flow battery (VRFB) which consists of vanadium salts dissolved in sulphuric acid is known to be stabilized by phosphoric acid to slow down the thermal aging at temperatures higher than 40 °C. To reveal the role of phosphoric acid, the thermally-induced aggregation is investigated using variable-temperature 51V, 31P, 17O, 1H nuclear magnetic resonance (NMR) spectroscopy and dynamic light scattering (DLS). The results indicate that the thermal stabilization of vanadium(V) electrolyte is attained by the involvement of monomeric and dimeric vanadium(V) species in the reaction with phosphoric acid which is concurrent to the formation of neutral hydroxo-aqua vanadium(V) precipitation precursor. The dimers are stabilized by counter ions due to association reaction or if such stabilization is not possible, precipitation of vanadium pentoxide is favored. The evolution of particles size distributions at 50 °C in electrolyte samples containing 1.6 M vanadium and 4.0 M total sulphate and the pathways of precipitate formation are discussed. The optimal total phosphate concentration is found to be of 0.15 M. However, the induction time is assumed to be dependent not only on the total phosphate concentrations, but also on the ratio of total vanadium(V) to sulphate concentrations.

Critical safety features of the vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Whitehead, A. H.; Rabbow, T. J.; Trampert, M.; Pokorny, P.

2017-05-01

In this work the behaviour of the vanadium redox flow battery is examined under a variety of short-circuit conditions (e.g. with and without the pumps stopping as a result of the short). In contrast to other battery types, only a small proportion of the electroactive material, in a flow battery, is held between the electrodes at any given time. Therefore, together with the relatively low energy density of the vanadium electrolyte, the immediate release of energy, which occurs as a result of electrical shorting, is somewhat limited. The high heat capacity of the aqueous electrolyte is also beneficial in limiting the temperature rise. It will be seen that the flow battery is therefore considerably safer than other battery types, in this respect.

Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

PubMed

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2013-12-30

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

Effectively suppressing vanadium permeation in vanadium redox flow battery application with modified Nafion membrane with nacre-like nanoarchitectures

NASA Astrophysics Data System (ADS)

Zhang, Lesi; Ling, Ling; Xiao, Min; Han, Dongmei; Wang, Shuanjin; Meng, Yuezhong

2017-06-01

A novel self-assembled composite membrane, Nafion-[PDDA/ZrP]n with nacre-like nanostructures was successfully fabricated by a layer-by-layer (LbL) method and used as proton exchange membrane for vanadium redox flow battery applications. Poly(diallyldimethylammonium chloride) (PDDA) with positive charges and zirconium phosphate (ZrP) nanosheets with negative charges can form ultra-thin nacre-like nanostructure on the surface of Nafion membrane via the ionic crosslinking of tightly folded macromolecules. The lamellar structure of ZrP nanosheets and Donnan exclusion effect of PDDA can greatly decrease the vanadium ion permeability and improve the selectivity of proton conductivity. The fabricated Nafion-[PDDA/ZrP]4 membrane shows two orders of magnitude lower vanadium ion permeability (1.05 × 10-6 cm2 min-1) and 12 times higher ion selectivity than those of pristine Nafion membrane at room temperature. Consequently, the performance of vanadium redox flow batteries (VRFBs) assembled with Nafion-[PDDA/ZrP]3 membrane achieved a highly coulombic efficiency (CE) and energy efficiency (EE) together with a very slow self-discharge rate. When comparing with pristine Nafion VRFB, the CE and EE values of Nafion-[PDDA/ZrP]3 VRFB are 10% and 7% higher at 30 mA cm-2, respectively.

A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Intan, Nadia N.; Klyukin, Konstantin; Zimudzi, Tawanda J.; Hickner, Michael A.; Alexandrov, Vitaly

2018-01-01

Vanadium redox flow batteries (VRFBs) are a promising solution for large-scale energy storage, but a number of problems still impede the deployment of long-lifetime VRFBs. One important aspect of efficient operation of VRFBs is understanding interactions between vanadium species and the membrane. Herein, we investigate the interactions between all four vanadium cations and Nafion membrane by a combination of infrared (IR) spectroscopy and density-functional-theory (DFT)-based static and molecular dynamics simulations. It is observed that vanadium species primarily lead to changes in the IR spectrum of Nafion in the SO3- spectral region which is attributed to the interaction between vanadium species and the SO3- exchange sites. DFT calculations of vanadium -Nafion complexes in the gas phase show that it is thermodynamically favorable for all vanadium cations to bind to SO3- via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that V2+ and V3+ species coordinate spontaneously to SO3-, which is not the case for VO2+ and VO2+ . The interaction behavior of the uncycled membrane determined in this study is used to explain the experimentally observed changes in the vibrational spectra, and is discussed in light of previous results on device-cycled membranes.

Practical thermodynamic quantities for aqueous vanadium- and iron-based flow batteries

DOE PAGES

Hudak, Nicholas S.

2013-12-31

A simple method for experimentally determining thermodynamic quantities for flow battery cell reactions is presented. Equilibrium cell potentials, temperature derivatives of cell potential (d E/d T), Gibbs free energies, and entropies are reported here for all-vanadium, iron–vanadium, and iron–chromium flow cells with state-of-the-art solution compositions. Proof is given that formal potentials and formal temperature coefficients can be used with modified forms of the Nernst Equation to quantify the thermodynamics of flow cell reactions as a function of state-of-charge. Such empirical quantities can be used in thermo-electrochemical models of flow batteries at the cell or system level. In most cases, themore » thermodynamic quantities measured here are significantly different from standard values reported and used previously in the literature. The data reported here are also useful in the selection of operating temperatures for flow battery systems. Because higher temperatures correspond to lower equilibrium cell potentials for the battery chemistries studied here, it can be beneficial to charge a cell at higher temperature and discharge at lower temperature. As a result, proof-of-concept of improved voltage efficiency with the use of such non-isothermal cycling is given for the all-vanadium redox flow battery, and the effect is shown to be more pronounced at lower current densities.« less

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

PubMed

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tackling capacity fading in vanadium flow batteries with amphoteric membranes

NASA Astrophysics Data System (ADS)

Oldenburg, Fabio J.; Schmidt, Thomas J.; Gubler, Lorenz

2017-11-01

Capacity fading and poor electrolyte utilization caused by electrolyte imbalance effects are major drawbacks for the commercialization of vanadium flow batteries (VFB). The influence of membrane type (cationic, anionic, amphoteric) on these effects is studied by determining the excess and net flux of each vanadium ion in an operating VFB assembled with a cation exchange membrane (CEM), Nafion® NR212, an anion exchange membrane (AEM), Fumatech FAP-450, and an amphoteric ion exchange membrane (AIEM) synthesized in-house. It is shown that the net vanadium flux, accompanied by water transport, is directed towards the positive side for the CEM and towards the negative side for the AEM. The content of cation and anion exchange groups in the AIEM is adjusted via radiation grafting to balance the vanadium flux between the two electrolyte sides. With the AIEM the net vanadium flux is significantly reduced and capacity fading due to electrolyte imbalances can be largely eliminated. The membrane's influence on electrolyte imbalance effects is characterized and quantified in one single charge-discharge cycle by analyzing the content of the four different vanadium species in the two electrolytes. The experimental data recorded herewith conclusively explains the electrolyte composition after 80 cycles.

Low Permeable Hydrocarbon Polymer Electrolyte Membrane for Vanadium Redox Flow Battery.

PubMed

Jung, Ho-Young; Moon, Geon-O; Jung, Seunghun; Kim, Hee Tak; Kim, Sang-Chai; Roh, Sung-Hee

2017-04-01

Polymer electrolyte membrane (PEM) confirms the life span of vanadium redox flow battery (VRFB). Products from Dupont, Nafion membrane, is mainly used for PEM in VRFB. However, permeation of vanadium ion occurs because of Nafion’s high permeability. Therefore, the efficiency of VRFB decreases and the prices becomes higher, which hinders VRFB’s commercialization. In order to solve this problem, poly(phenylene oxide) (PPO) is sulfonated for the preparation of low-priced hydrocarbon polymer electrolyte membrane. sPPO membrane is characterized by fundamental properties and VRFB cell test.

In situ potential distribution measurement in an all-vanadium flow battery.

PubMed

Liu, Qinghua; Turhan, Ahmet; Zawodzinski, Thomas A; Mench, Matthew M

2013-07-18

An experimental method for measurement of local redox potential within multilayer electrodes was developed and applied to all-vanadium redox flow batteries (VRFBs). Through-plane measurement at the positive side reveals several important phenomena including potential distribution, concentration distribution of active species and the predominant reaction location within the porous carbon electrodes.

Modeling of ion transport through a porous separator in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

2016-09-01

In this work, we develop a two-dimensional, transient model to investigate the mechanisms of ion-transport through a porous separator in VRFBs and their effects on battery performance. Commercial-available separators with pore sizes of around 45 nm are particularly investigated and effects of key separator design parameters and operation modes are explored. We reveal that: i) the transport mechanism of vanadium-ion crossover through available separators is predominated by convection; ii) reducing the pore size below 15 nm effectively minimizes the convection-driven vanadium-ion crossover, while further reduction in migration- and diffusion-driven vanadium-ion crossover can be achieved only when the pore size is reduced to the level close to the sizes of vanadium ions; and iii) operation modes that can affect the pressure at the separator/electrode interface, such as the electrolyte flow rate, exert a significant influence on the vanadium-ion crossover rate through the available separators, indicating that it is critically important to equalize the pressure on each half-cell of a power pack in practical applications.

Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery

PubMed Central

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2014-01-01

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion. PMID:24957118

Amphiphilic block copolymer membrane for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wang, Fei; Sylvia, James M.; Jacob, Monsy M.; Peramunage, Dharmasena

2013-11-01

An amphiphilic block copolymer comprised of hydrophobic polyaryletherketone (PAEK) and hydrophilic sulfonated polyaryletherketone (SPAEK) blocks has been synthesized and characterized. A membrane prepared from the block copolymer is used as the separator in a single cell vanadium redox flow battery (VRB). The proton conductivity, mechanical property, VO2+ permeability and single VRB cell performance of this block copolymer membrane are investigated and compared to Nafion™ 117. The block copolymer membrane showed significantly improved vanadium ion selectivity, higher mechanical strength and lower conductivity than Nafion™ 117. The VRB containing the block copolymer membrane exhibits higher coulombic efficiency and similar energy efficiency compared to a VRB using Nafion™ 117. The better vanadium ion selectivity of the block copolymer membrane has led to a much smaller capacity loss during 50 charge-discharge cycles for the VRB.

Investigation of crossover processes in a unitized bidirectional vanadium/air redox flow battery

NASA Astrophysics Data System (ADS)

grosse Austing, Jan; Nunes Kirchner, Carolina; Komsiyska, Lidiya; Wittstock, Gunther

2016-02-01

In this paper the losses in coulombic efficiency are investigated for a vanadium/air redox flow battery (VARFB) comprising a two-layered positive electrode. Ultraviolet/visible (UV/Vis) spectroscopy is used to monitor the concentrations cV2+ and cV3+ during operation. The most likely cause for the largest part of the coulombic losses is the permeation of oxygen from the positive to the negative electrode followed by an oxidation of V2+ to V3+. The total vanadium crossover is followed by inductively coupled plasma mass spectroscopy (ICP-MS) analysis of the positive electrolyte after one VARFB cycle. During one cycle 6% of the vanadium species initially present in the negative electrolyte are transferred to the positive electrolyte, which can account at most for 20% of the coulombic losses. The diffusion coefficients of V2+ and V3+ through Nafion® 117 are determined as DV2+ ,N 117 = 9.05 ·10-6 cm2 min-1 and DV3+ ,N 117 = 4.35 ·10-6 cm2 min-1 and are used to calculate vanadium crossover due to diffusion which allows differentiation between vanadium crossover due to diffusion and migration/electroosmotic convection. In order to optimize coulombic efficiency of VARFB, membranes need to be designed with reduced oxygen permeation and vanadium crossover.

Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-11-01

The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

Highly stable pyridinium-functionalized cross-linked anion exchange membranes for all vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

2016-11-01

It has recently been demonstrated that the use of anion exchange membranes (AEMs) in vanadium redox flow batteries (VRFBs) can reduce the migration of vanadium ions through the membrane due to the Donnan exclusion effect among the positively charged functional groups and vanadium ions. However, AEMs are plagued by low chemical stability in harsh chemical environments. Here we propose and fabricate a pyridinium-functionalized cross-linked AEM for VRFBs. The pyridinium-functionalized bromomethylated poly (2,6-dimethyl-1,4-phenylene oxide) exhibits a superior chemical stability as a result of the strengthened internal cross-linking networks and the chemical inertness of the polymer backbone. Therefore, the membrane exhibits littler decay in a harsh environment for 20 days during the course of an ex situ immersion test. A cycling test also demonstrates that the VRFB assembled with the membrane enable to retain 80% of the initial discharge capacity over 537 cycles with a capacity decay rate of 0.037% cycle-1. Meanwhile, the membrane also shows a low vanadium permeability and a reasonably high conductivity in supporting electrolytes. Hence, all the measurements and performance tests reported in this work suggest that the membrane is a promising AEM for redox flow batteries to achieve excellent cycling stability and superior cell performance.

Extended dynamic model for ion diffusion in all-vanadium redox flow battery including the effects of temperature and bulk electrolyte transfer

NASA Astrophysics Data System (ADS)

Badrinarayanan, Rajagopalan; Zhao, Jiyun; Tseng, K. J.; Skyllas-Kazacos, Maria

2014-12-01

As with all redox flow batteries, the Vanadium Redox flow Battery (VRB) can suffer from capacity loss as the vanadium ions diffuse at different rates leading to a build-up on one half-cell and dilution on the other. In this paper an extended dynamic model of the vanadium ion transfer is developed including the effect of temperature and bulk electrolyte transfer. The model is used to simulate capacity decay for a range of different ion exchange membranes that are being used in the VRB. The simulations show that Selemion CMV and Nafion 115 membranes have similar behavior where the impact of temperature on capacity loss is highest within the first 100 cycles. The results for Selemion AMV membrane however are seen to be very different where the capacity loss at different temperatures observed to increase linearly with increasing charging/discharging cycles. The model is made more comprehensive by including the effect of bulk electrolyte transfer. A volume change of 19% is observed in each half-cell for Nafion 115 membrane based on the simulation parameters. The effect of this change in volume directly affects concentration, and the characteristics are analyzed for each vanadium species as well as the overall concentration in the half-cells.

Activated Carbon Fiber Paper Based Electrodes with High Electrocatalytic Activity for Vanadium Flow Batteries with Improved Power Density.

PubMed

Liu, Tao; Li, Xianfeng; Xu, Chi; Zhang, Huamin

2017-02-08

Vanadium flow batteries (VFBs) have received high attention for large-scale energy storage due to their advantages of flexibility design, long cycle life, high efficiency, and high safety. However, commercial progress of VFBs has so far been limited by its high cost induced by its low power density. Ultrathin carbon paper is believed to be a very promising electrode for VFB because it illustrates super-low ohmic polarization, however, is limited by its low electrocatalytic activity. In this paper, a kind of carbon paper (CP) with super-high electrocatalytic activity was fabricated via a universal and simple CO 2 activation method. The porosity and oxygen functional groups can be easily tuned via this method. The charge transfer resistance (denoting the electrochemical polarization) of a VFB with CP electrode after CO 2 activation decreased dramatically from 970 to 120 mΩcm 2 . Accordingly, the energy efficiency of a VFB with activated carbon paper as the electrode increased by 13% as compared to one without activation and reaches nearly 80% when the current density is 140 mAcm -2 . This paper provides an effective way to prepare high-performance porous carbon electrodes for VFBs and even for other battery systems.

Pulsating electrolyte flow in a full vanadium redox battery

NASA Astrophysics Data System (ADS)

Ling, C. Y.; Cao, H.; Chng, M. L.; Han, M.; Birgersson, E.

2015-10-01

Proper management of electrolyte flow in a vanadium redox battery (VRB) is crucial to achieve high overall system efficiency. On one hand, constant flow reduces concentration polarization and by extension, energy efficiency; on the other hand, it results in higher auxiliary pumping costs, which can consume around 10% of the discharge power. This work seeks to reduce the pumping cost by adopting a novel pulsing electrolyte flow strategy while retaining high energy efficiency. The results indicate that adopting a short flow period, followed by a long flow termination period, results in high energy efficiencies of 80.5% with a pumping cost reduction of over 50%.

Application of Novel Anion-Exchange Blend Membranes (AEBMs) to Vanadium Redox Flow Batteries.

PubMed

Cho, Hyeongrae; Krieg, Henning M; Kerres, Jochen A

2018-06-19

Both cation-exchange membranes and anion-exchange membranes are used as ion conducting membranes in vanadium redox flow batteries (VRFBs). Anion-exchange membranes (AEMs) are applied in vanadium redox flow batteries due to the high blocking property of vanadium ions via the Donnan exclusion effect. In this study, novel anion-exchange blend membranes (AEBMs) were prepared, characterized, and applied in VRFBs. Bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide), poly[(1-(4,4′-diphenylether)-5-oxybenzimidazole)-benzimidazole] (PBI-OO) and sulfonated polyether sulfone polymer were combined to prepare 3-component AEBMs with 1,2,4,5-tetramethylimidazole (TMIm) for quaternization. 3-component AEBMs showed significantly enhanced chemical and mechanical properties compared with those of 2-component AEBMs, resulting in an improved performance in VRFBs. The compositions of the anion-exchange polymers in 3-component AEBMs were systematically varied to optimize the AEBMs for the redox-flow battery application. While the 3-component AEBMs showed comparable efficiencies with Nafion ® 212 membranes, they displayed improved vanadium ions cross-over as was confirmed by open circuit voltage tests and capacity fade tests conducted in VRFBs. In addition, one of the synthesized 3-component AEBM had a superior coulombic efficiency and capacity retention in a charging⁻discharging test over 300 cycles at a current density of 40 mA/cm². It can thus be concluded that 3-component AEBMs are promising candidates for long-term operation in VRFBs.

Extraction of vanadium into isobutyl methyl ketone1 1 Publication authorized by the Director, U.S. Geological Survey.

USGS Publications Warehouse

Crump-Wiesner, Hans J.; Purdy, W.C.

1969-01-01

Because of its advantages in atomic-absorption spectroscopy, isobutyl methyl ketone was chosen as organic solvent for an extraction study on vanadium. Of eight chelating agents which were evaluated for completeness of extraction, ease of use, working pH range, and freedom from interference, cupferron was judged best. ?? 1969.

A Step-by-Step Design Methodology for a Base Case Vanadium Redox-Flow Battery

ERIC Educational Resources Information Center

Moore, Mark; Counce, Robert M.; Watson, Jack S.; Zawodzinski, Thomas A.; Kamath, Haresh

2012-01-01

The purpose of this work is to develop an evolutionary procedure to be used by Chemical Engineering students for the base-case design of a Vanadium Redox-Flow Battery. The design methodology is based on the work of Douglas (1985) and provides a profitability analysis at each decision level so that more profitable alternatives and directions can be…

Glassy carbon/multi walled carbon nanotube/cadmium sulphide photoanode for light energy storage in vanadium photoelectrochemical cell

NASA Astrophysics Data System (ADS)

Peimanifard, Zahra; Rashid-Nadimi, Sahar

2015-12-01

The aim of this study is utilizing the artificial photosynthesis, which is an attractive and challenging theme in the photoelectrocatalytic water splitting, to charge the vanadium redox flow battery (VRFB). In this work multi walled carbon nanotube/cadmium sulphide hybrid is employed as a photoanode material to oxidize VO2+ toVO2+ for charging the positive vanadium redox flow battery's half-cell. Characterization studies are also described using the scanning electron microscopic-energy-dispersive X-ray spectroscopy (SEM-EDS), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and UV-Visible methods. The phtoelectrochemical performance is characterized by cyclic voltammetry and chronoamperometry. Applied bias photon-to-current efficiency (ABPE) is achieved for both two and three-electrode configurations. The glassy carbon/multi walled carbon nanotube/cadmium sulphide yields high maximum ABPE of 2.6% and 2.12% in three and two-electrode setups, respectively. These results provide a useful guideline in designing photoelectrochemical cells for charging the vanadium redox flow batteries by sunlight as a low cost, free and abundant energy source, which does not rely on an external power input.

Vanadium recycling in the United States in 2004

USGS Publications Warehouse

Goonan, Thomas G.

2011-01-01

As one of a series of reports that describe the recycling of metal commodities in the United States, this report discusses the flow of vanadium in the U.S. economy in 2004. This report includes a description of vanadium supply and demand in the United States and illustrates the extent of vanadium recycling and recycling trends. In 2004, apparent vanadium consumption, by end use, in the United States was 3,820 metric tons (t) in steelmaking and 232 t in manufacturing, of which 17 t was for the production of superalloys and 215 t was for the production of other alloys, cast iron, catalysts, and chemicals. Vanadium use in steel is almost entirely dissipative because recovery of vanadium from steel scrap is chemically impeded under the oxidizing conditions in steelmaking furnaces. The greatest amount of vanadium recycling is in the superalloy, other-alloy, and catalyst sectors of the vanadium market. Vanadium-bearing catalysts are associated with hydrocarbon recovery and refining in the oil industry. In 2004, 2,850 t of vanadium contained in alloy scrap and spent catalysts was recycled, which amounted to about 44 percent of U.S. domestic production. About 94 percent of vanadium use in the United States was dissipative (3,820 t in steel/4,050 t in steel+fabricated products).

Thermodynamic derivation of open circuit voltage in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Pavelka, Michal; Wandschneider, Frank; Mazur, Petr

2015-10-01

Open circuit voltage of vanadium redox flow batteries is carefully calculated using equilibrium thermodynamics. This analysis reveals some terms in the Nernst relation which are usually omitted in literature. Due to the careful thermodynamic treatment, all uncertainties about the form of Nernst relation are removed except for uncertainties in activity coefficients of particular species. Moreover, it is shown (based again on equilibrium thermodynamics) that batteries with anion-exchange membranes follow different Nernst relation than batteries with cation-exchange membranes. The difference is calculated, and it is verified experimentally that the formula for anion-exchange membranes describes experiments with anion-exchange membranes better than the corresponding formula for cation-exchange membranes. In summary, careful thermodynamic calculation of open circuit voltage of vanadium redox flow batteries is presented, and the difference between voltage for anion-exchange and cation-exchange membranes is revealed.

Measuring the state of charge of the electrolyte solution in a vanadium redox flow battery using a four-pole cell device

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-12-01

The decrease in the efficiency and capacity of a vanadium redox flow battery (VRB) caused by an electrolyte imbalance is an important impediment to its long-term operation. Knowing the state of charge (SOC) of an electrolyte solution can quantify the level of the electrolyte imbalance in the VRB. In this study, a four-pole cell device is devised and employed to predict the SOC. The proposed method directly measures the ionic resistance of the electrolyte solution and is sufficiently precise to be applied in real-time mode. Experimental studies on the effects of the operating current on the four-pole cell and the concentrations of vanadium and sulfuric acid in the electrolyte solution are carried out. The results show that the four-pole cell method can be utilized to measure the electrolyte SOC. The concentrations of vanadium and sulfuric acid in the electrolyte solution affect the ionic resistance of the solution. Regarding the capacity and efficiency of the VRB system, the results indicate that the electrical charge is determined from the concentration of vanadium and that the cell voltage depends on the concentration of sulfuric acid in the electrolyte solution. The decreased vanadium concentration and increased sulfuric acid concentration improves the cell voltage efficiency.

Pore-Size-Tuned Graphene Oxide Frameworks as Ion-Selective and Protective Layers on Hydrocarbon Membranes for Vanadium Redox-Flow Batteries.

PubMed

Kim, Soohyun; Choi, Junghoon; Choi, Chanyong; Heo, Jiyun; Kim, Dae Woo; Lee, Jang Yong; Hong, Young Taik; Jung, Hee-Tae; Kim, Hee-Tak

2018-05-07

The laminated structure of graphene oxide (GO) membranes provides exceptional ion-separation properties due to the regular interlayer spacing ( d) between laminate layers. However, a larger effective pore size of the laminate immersed in water (∼11.1 Å) than the hydrated diameter of vanadium ions (>6.0 Å) prevents its use in vanadium redox-flow batteries (VRFB). In this work, we report an ion-selective graphene oxide framework (GOF) with a d tuned by cross-linking the GO nanosheets. Its effective pore size (∼5.9 Å) excludes vanadium ions by size but allows proton conduction. The GOF membrane is employed as a protective layer to address the poor chemical stability of sulfonated poly(arylene ether sulfone) (SPAES) membranes against VO 2 + in VRFB. By effectively blocking vanadium ions, the GOF/SPAES membrane exhibits vanadium-ion permeability 4.2 times lower and a durability 5 times longer than that of the pristine SPAES membrane. Moreover, the VRFB with the GOF/SPAES membrane achieves an energy efficiency of 89% at 80 mA cm -2 and a capacity retention of 88% even after 400 cycles, far exceeding results for Nafion 115 and demonstrating its practical applicability for VRFB.

3D-printed conductive static mixers enable all-vanadium redox flow battery using slurry electrodes

NASA Astrophysics Data System (ADS)

Percin, Korcan; Rommerskirchen, Alexandra; Sengpiel, Robert; Gendel, Youri; Wessling, Matthias

2018-03-01

State-of-the-art all-vanadium redox flow batteries employ porous carbonaceous materials as electrodes. The battery cells possess non-scalable fixed electrodes inserted into a cell stack. In contrast, a conductive particle network dispersed in the electrolyte, known as slurry electrode, may be beneficial for a scalable redox flow battery. In this work, slurry electrodes are successfully introduced to an all-vanadium redox flow battery. Activated carbon and graphite powder particles are dispersed up to 20 wt% in the vanadium electrolyte and charge-discharge behavior is inspected via polarization studies. Graphite powder slurry is superior over activated carbon with a polarization behavior closer to the standard graphite felt electrodes. 3D-printed conductive static mixers introduced to the slurry channel improve the charge transfer via intensified slurry mixing and increased surface area. Consequently, a significant increase in the coulombic efficiency up to 95% and energy efficiency up to 65% is obtained. Our results show that slurry electrodes supported by conductive static mixers can be competitive to state-of-the-art electrodes yielding an additional degree of freedom in battery design. Research into carbon properties (particle size, internal surface area, pore size distribution) tailored to the electrolyte system and optimization of the mixer geometry may yield even better battery properties.

A Review on the Potential Use of Austenitic Stainless Steels in Nuclear Fusion Reactors

NASA Astrophysics Data System (ADS)

Şahin, Sümer; Übeyli, Mustafa

2008-12-01

Various engineering materials; austenitic stainless steels, ferritic/martensitic steels, vanadium alloys, refractory metals and composites have been suggested as candidate structural materials for nuclear fusion reactors. Among these structural materials, austenitic steels have an advantage of extensive technological database and lower cost compared to other non-ferrous candidates. Furthermore, they have also advantages of very good mechanical properties and fission operation experience. Moreover, modified austenitic stainless (Ni and Mo free) have relatively low residual radioactivity. Nevertheless, they can't withstand high neutron wall load which is required to get high power density in fusion reactors. On the other hand, a protective flowing liquid wall between plasma and solid first wall in these reactors can eliminate this restriction. This study presents an overview of austenitic stainless steels considered to be used in fusion reactors.

Porous glass membranes for vanadium redox-flow battery application - Effect of pore size on the performance

NASA Astrophysics Data System (ADS)

Mögelin, H.; Yao, G.; Zhong, H.; dos Santos, A. R.; Barascu, A.; Meyer, R.; Krenkel, S.; Wassersleben, S.; Hickmann, T.; Enke, D.; Turek, T.; Kunz, U.

2018-02-01

The improvement of redox-flow batteries requires the development of chemically stable and highly conductive separators. Porous glass membranes can be an attractive alternative to the nowadays most common polymeric membranes. Flat porous glass membranes with a pore size in the range from 2 to 50 nm and a thickness of 300 and 500 μm have been used for that purpose. Maximum values for voltage efficiency of 85.1%, coulombic efficiency of 97.9% and energy efficiency of 76.3% at current densities in the range from 20 to 60 mA cm-2 have been achieved. Furthermore, a maximum power density of 95.2 mW cm-2 at a current density of 140 mA cm-2 was gained. These results can be related to small vanadium crossover, high conductivity and chemical stability, confirming the great potential of porous glass membranes for vanadium redox-flow applications.

State of charge monitoring of vanadium redox flow batteries using half cell potentials and electrolyte density

NASA Astrophysics Data System (ADS)

Ressel, Simon; Bill, Florian; Holtz, Lucas; Janshen, Niklas; Chica, Antonio; Flower, Thomas; Weidlich, Claudia; Struckmann, Thorsten

2018-02-01

The operation of vanadium redox flow batteries requires reliable in situ state of charge (SOC) monitoring. In this study, two SOC estimation approaches for the negative half cell are investigated. First, in situ open circuit potential measurements are combined with Coulomb counting in a one-step calibration of SOC and Nernst potential which doesn't need additional reference SOCs. In-sample and out-of-sample SOCs are estimated and analyzed, estimation errors ≤ 0.04 are obtained. In the second approach, temperature corrected in situ electrolyte density measurements are used for the first time in vanadium redox flow batteries for SOC estimation. In-sample and out-of-sample SOC estimation errors ≤ 0.04 demonstrate the feasibility of this approach. Both methods allow recalibration during battery operation. The actual capacity obtained from SOC calibration can be used in a state of health model.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Shifeng; Wang, Shuyu; Lu, Ming

In this paper, vanadium thin films were deposited on sapphire substrates by DC magnetron sputtering and then oxidized in a tube furnace filled with oxygen under different temperatures and oxygen flow rates. The significant influence of the oxygen flow rate and oxidation temperature on the electrical and structural properties of the vanadium oxide thin films were investigated systematically. It shows the pure vanadium dioxide (VO 2) state can only be obtained in a very narrow temperature and oxygen flow rate range. The resistivity change during the metal-insulator transition varies from 0.2 to 4 orders of magnitude depending on the oxidationmore » condition. Large thermal hysteresis during the metal-insulator phase transition was observed during the transition compared to the results in literature. Proper oxidation conditions can significantly reduce the thermal hysteresis. Finally, the fabricated VO 2 thin films showed the potential to be applied in the development of electrical sensors and other smart devices.« less

Porous poly(benzimidazole) membrane for all vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Luo, Tao; David, Oana; Gendel, Youri; Wessling, Matthias

2016-04-01

Porous poly(benzimidazole) (PBI) membranes of low vanadium ions permeability are described for an all vanadium redox flow battery (VRFB). The PBI membrane was prepared by a water vapour induced phase inversion process of a PBI polymer solution. The membrane has a symmetrical cross-sectional morphology. A low water permeability of 16.5 L (m2 h bar)-1 indicates the high hydraulic resistance stemming from a closed cell morphology with nanoporous characteristics. The PBI membrane doped with 2.5 M H2SO4 shows a proton conductivity of 16.6 mS cm-1 and VO2+ permeability as low as 4.5 × 10-8 cm2 min-1. The stability test of dense PBI membrane in VO2+ solution indicates good chemical stability. An all vanadium redox flow battery (VRFB) operated with the porous PBI membrane shows 98% coulombic efficiency and more than 10% higher energy efficiency compared to VRFB operated with Nafion 112 at applied current densities of 20-40 mA cm-2. High in situ stability of the porous PBI membrane was confirmed by about 50 cycles of continuous charge and discharge operation of the battery.

Anion-conductive membranes with ultralow vanadium permeability and excellent performance in vanadium flow batteries.

PubMed

Mai, Zhensheng; Zhang, Huamin; Zhang, Hongzhang; Xu, Wanxing; Wei, Wenping; Na, Hui; Li, Xianfeng

2013-02-01

Anion exchange membranes prepared from quaternized poly(tetramethyl diphenyl ether sulfone) (QAPES) were first investigated in the context of vanadium flow battery (VFB) applications. The membranes showed an impressive suppression effect on vanadium ions. The recorded vanadium permeability was 0.02×10(-7)-0.09×10(-7) cm(2) min(-1), which was two orders of magnitude lower than that of Nafion 115. The self-discharge duration of a VFB single cell with a QAPES membrane is four times longer than that of Nafion 115. The morphological difference in hydrophilic domains between QAPES and Nafion was confirmed by TEM. After soaking the membranes in VO(2)(+) solution, adsorbed vanadium ions can barely be found in QAPES, whereas the hydrophilic domains of Nafion were stained. In the ex situ chemical stability test, QAPES showed a high tolerance to VO(2)(+) and remained intact after immersion in VO(2)(+) solution for over 250 h. The performance of a VFB single cell assembled with QAPES membranes is equal to or even better than that of Nafion 115 and remains stable in a long-term cycle test. These results indicate that QAPES membranes can be an ideal option in the fabrication of high-performance VFBs with low electric capacity loss. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfonated graphene oxide/nafion composite membrane for vanadium redox flow battery.

PubMed

Kim, Byung Guk; Han, Tae Hee; Cho, Chang Gi

2014-12-01

Nafion is the most frequently used as the membrane material due to its good proton conductivity, and excellent chemical and mechanical stabilities. But it is known to have poor barrier property due to its well-developed water channels. In order to overcome this drawback, graphene oxide (GO) derivatives were introduced for Nafion composite membranes. Sulfonated graphene oxide (sGO) was prepared from GO. Both sGO and GO were treated each with phenyl isocyanate and transformed into corresponding isGO and iGO in order to promote miscibility with Nafion. Then composite membranes were obtained, and the adaptability as a membrane for vanadium redox flow battery (VRFB) was investigated in terms of proton conductivity and vanadium permeability. Compared to a pristine Nafion, proton conductivities of both isGO/Nafion and iGO/Nafion membranes showed less temperature sensitivity. Both membranes also showed quite lower vanadium permeability at room temperature. Selectivity of the membrane was the highest for isGO/Nafion and the lowest for the pristine Nafion.

Stopped-in-loop flow analysis of trace vanadium in water.

PubMed

Teshima, Norio; Ohno, Shinsuke; Sakai, Tadao

2007-01-01

The new concept of stopped-in-loop flow analysis (SIL-FA) is proposed, and an SIL-FA method for the catalytic determination of vanadium is demonstrated. In an SIL format, a sample solution merges with reagent(s), and the well-mixed solution is loaded into a loop. The solution in the loop is separated by a six-way switching valve from the main stream. While the reaction proceeds in the stationary loop, the SIL-FA system does not need to establish a baseline continuously. This leads to a reduction in reagent consumption and waste generation compared with traditional flow injection analysis.

Polarization curve measurements combined with potential probe sensing for determining current density distribution in vanadium redox-flow batteries

NASA Astrophysics Data System (ADS)

Becker, Maik; Bredemeyer, Niels; Tenhumberg, Nils; Turek, Thomas

2016-03-01

Potential probes are applied to vanadium redox-flow batteries for determination of effective felt resistance and current density distribution. During the measurement of polarization curves in 100 cm2 cells with different carbon felt compression rates, alternating potential steps at cell voltages between 0.6 V and 2.0 V are applied. Polarization curves are recorded at different flow rates and states of charge of the battery. Increasing compression rates lead to lower effective felt resistances and a more uniform resistance distribution. Low flow rates at high or low state of charge result in non-linear current density distribution with high gradients, while high flow rates give rise to a nearly linear behavior.

Structure and stability of hexa-aqua V(III) cations in vanadium redox flow battery electrolytes.

PubMed

Vijayakumar, M; Li, Liyu; Nie, Zimin; Yang, Zhenguo; Hu, JianZhi

2012-08-07

The vanadium(III) cation structure in mixed acid based electrolyte solution from vanadium redox flow batteries is studied by (17)O and (35/37)Cl nuclear magnetic resonance (NMR) spectroscopy, electronic spectroscopy and density functional theory (DFT) based computational modelling. Both computational and experimental results reveal that the V(III) species can complex with counter anions (sulfate/chlorine) depending on the composition of its solvation sphere. By analyzing the powder precipitate it was found that the formation of sulfate complexed V(III) species is the crucial process in the precipitation reaction. The precipitation occurs through nucleation of neutral species formed through deprotonation and ion-pair formation process. However, the powder precipitate shows a multiphase nature which warrants multiple reaction pathways for precipitation reaction.

Polyvinylpyrrolidone-based semi-interpenetrating polymer networks as highly selective and chemically stable membranes for all vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

2016-09-01

Vanadium redox flow batteries (VRFBs) with their high flexibility in configuration and operation, as well as long cycle life are competent for the requirement of future energy storage systems. Nevertheless, due to the application of perfluorinated membranes, VRFBs are plagued by not only the severe migration issue of vanadium ions, but also their high cost. Herein, we fabricate semi-interpenetrating polymer networks (SIPNs), consisting of cross-linked polyvinylpyrrolidone (PVP) and polysulfone (PSF), as alternative membranes for VRFBs. It is demonstrated that the PVP-based SIPNs exhibit extremely low vanadium permeabilities, which contribute to the well-established hydrophilic/hydrophobic microstructures and the Donnan exclusion effect. As a result, the coulombic efficiencies of VRFBs with PVP-based SIPNs reach almost 100% at 40 mA cm-2 to 100 mA cm-2; the energy efficiencies are more than 3% higher than those of VRFBs with Nafion 212. More importantly, the PVP-based SIPNs exhibit a superior chemical stability, as demonstrated both by an ex situ immersion test and continuously cycling test. Hence, all the characterizations and performance tests reported here suggest that PVP-based SIPNs are a promising alternative membrane for redox flow batteries to achieve superior cell performance and excellent cycling stability at the fraction of the cost of perfluorinated membranes.

Characterization of Sulfonated Diels-Alder Poly(phenylene) Membranes for Electrolyte Separators in Vanadium Redox Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Zhijiang; Lawton, Jamie S.; Sun, Che-Nan

2014-09-03

Here, sulfonated Diels-Alder poly(phenylene) (SDAPP) membranes were synthesized and characterized as potential electrolyte separators for vanadium redox flow batteries. The SDAPP membranes studied had ion exchange capacities of 1.4, 1.8 and 2.3 meq/g. Transmission electron microscopy imaging shows that the ionic domains in SDAPP are roughly 0.5 nm in dimension, while Nafion has a hydrophilic phase width of around 5 nm. The sulfuric acid uptake by SDAPP was higher than that for Nafion, but the materials had similar water uptake from solutions of various sulfuric acid concentrations. In equilibration with sulfuric acid concentrations ranging from 0–17.4 mol·kg -1, SDAPP withmore » a IEC of 2.3 meq/g had the highest conductivity, ranging from 0.21 to 0.05 S·cm -1, while SDAPP with a IEC of 1.8 had conductivity close to Nafion 117, ranging from 0.11 to 0.02 S·cm -1. With varying sulfuric acid concentration and temperature, vanadium permeability in SDAPP is positively correlated to the membrane's IEC. The vanadium permeability of SDAPP 2.3 is similar to that of Nafion, but permeability values for SDAPP 1.8 and SDAPP 1.4 are substantially lower. The vanadium permeation decreases with increasing electrolyte sulfuric acid concentration. Lastly, vanadium diffusion activation energy is about 20 kJ·mol -1 in both SDAPP and Nafion.« less

A metal-insulator transition study of VO 2 thin films grown on sapphire substrates

DOE PAGES

Yu, Shifeng; Wang, Shuyu; Lu, Ming; ...

2017-12-15

In this paper, vanadium thin films were deposited on sapphire substrates by DC magnetron sputtering and then oxidized in a tube furnace filled with oxygen under different temperatures and oxygen flow rates. The significant influence of the oxygen flow rate and oxidation temperature on the electrical and structural properties of the vanadium oxide thin films were investigated systematically. It shows the pure vanadium dioxide (VO 2) state can only be obtained in a very narrow temperature and oxygen flow rate range. The resistivity change during the metal-insulator transition varies from 0.2 to 4 orders of magnitude depending on the oxidationmore » condition. Large thermal hysteresis during the metal-insulator phase transition was observed during the transition compared to the results in literature. Proper oxidation conditions can significantly reduce the thermal hysteresis. Finally, the fabricated VO 2 thin films showed the potential to be applied in the development of electrical sensors and other smart devices.« less

Three-dimensional Nitrogen-Doped Reduced Graphene Oxide/Carbon Nanotube Composite Catalysts for Vanadium Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

The development of vanadium redox flow battery is limited by the sluggish kinetics of the reaction, especially the cathodic VO2+/VO2+ redox couples. Therefore, it is vital to develop new electrocatalyst with enhanced activity to improve the battery performance. Herein, we first synthesized the hydrogel precursor by a facile hydrothermal method. After the following carbonization, nitrogen-doped reduced graphene oxide/carbon nanotube composite was obtained. By virtue of the large surface area and good conductivey, which are ensured by the unique hybrid structure, as well as the proper nitrogen doping, the as-prepared composite presents enhanced catalytic performance toward the VO2+/VO2+ redox reaction. Wemore » also demonstrated the composite with carbon nanotube loading of 2 mg/mL exhibits the highest activity and remarkable stability in aqueous solution due to the strong synergy between reduced graphene oxide and carbon nanotubes, indicating that this composite might show promising applications in vanadium redox flow battery.« less

The oxidation of organic additives in the positive vanadium electrolyte and its effect on the performance of vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Nguyen, Tam D.; Whitehead, Adam; Scherer, Günther G.; Wai, Nyunt; Oo, Moe O.; Bhattarai, Arjun; Chandra, Ghimire P.; Xu, Zhichuan J.

2016-12-01

Despite many desirable properties, the vanadium redox flow battery is limited, in the maximum operation temperature that can be continuously endured, before precipitation begins in the positive electrolyte. Many additives have been proposed to improve the thermal stability of the charged positive electrolyte. However, we have found that the apparent stability, revealed in laboratory testing, is often simply an artifact of the test method and arises from the oxidation of the additive, with corresponding partial reduction of V(V) to V(IV). This does not improve the stability of the electrolyte in an operating system. Here, we examined the oxidation of some typical organic additives with carboxyl, alcohol, and multi-functional groups, in sulfuric acid solutions containing V(V). The UV-vis measurements and titration results showed that many compounds reduced the state-of-charge (SOC) of vanadium electrolyte, for example, by 27.8, 88.5, and 81.9% with the addition of 1%wt of EDTA disodium salt, pyrogallol, and ascorbic acid, respectively. The cell cycling also indicated the effect of organic additives on the cell performance, with significant reduction in the usable charge capacity. In addition, a standard screening method for thermally stable additives was introduced, to quickly screen suitable additives for the positive vanadium electrolyte.

Stopped-in-loop flow analysis system for successive determination of trace vanadium and iron in drinking water using their catalytic reactions.

PubMed

Ayala Quezada, Alejandro; Ohara, Keisuke; Ratanawimarnwong, Nuanlaor; Nacapricha, Duangjai; Murakami, Hiroya; Teshima, Norio; Sakai, Tadao

2015-11-01

An automated stopped-in-loop flow analysis (SILFA) system is proposed for the successive catalytic determination of vanadium and iron. The determination of vanadium was based on the p-anisidine oxidation by potassium bromate in the presence of Tiron as an activator to form a reddish dye, which has an absorption maximum at 510 nm. The selectivity of the vanadium determination was greatly improved by adding diphosphate as a masking agent of iron. For the iron determination, an iron-catalyzed oxidative reaction of p-anisidine by hydrogen peroxide with 1,10-phenanthroline as an activator to produce a reddish dye (510 nm) was employed. The SILFA system consisted of two peristaltic pumps, two six-port injection valves, a four-port selection valve, a heater device, a spectrophotometric detector and a data acquisition device. One six-port injection valve was used for the isolation of a mixed solution of standard/sample and reagent to promote each catalytic reaction, and another six-port injection valve was used for switching the reagent for vanadium or iron to achieve selective determination of each analyte. The above mentioned four-port selection valve was used to select standard solutions or sample. These three valves and the two peristaltic pumps were controlled by a built-in programmable logic controller in a touchscreen controller. The obtained results showed that the proposed SILFA monitoring system constituted an effective approach for the selective determination of vanadium and iron. The limits of detection, 0.052 and 0.55 µg L(-1), were obtained for vanadium and iron, respectively. The proposed system was successfully applied to drinking water samples without any preconcentration procedures. Copyright © 2015 Elsevier B.V. All rights reserved.

Capacity Decay Mitigation by Asymmetric Positive/Negative Electrolyte Volumes in Vanadium Redox Flow Batteries.

PubMed

Park, Jong Ho; Park, Jung Jin; Park, O Ok; Yang, Jung Hoon

2016-11-23

Capacity decay in vanadium redox flow batteries during charge-discharge cycling has become an important issue because it lowers the practical energy density of the battery. The battery capacity tends to drop rapidly within the first tens of cycles and then drops more gradually over subsequent cycles during long-term operation. This paper analyzes and discusses the reasons for this early capacity decay. The imbalanced crossover rate of vanadium species was found to remain high until the total difference in vanadium concentration between the positive and negative electrolytes reached almost 1 mol dm -3 . To minimize the initial crossover imbalance, we introduced an asymmetric volume ratio between the positive and negative electrolytes during cell operation. Changing this ratio significantly reduced the capacity fading rate of the battery during the early cycles and improved its capacity retention at steady state. As an example, the practical energy density of the battery increased from 15.5 to 25.2 Wh L -1 simply after reduction of the positive volume by 25 %. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Random quaternary ammonium Diels-Alder poly(phenylene) copolymers for improved vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Largier, Timothy D.; Cornelius, Chris J.

2017-06-01

This study analyzes the effect of quaternary ammonium homopolymer (AmPP) and ionic and non-ionic random unit copolymerization (AmPP-PP) of Diels-Alder poly(phenylene)s on electrochemical and transport properties, vanadium redox flow battery performance, and material stability. AmPP-PP materials were synthesized with IEC's up to 2.2 meq/g, displaying a carbonate form ion conductivity of 17.3 mS/cm and water uptake of 57.3%. Vanadium ion permeability studies revealed that the random copolymers possess superior charge carrier selectivity. For materials of comparable ion content, at 10 mA/cm2 the random copolymer displayed a 14% increase in coulombic efficiency (CE) corresponding to a 7% increase in energy efficiency. All quaternary ammonium materials displayed ex situ degradation in a 0.5 M V5+ + 5 M H2SO4 solution, with the rate of degradation appearing to increase with IEC. Preliminary studies reveal that the neutralizing counter-ion has a significant effect on VRB performance, proportional to changes in vanadium ion molecular diffusion.

A new electrocatalyst and its application method for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wei, Guanjie; Jing, Minghua; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei

2015-08-01

The edge plane in carbon structure has good electrocatalytic activity toward vanadium redox reaction. To apply it in vanadium redox flow battery (VRFB) practically, the graphite nanopowders (GNPs) containing amounts of edge planes are used as electrocatalyst and embedded in the electrospun carbon nanofibers (ECNFs) by different mass ratios to make composite electrodes. The morphology and electrochemical activity of the GNPs and the composite electrodes containing them are characterized. Compared with the pristine ECNFs, the composite electrodes show much higher electrochemical activity. With the increase of GNPs content in composite electrodes, the electrochemical reversibility of the vanadium redox couples also increases. It proves the addition of GNPs can surely improve the electrochemical activity of ECNFs. Among the composite electrodes, the ECNFs containing 30 nm GNP by mass ratio of 1:50 show the best electrochemical activity, largest active surface area and excellent stability. Due to the high performance of GNP/ECNFs composite electrode and its relatively low cost preparation process, the GNPs are expected to be used as electrocatalyst in VRFB on a large scale to improve the cell performance.

Lithium vanadium oxides (Li1+xV3O8) as cathode materials in lithium-ion batteries for soldier portable power systems

NASA Astrophysics Data System (ADS)

Wang, Gaojun; Chen, Linfeng; Mathur, Gyanesh N.; Varadan, Vijay K.

2011-04-01

Improving soldier portable power systems is very important for saving soldiers' lives and having a strategic advantage in a war. This paper reports our work on synthesizing lithium vanadium oxides (Li1+xV3O8) and developing their applications as the cathode (positive) materials in lithium-ion batteries for soldier portable power systems. Two synthesizing methods, solid-state reaction method and sol-gel method, are used in synthesizing lithium vanadium oxides, and the chemical reaction conditions are determined mainly based on thermogravimetric and differential thermogravimetric (TG-DTG) analysis. The synthesized lithium vanadium oxides are used as the active positive materials in the cathodes of prototype lithium-ion batteries. By using the new solid-state reaction technique proposed in this paper, lithium vanadium oxides can be synthesized at a lower temperature and in a shorter time, and the synthesized lithium vanadium oxide powders exhibit good crystal structures and good electrochemical properties. In the sol-gel method, different lithium source materials are used, and it is found that lithium nitrate (LiNO3) is better than lithium carbonate (Li2CO3) and lithium hydroxide (LiOH). The lithium vanadium oxides synthesized in this work have high specific charge and discharge capacities, which are helpful for reducing the sizes and weights, or increasing the power capacities, of soldier portable power systems.

[Determination of Fe, Ti and V in vanadium and titanium magnetite by ICP-OES and microwave-assisted digestion].

PubMed

Zhu, Xia-ping; Yin, Ji-xian; Chen, Wei-dong; Hu, Zi-Wen; Liang, Qing-xun; Chen, Tie-yao

2010-08-01

The method of determination of iron, titanium and vanadium in indissolvable vanadium and titanium magnetite has been established by inductively coupled plasma atomic emission spectroscopy through adding the complexant A and using microwave-assisted digestion. The optimal conditions are confirmed by orthogonal experiment: 0.1 g vanadium and titanium magnetite, 0.04 g complexant A, 12 mL concentrated HC1, 10 min digestion time, and 385 W microwave power. The newly-established method has been applied to digest vanadium and titanium magnetite of Panzhihua Iron and Steel Institute (GBW07226). The iron, titanium and vanadium were detected by ICP-OES, and both comparative error (Er%) and comparative standard deviation (RSD%) met the demand of analytical chemistry, and the complexant A can significantly accelerate the dissolution of vanadium and titanium magnetite through the complexation with the dissolved metal ions, and making the surface of sample and hydrochloric acid medium to update constantly. The determination of the main and trace elements of digestion solution at the same time was achieved by ICP-OES. The method has the advantages of less use of reagents, economy, rapidness, and being friendly to environment, and it meets the requirement for rapid and volume determination. So the method has the value of practical application for the entry-exit inspection and quarantine department of the state and other relevant inspection units.

Advanced porous electrodes with flow channels for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Bhattarai, Arjun; Wai, Nyunt; Schweiss, Ruediger; Whitehead, Adam; Lim, Tuti M.; Hng, Huey Hoon

2017-02-01

Improving the overall energy efficiency by reducing pumping power and improving flow distribution of electrolyte, is a major challenge for developers of flow batteries. The use of suitable channels can improve flow distribution through the electrodes and reduce flow resistance, hence reducing the energy consumption of the pumps. Although several studies of vanadium redox flow battery have proposed the use of bipolar plates with flow channels, similar to fuel cell designs, this paper presents the use of flow channels in the porous electrode as an alternative approach. Four types of electrodes with channels: rectangular open channel, interdigitated open cut channel, interdigitated circular poked channel and cross poked circular channels, are studied and compared with a conventional electrode without channels. Our study shows that interdigitated open channels can improve the overall energy efficiency up to 2.7% due to improvement in flow distribution and pump power reduction while interdigitated poked channel can improve up to 2.5% due to improvement in flow distribution.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pezeshki, Alan M.; Sacci, Robert L.; Delnick, Frank M.

Here, an improved method for quantitative measurement of the charge transfer, finite diffusion, and ohmic overpotentials in redox flow batteries using electrochemical impedance spectroscopy is presented. The use of a pulse dampener in the hydraulic circuit enables the collection of impedance spectra at low frequencies with a peristaltic pump, allowing the measurement of finite diffusion resistances at operationally relevant flow rates. This method is used to resolve the rate-limiting processes for the V 2+/V 3+ redox couple on carbon felt and carbon paper electrodes in the vanadium redox flow battery. Carbon felt was limited by both charge transfer and ohmicmore » resistance, while carbon paper was limited by charge transfer, finite diffusion, and ohmic resistances. The influences of vanadium concentration and flow field design also are quantified.« less

Effect of electrode intrusion on pressure drop and electrochemical performance of an all-vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Kumar, S.; Jayanti, S.

2017-08-01

In this paper, we present a study of the effect of electrode intrusion into the flow channel in an all-vanadium redox flow battery. Permeability, pressure drop and electrochemical performance have been measured in a cell with active area 100 cm2and 414 cm2 fitted with a carbon felt electrode of thickness of 3, 6 or 9 mm compressed to 1.5, 2.5 or 4 mm, respectively, during assembly. Results show that the pressure drop is significantly higher than what can be expected in the thick electrode case while its electrochemical performance is lower. Detailed flow analysis using computational fluid dynamics simulations in two different flow fields shows that both these results can be attributed to electrode intrusion into the flow channel leading to increased resistance to electrolyte flow through the electrode. A correlation is proposed to evaluate electrode intrusion depth as a function of compression.

PROCESS FOR RECOVERY OF URANIUM AND VANADIUM FROM CARBONATE SOLUTIONS BY REDUCTION-PRECIPITATION

DOEpatents

Ellis, D.A.; Lindblom, R.O.

1957-09-24

A process employing carbonate leaching of ores and an advantageous methcd of recovering the uranium and vanadium from the leach solution is described. The uranium and vanadium can be precipitated from carbonate leach solutions by reaction with sodium amalgam leaving the leach solution in such a condition that it is economical to replenish for recycling. Such a carbonate leach solution is treated with a dilute sodium amalgam having a sodium concentration within a range of about 0.01 to 0.5% of sodium. Efficiency of the treatment is dependent on at least three additional factors, intimacy of contact of the amalgam with the leach solution, rate of addition of the amalgam and exclusion of oxygen (air).

Bifunctional Crosslinking Agents Enhance Anion Exchange Membrane Efficacy for Vanadium Redox Flow Batteries.

PubMed

Wang, Wenpin; Xu, Min; Wang, Shubo; Xie, Xiaofeng; Lv, Yafei; Ramani, Vijay K

2014-06-02

A series of cross-linked fluorinated poly (aryl ether oxadiazole) membranes (FPAEOM) derivatized with imidazolium groups were prepared. Poly (N-vinylimidazole) (PVI) was used as the bifunctional cross-linking agent to: a) lower vanadium permeability, b) enhance dimensional stability, and c) concomitantly provide added ion exchange capacity in the resultant anion exchange membranes. At a molar ratio of PVI to FPAEOM of 1.5, the resultant membrane (FPAEOM-1.5 PVI) had an ion exchange capacity of 2.2 meq g-1, a vanadium permeability of 6.8×10-7 cm2 min-1, a water uptake of 68 wt.%, and an ionic conductivity of 22.0 mS cm-1, all at 25°C. Single cells prepared with the FPAEOM-1.5 PVI membrane exhibited a higher coulombic efficiency (> 92%) and energy efficiency (> 86%) after 40 test cycles in vanadium redox flow battery. The imidazolium cation showed high chemical stability in highly acidic and oxidizing vanadium solution as opposed to poor stability in alkaline solutions. Based on our DFT studies, this was attributed to the lower HOMO energy (-7.265 eV) of the HSO4- ion (compared to the OH- ion; -5.496 eV) and the larger HOMO-LUMO energy gap (6.394 eV) of dimethylimidazolium bisulfate ([DMIM] [HSO4]) as compared to [DMIM] [OH] (5.387 eV).

Influence of Membrane Equivalent Weight and Reinforcement on Ionic Species Crossover in All-Vanadium Redox Flow Batteries.

PubMed

Ashraf Gandomi, Yasser; Aaron, Doug S; Mench, Matthew M

2017-06-06

One of the major sources of lost capacity in all-vanadium redox flow batteries (VRFBs) is the undesired transport (usually called crossover) of water and vanadium ions through the ion-exchange membrane. In this work, an experimental assessment of the impact of ion-exchange membrane properties on vanadium ion crossover and capacity decay of VRFBs has been performed. Two types of cationic membranes (non-reinforced and reinforced) with three equivalent weights of 800, 950 and 1100 g·mol -1 were investigated via a series of in situ performance and capacity decay tests along with ex situ vanadium crossover measurement and membrane characterization. For non-reinforced membranes, increasing the equivalent weight (EW) from 950 to 1100 g·mol -1 decreases the V(IV) permeability by ~30%, but increases the area-specific resistance (ASR) by ~16%. This increase in ASR and decrease in V(IV) permeability was accompanied by increased through-plane membrane swelling. Comparing the non-reinforced with reinforced membranes, membrane reinforcement increases ASR, but V(IV) permeability decreases. It was also shown that there exists a monotonic correlation between the discharge capacity decay over long-term cycling and V(IV) permeability values. Thus, V(IV) permeability is considered a representative diagnostic for assessing the overall performance of a particular ion-exchange membrane with respect to capacity fade in a VRFB.

Influence of Membrane Equivalent Weight and Reinforcement on Ionic Species Crossover in All-Vanadium Redox Flow Batteries

PubMed Central

Ashraf Gandomi, Yasser; Aaron, Doug S.; Mench, Matthew M.

2017-01-01

One of the major sources of lost capacity in all-vanadium redox flow batteries (VRFBs) is the undesired transport (usually called crossover) of water and vanadium ions through the ion-exchange membrane. In this work, an experimental assessment of the impact of ion-exchange membrane properties on vanadium ion crossover and capacity decay of VRFBs has been performed. Two types of cationic membranes (non-reinforced and reinforced) with three equivalent weights of 800, 950 and 1100 g·mol−1 were investigated via a series of in situ performance and capacity decay tests along with ex situ vanadium crossover measurement and membrane characterization. For non-reinforced membranes, increasing the equivalent weight (EW) from 950 to 1100 g·mol−1 decreases the V(IV) permeability by ~30%, but increases the area-specific resistance (ASR) by ~16%. This increase in ASR and decrease in V(IV) permeability was accompanied by increased through-plane membrane swelling. Comparing the non-reinforced with reinforced membranes, membrane reinforcement increases ASR, but V(IV) permeability decreases. It was also shown that there exists a monotonic correlation between the discharge capacity decay over long-term cycling and V(IV) permeability values. Thus, V(IV) permeability is considered a representative diagnostic for assessing the overall performance of a particular ion-exchange membrane with respect to capacity fade in a VRFB. PMID:28587268

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crawford, Aladsair J.; Viswanathan, Vilayanur V.; Stephenson, David E.

A robust performance-based cost model is developed for all-vanadium, iron-vanadium and iron chromium redox flow batteries. Systems aspects such as shunt current losses, pumping losses and thermal management are accounted for. The objective function, set to minimize system cost, allows determination of stack design and operating parameters such as current density, flow rate and depth of discharge (DOD). Component costs obtained from vendors are used to calculate system costs for various time frames. A 2 kW stack data was used to estimate unit energy costs and compared with model estimates for the same size electrodes. The tool has been sharedmore » with the redox flow battery community to both validate their stack data and guide future direction.« less

Tuning the Perfluorosulfonic Acid Membrane Morphology for Vanadium Redox-Flow Batteries.

PubMed

Vijayakumar, M; Luo, Qingtao; Lloyd, Ralph; Nie, Zimin; Wei, Xiaoliang; Li, Bin; Sprenkle, Vincent; Londono, J-David; Unlu, Murat; Wang, Wei

2016-12-21

The microstructure of perfluorinated sulfonic acid proton-exchange membranes such as Nafion significantly affects their transport properties and performance in a vanadium redox-flow battery (VRB). In this work, Nafion membranes with various equivalent weights ranging from 1000 to 1500 are prepared and the morphology-property-performance relationship is investigated. NMR and small-angle X-ray scattering studies revealed their composition and morphology variances, which lead to major differences in key transport properties related to proton conduction and vanadium-ion permeation. Their performances are further characterized as VRB membranes. On the basis of this understanding, a new perfluorosulfonic acid membrane is designed with optimal pore geometry and thickness, leading to higher ion selectivity and lower cost compared with the widely used Nafion 115. Excellent VRB single-cell performance (89.3% energy efficiency at 50 mA·cm -2 ) was achieved along with a stable cyclical capacity over prolonged cycling.

Nitrogen-Doped Carbon Nanotube/Graphite Felts as Advanced Electrode Materials for Vanadium Redox Flow Batteries.

PubMed

Wang, Shuangyin; Zhao, Xinsheng; Cochell, Thomas; Manthiram, Arumugam

2012-08-16

Nitrogen-doped carbon nanotubes have been grown, for the first time, on graphite felt (N-CNT/GF) by a chemical vapor deposition approach and examined as an advanced electrode for vanadium redox flow batteries (VRFBs). The unique porous structure and nitrogen doping of N-CNT/GF with increased surface area enhances the battery performance significantly. The enriched porous structure of N-CNTs on graphite felt could potentially facilitate the diffusion of electrolyte, while the N-doping could significantly contribute to the enhanced electrode performance. Specifically, the N-doping (i) modifies the electronic properties of CNT and thereby alters the chemisorption characteristics of the vanadium ions, (ii) generates defect sites that are electrochemically more active, (iii) increases the oxygen species on CNT surface, which is a key factor influencing the VRFB performance, and (iv) makes the N-CNT electrochemically more accessible than the CNT.

Techno-economic assessment of novel vanadium redox flow batteries with large-area cells

NASA Astrophysics Data System (ADS)

Minke, Christine; Kunz, Ulrich; Turek, Thomas

2017-09-01

The vanadium redox flow battery (VRFB) is a promising electrochemical storage system for stationary megawatt-class applications. The currently limited cell area determined by the bipolar plate (BPP) could be enlarged significantly with a novel extruded large-area plate. For the first time a techno-economic assessment of VRFB in a power range of 1 MW-20 MW and energy capacities of up to 160 MWh is presented on the basis of the production cost model of large-area BPP. The economic model is based on the configuration of a 250 kW stack and the overall system including stacks, power electronics, electrolyte and auxiliaries. Final results include a simple function for the calculation of system costs within the above described scope. In addition, the impact of cost reduction potentials for key components (membrane, electrode, BPP, vanadium electrolyte) on stack and system costs is quantified and validated.

Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

DOE PAGES

Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; ...

2015-11-14

In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm 2.« less

Elucidating the Higher Stability of Vanadium (V) Cations in Mixed Acid Based Redox Flow Battery Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, M.; Wang, Wei; Nie, Zimin

2013-11-01

The Vanadium (V) cation structures in mixed acid based electrolyte solution were analysed by density functional theory (DFT) based computational modelling and 51V and 35Cl Nuclear Magnetic Resonance (NMR) spectroscopy. The Vanadium (V) cation exists as di-nuclear [V2O3Cl2.6H2O]2+ compound at higher vanadium concentrations (≥1.75M). In particular, at high temperatures (>295K) this di-nuclear compound undergoes ligand exchange process with nearby solvent chlorine molecule and forms chlorine bonded [V2O3Cl2.6H2O]2+ compound. This chlorine bonded [V2O3Cl2.6H2O]2+ compound might be resistant to the de-protonation reaction which is the initial step in the precipitation reaction in Vanadium based electrolyte solutions. The combined theoretical and experimental approachmore » reveals that formation of chlorine bonded [V2O3Cl2.6H2O]2+ compound might be central to the observed higher thermal stability of mixed acid based Vanadium (V) electrolyte solutions.« less

The fabrication and visible-near-infrared optical modulation of vanadium dioxide/silicon dioxide composite photonic crystal structure

NASA Astrophysics Data System (ADS)

Liang, Jiran; Li, Peng; Song, Xiaolong; Zhou, Liwei

2017-12-01

We demonstrated a visible and near-infrared light tunable photonic nanostructure, which is composed of vanadium dioxide (VO2) thin film and silicon dioxide (SiO2) ordered nanosphere arrays. The vanadium films were sputtered on two-dimensional (2D) SiO2 sphere arrays. VO2 thin films were prepared by rapid thermal annealing (RTA) method with different oxygen flow rates. The close-packed VO2 shell formed a continuous surface, the composition of VO2 films in the structure changed when the oxygen flow rates increased. The 2D VO2/SiO2 composite photonic crystal structure exhibited transmittance trough tunability and near-infrared (NIR) transmittance modulation. When the oxygen flow rate increased from 3 slpm to 4 slpm, the largest transmittance trough can be regulated from 904 to 929 nm at low temperature, the transmittance troughs also appear blue shift when the VO2 phase changes from insulator to metal. The composite nanostructure based on VO2 films showed visible transmittance tunability, which would provide insights into the glass color changing in smart windows.

Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

PubMed

Sepehr, Fatemeh; Paddison, Stephen J

2015-06-04

Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane.

Influence of architecture and material properties on vanadium redox flow battery performance

NASA Astrophysics Data System (ADS)

Houser, Jacob; Clement, Jason; Pezeshki, Alan; Mench, Matthew M.

2016-01-01

This publication reports a design optimization study of all-vanadium redox flow batteries (VRBs), including performance testing, distributed current measurements, and flow visualization. Additionally, a computational flow simulation is used to support the conclusions made from the experimental results. This study demonstrates that optimal flow field design is not simply related to the best architecture, but is instead a more complex interplay between architecture, electrode properties, electrolyte properties, and operating conditions which combine to affect electrode convective transport. For example, an interdigitated design outperforms a serpentine design at low flow rates and with a thin electrode, accessing up to an additional 30% of discharge capacity; but a serpentine design can match the available discharge capacity of the interdigitated design by increasing the flow rate or the electrode thickness due to differing responses between the two flow fields. The results of this study should be useful to design engineers seeking to optimize VRB systems through enhanced performance and reduced pressure drop.

Properties investigation of sulfonated poly(ether ether ketone)/polyacrylonitrile acid-base blend membrane for vanadium redox flow battery application.

PubMed

Li, Zhaohua; Dai, Wenjing; Yu, Lihong; Liu, Le; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

2014-11-12

Acid-base blend membrane prepared from sulfonated poly(ether ether ketone) (SPEEK) and polyacrylonitrile (PAN) was detailedly evaluated for vanadium redox flow battery (VRFB) application. SPEEK/PAN blend membrane exhibited dense and homogeneous cross-section morphology as scanning electron microscopy and energy-dispersive X-ray spectroscopy images show. The acid-base interaction of ionic cross-linking and hydrogen bonding between SPEEK and PAN could effectively reduce water uptake, swelling ratio, and vanadium ion permeability, and improve the performance and stability of blend membrane. Because of the good balance of proton conductivity and vanadium ion permeability, blend membrane with 20 wt % PAN (S/PAN-20%) showed higher Coulombic efficiency (96.2% vs 91.1%) and energy efficiency (83.5% vs 78.4%) than Nafion 117 membrane at current density of 80 mA cm(-2) when they were used in VRFB single cell. Besides, S/PAN-20% membrane kept a stable performance during 150 cycles at current density of 80 mA cm(-2) in the cycle life test. Hence the SPEEK/PAN acid-base blend membrane could be used as promising candidate for VRFB application.

Modelling and simulation of thermal behaviour of vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Yan, Yitao; Li, Yifeng; Skyllas-Kazacos, Maria; Bao, Jie

2016-08-01

This paper extends previous thermal models of the vanadium redox flow battery to predict temperature profiles within multi-cell stacks. This involves modelling the thermal characteristics of the stack as a whole to modelling each individual cell. The study investigates the thermal behaviour for two different scenarios: during standby periods when the pumps are turned off, and in a residential power arbitrage scenario for two types of membranes. It was found that the temperature gradient across the cells is most significant during the standby case, with the simulation results showing completely different thermal behaviours between the two systems.

Studies on Molecular and Ion Transport in Silicalite Membranes and Applications as Ion Separator for Redox Flow Battery

NASA Astrophysics Data System (ADS)

Yang, Ruidong

Microporous zeolite membranes have been widely studied for molecular separations based on size exclusion or preferential adsorption-diffusion mechanisms. The MFI-type zeolite membranes were also demonstrated for brine water desalination by molecular sieving effect. In this research, the pure silica MFI-type zeolite (i.e. silicalite) membrane has been for the first time demonstrated for selective permeation of hydrated proton (i.e. H3O+) in acidic electrolyte solutions. The silicalite membrane allows for permeation of H 3O+ ions, but is inaccessible to the large hydrated multivalent vanadium ions due to steric effect. The silicalite membrane has been further demonstrated as an effective ion separator in the all-vanadium redox flow battery (RFB).The silicalite is nonionic and its proton conductivity relies on the electric field-driven H3O+ transport through the sub nanometer-sized pores under the RFB operation conditions. The silicalite membrane displayed a significantly reduced self-discharge rate because of its high proton-to-vanadium ion transport selectivity. However, the nonionic nature of the silicalite membrane and very small diffusion channel size render low proton conductivity and is therefore inefficient as ion exchange membranes (IEMs) for practical applications. The proton transport efficiency may be improved by reducing the membrane thickness. However, the zeolite thin films are extremely fragile and must be supported on mechanically strong and rigid porous substrates. In this work, silicalite-Nafion composite membranes were synthesized to achieve a colloidal silicalite skin on the Nafion thin film base. The "colloidal zeolite-ionic polymer" layered composite membrane combines the advantages of high proton-selectivity of the zeolite layer and the mechanical flexibility and low proton transport resistance of the ionic polymer membrane. The composite membrane exhibited higher proton/vanadium ion separation selectivity and lower electrical resistance than the commercial Nafion 117 membrane. The high proton transport selectivity is a result of the molecular sieving effect between the H3O+ and multivalent vanadium ions by the zeolitic pores; thus the zeolite particles significantly reduced the effective membrane surface area for vanadium ion permeation. The low resistance of the composite membrane can be attributed to the reduced thickness of the Nafion base film and the thinness of the colloidal silicalite top layer. The composite membrane outperformed the Nafion 117 membrane in the vanadium RFB operation in terms of the overall charge-discharge energy efficiency. Efforts have been made in further investigation of ion and molecular transport diffusivity in the polycrystalline silicalite film using zeolite-coated optical fiber interferometers. A physical model has been established for analyzing the molecular diffusivity in the zeolite layer based on the temporal responses of the optical interferometric signals during the transient process of molecular sorption. Experiments were first carried out to study the diffusivity of isobutane to evaluate the effectiveness of the proposed optical method. The isobutane diffusivities in silicalite measured by this method were in good agreement with the values reported in literature. The zeolite coated fiber optic interferometer was however ineffective in monitoring ion sorption or ion exchange in the silicalite films. It is suggested that more sensitive fiber optic devices are needed for studying the ion diffusion.

Vanadium(III)-l-cysteine enhances the sensitivity of murine breast adenocarcinoma cells to cyclophosphamide by promoting apoptosis and blocking angiogenesis.

PubMed

Basu, Abhishek; Bhattacharjee, Arin; Baral, Rathindranath; Biswas, Jaydip; Samanta, Amalesh; Bhattacharya, Sudin

2017-05-01

Various epidemiological and preclinical studies have already established the cancer chemopreventive potential of vanadium-based compounds. In addition to its preventive efficacy, studies have also indicated the abilities of vanadium-based compounds to induce cell death selectively toward malignant cells. Therefore, the objective of the present investigation is to improve the therapeutic efficacy and toxicity profile of an alkylating agent, cyclophosphamide, by the concurrent use of an organovanadium complex, vanadium(III)-l-cysteine. In this study, vanadium(III)-l-cysteine (1 mg/kg body weight, per os) was administered alone as well as in combination with cyclophosphamide (25 mg/kg body weight, intraperitoneal) in concomitant and pretreatment schedule in mice bearing breast adenocarcinoma cells. The results showed that the combination treatment significantly decreased the tumor burden and enhanced survivability of tumor-bearing mice through generation of reactive oxygen species in tumor cells. These ultimately led to DNA damage, depolarization of mitochondrial membrane potential, and apoptosis in tumor cells. Further insight into the molecular pathway disclosed that the combination treatment caused upregulation of p53 and Bax and suppression of Bcl-2 followed by the activation of caspase cascade and poly (ADP-ribose) polymerase cleavage. Administration of vanadium(III)-l-cysteine also resulted in significant attenuation of peritoneal vasculature and sprouting of the blood vessels by decreasing the levels of vascular endothelial growth factor A and matrix metalloproteinase 9 in the ascites fluid of tumor-bearing mice. Furthermore, vanadium(III)-l-cysteine significantly attenuated cyclophosphamide-induced hematopoietic, hepatic, and genetic damages and provided additional survival advantages. Hence, this study suggested that vanadium(III)-l-cysteine may offer potential therapeutic benefit in combination with cyclophosphamide by augmenting anticancer efficacy and diminishing toxicity to the host.

Automated stopped-in-dual-loop flow analysis system for catalytic determination of vanadium in drinking water.

PubMed

Teshima, Norio; Kuno, Masami; Ueda, Minoru; Ueda, Hisashi; Ohno, Shinsuke; Sakai, Tadao

2009-07-15

An automated stopped-in-dual-loop flow analysis (SIDL-FA) system is proposed for the determination of vanadium in drinking water. The chemistry is based on the vanadium-catalyzed oxidation reaction of p-anisidine by bromate in the presence of Tiron as an activator to produce a dye (lambda(max)=510 nm). A SIDL-FA system basically consists of a selection valve, three pumps (one is for delivering of standard/sample, and others are for reagents), two six-way injection valves, a spectrophotometric detector and a data acquisition device. A 100-microL coiled loop around a heated device is fitted onto each six-way injection valve. A well-mixed solution containing reagents and standard/sample is loaded into the first loop on a six-way valve, and then the same solution is loaded into the second loop on another six-way valve. The solutions are isolated by switching these two six-way valves, so that the catalytic reaction can be promoted. The net waste can be zero in this stage, because all pumps are turned off. Then each resulting solution is dispensed to the detector with suitable time lag. A touchscreen controller is developed to automatically carry out the original SIDL-FA protocol. The proposed SIDL-FA method allows vanadium to be quantified in the range of 0.1-2 microg L(-1) and is applied to the determination of vanadium in drinking water samples.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, David; Thomsen, Edwin; Li, Bin

Three flow designs were operated in a 3-cell 1 kW class all vanadium mixed acid redox flow battery. The influence of electrode surface area and flow rate on the coulombic, voltage, and energy efficiency and the pressure drop in the flow circuit will be discussed and correlated to the flow design. Material cost associated with each flow design will also be discussed.

Vanadium Flow Battery Electrolyte Synthesis via Chemical Reduction of V2O5 in Aqueous HCl and H2SO4.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Small, Leo J.; Pratt, Harry; Staiger, Chad

We report a simple method to synthesize V 4+ (VO 2+ ) electrolytes as feedstock for all- vanadium redox flow batteries (RFB). By dissolving V 2 O 5 in aqueous HCl and H 2 SO 4 , subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V 4+ (VO 2+ ). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65 degC) for V 4+ (VO 2+ ) electrolytes in HCl compared to in H 2 SO 4 electrolytes.

Influence of aminosilane precursor concentration on physicochemical properties of composite Nafion membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Kondratenko, Mikhail S.; Karpushkin, Evgeny A.; Gvozdik, Nataliya A.; Gallyamov, Marat O.; Stevenson, Keith J.; Sergeyev, Vladimir G.

2017-02-01

A series of composite proton-exchange membranes have been prepared via sol-gel modification of commercial Nafion membranes with [N-(2-aminoethyl)-3-aminopropyl]trimethoxysilane. The structure and physico-chemical properties (water uptake, ion-exchange capacity, vanadyl ion permeability, and proton conductivity) of the prepared composite membranes have been studied as a function of the precursor loading (degree of the membrane modification). If the amount of the precursor is below 0.4/1 M ratio of the amino groups of the precursor to the sulfonic groups of Nafion, the composite membranes exhibit decreased vanadium ion permeability while having relatively high proton conductivity. With respect to the use of a non-modified Nafion membrane, the performance of the composite membrane with an optimum precursor loading in a single-cell vanadium redox flow battery demonstrates enhanced energy efficiency in 20-80 mA cm-2 current density range. The maximum efficiency increase of 8% is observed at low current densities.

SPEEK/PVDF/PES Composite as Alternative Proton Exchange Membrane for Vanadium Redox Flow Batteries

NASA Astrophysics Data System (ADS)

Fu, Zhimin; Liu, Jinying; Liu, Qifeng

2016-01-01

A membrane consisting of a blend of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and poly(ether sulfone) (PES) has been fabricated and used as an ion exchange membrane for application in vanadium redox flow batteries (VRBs). The vanadium ion permeability of the SPEEK/PVDF/PES membrane was one order of magnitude lower than that of Nafion 117 membrane. The low-cost composite membrane exhibited better performance than Nafion 117 membrane at the same operating condition. A VRB single cell with SPEEK/PVDF/PES membrane showed significantly lower capacity loss, higher coulombic efficiency (>95%), and higher energy efficiency (>82%) compared with Nafion 117 membrane. In the self-discharge test, the duration of the cell with the SPEEK/PVDF/PES membrane was nearly two times longer than that with Nafion 117 membrane. Considering these good properties and its low cost, SPEEK/PVDF/PES membrane is expected to have excellent commercial prospects as an ion exchange membrane for VRB systems.

Detection of capacity imbalance in vanadium electrolyte and its electrochemical regeneration for all-vanadium redox-flow batteries

NASA Astrophysics Data System (ADS)

Roznyatovskaya, Nataliya; Herr, Tatjana; Küttinger, Michael; Fühl, Matthias; Noack, Jens; Pinkwart, Karsten; Tübke, Jens

2016-01-01

A vanadium electrolyte for redox-flow batteries (VRFB) with different VIII and VIV mole fractions has been studied by UV-vis spectroscopy. Spectrophotometric detection enables a rough estimate of the VIV and VIII content, which can be used to detect an electrolyte capacity imbalance, i.e. a deviation in the mole fraction of VIV or VIII away from 50%. The isosbestic point at 600 nm can be used as a reference point in the analysis of common VRFB electrolyte batches. The VRFB electrolyte is observed to have an imbalance after prolonged storage (a couple of years) in a tank under ambient conditions. A regeneration procedure, which involves pre-charging the unbalanced electrolyte and mixing part of it with a portion of initial unbalanced electrolyte, has been tested. The resulting rebalanced electrolyte has been compared with a common electrolyte in a charge-discharge cell test and is shown to be suitable for cell operation.

Crosslinked anion exchange membranes with primary diamine-based crosslinkers for vanadium redox flow battery application

NASA Astrophysics Data System (ADS)

Cha, Min Suc; Jeong, Hwan Yeop; Shin, Hee Young; Hong, Soo Hyun; Kim, Tae-Ho; Oh, Seong-Geun; Lee, Jang Yong; Hong, Young Taik

2017-09-01

A series of polysulfone-based crosslinked anion exchange membranes (AEMs) with primary diamine-based crosslinkers has been prepared via simple a crosslinking process as low-cost and durable membranes for vanadium redox flow batteries (VRFBs). Chloromethylated polysulfone is used as a precursor polymer for crosslinked AEMs (CAPSU-x) with different degrees of crosslinking. Among the developed AEMs, CAPSU-2.5 shows outstanding dimensional stability and anion (Cl-, SO42-, and OH-) conductivity. Moreover, CAPSU-2.5 exhibits much lower vanadium ion permeability (2.72 × 10-8 cm2 min-1) than Nafion 115 (2.88 × 10-6 cm2 min-1), which results in an excellent coulombic efficiency of 100%. The chemical and operational stabilities of the membranes have been investigated via ex situ soaking tests in 0.1 M VO2+ solution and in situ operation tests for 100 cycles, respectively. The excellent chemical, physical, and electrochemical properties of the CAPSU-2.5 membrane make it suitable for use in VRFBs.

A Highly Ion-Selective Zeolite Flake Layer on Porous Membranes for Flow Battery Applications.

PubMed

Yuan, Zhizhang; Zhu, Xiangxue; Li, Mingrun; Lu, Wenjing; Li, Xianfeng; Zhang, Huamin

2016-02-24

Zeolites are crystalline microporous aluminosilicates with periodic arrangements of cages and well-defined channels, which make them very suitable for separating ions of different sizes, and thus also for use in battery applications. Herein, an ultra-thin ZSM-35 zeolite flake was introduced onto a poly(ether sulfone) based porous membrane. The pore size of the zeolite (ca. 0.5 nm) is intermediary between that of hydrated vanadium ions (>0.6 nm) and protons (<0.24 nm). The resultant membrane can thus be used to perfectly separate vanadium ions and protons, making this technology useful in vanadium flow batteries (VFB). A VFB with a zeolite-coated membrane exhibits a columbic efficiency of >99 % and an energy efficiency of >81 % at 200 mA cm(-2), which is by far the highest value ever reported. These convincing results indicate that zeolite-coated membranes are promising in battery applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Low-Cost and High-Performance Sulfonated Polyimide Proton-Conductive Membrane for Vanadium Redox Flow/Static Batteries.

PubMed

Li, Jinchao; Yuan, Xiaodong; Liu, Suqin; He, Zhen; Zhou, Zhi; Li, Aikui

2017-09-27

A novel side-chain-type fluorinated sulfonated polyimide (s-FSPI) membrane is synthesized for vanadium redox batteries (VRBs) by high-temperature polycondensation and grafting reactions. The s-FSPI membrane has a vanadium ion permeability that is over an order of magnitude lower and has a proton selectivity that is 6.8 times higher compared to those of the Nafion 115 membrane. The s-FSPI membrane possesses superior chemical stability compared to most of the linear sulfonated aromatic polymer membranes reported for VRBs. Also, the vanadium redox flow/static batteries (VRFB/VRSB) assembled with the s-FSPI membranes exhibit stable battery performance over 100- and 300-time charge-discharge cycling tests, respectively, with significantly higher battery efficiencies and lower self-discharge rates than those with the Nafion 115 membranes. The excellent physicochemical properties and VRB performance of the s-FSPI membrane could be attributed to the specifically designed molecular structure with the hydrophobic trifluoromethyl groups and flexible sulfoalkyl pendants being introduced on the main chains of the membrane. Moreover, the cost of the s-FSPI membrane is only one-fourth that of the commercial Nafion 115 membrane. This work opens up new possibilities for fabricating high-performance proton-conductive membranes at low costs for VRBs.

Selective recovery of vanadium and scandium by ion exchange with D201 and solvent extraction using P507 from hydrochloric acid leaching solution of red mud.

PubMed

Zhu, Xiaobo; Li, Wang; Tang, Sen; Zeng, Majian; Bai, Pengyuan; Chen, Lunjian

2017-05-01

D201 resin and P507 extractant diluted with sulfonated kerosene were used to respectively separate vanadium and scandium, and impurity ions from hydrochloric acid leaching solution of red mud. More than 99% of vanadium was selectively adsorbed from the hydrochloric acid leaching solution under the conditions of pH value of 1.8, volume ratio of leaching solution to resin of 10, and flow rate of 3.33 mL/min. Maximum extraction and separation of scandium was observed from the acid leaching solution at an aqueous pH value of 0.2. More than 99% of scandium can be selectively extracted using 15% P507, 5% TBP at the aqueous solution/organic phase (A/O) ratio of 10:1 for 6 min. The loaded organic phase was washed with 0.3 mol/L sulfuric acid, wherein most impurities were removed. After the process of desorption or stripping, precipitation, and roasting, high-purity V 2 O 5 and Sc 2 O 3 were obtained. Finally, a conceptual flow sheet was established to separate and recover vanadium and scandium from red mud hydrochloric acid leaching solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of flow field on the performance of an all-vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Kumar, S.; Jayanti, S.

2016-03-01

A comparative study of the electrochemical energy conversion performance of a single-cell all-vanadium redox flow battery (VRFB) fitted with three flow fields has been carried out experimentally. The charge-discharge, polarization curve, Coulombic, voltage and round-trip efficiencies of a 100 cm2 active area VRFB fitted with serpentine, interdigitated and conventional flow fields have been obtained under nearly identical experimental conditions. The effect of electrolyte circulation rate has also been investigated for each flow field. Stable performance has been obtained for each flow field for at least 40 charge/discharge cycles. Ex-situ measurements of pressure drop have been carried out using water over a range of Reynolds numbers. Together, the results show that the cell fitted with the serpentine flow field gives the highest energy efficiency, primarily due to high voltaic efficiency and also the lowest pressure drop. The electrolyte flow rate is seen to have considerable effect on the performance; a high round-trip energy efficiency of about 80% has been obtained at the highest flow rate with the serpentine flow field. The data offer interesting insights into the effect of electrolyte circulation on the performance of VRFB.

Cost and performance model for redox flow batteries

NASA Astrophysics Data System (ADS)

Viswanathan, Vilayanur; Crawford, Alasdair; Stephenson, David; Kim, Soowhan; Wang, Wei; Li, Bin; Coffey, Greg; Thomsen, Ed; Graff, Gordon; Balducci, Patrick; Kintner-Meyer, Michael; Sprenkle, Vincent

2014-02-01

A cost model is developed for all vanadium and iron-vanadium redox flow batteries. Electrochemical performance modeling is done to estimate stack performance at various power densities as a function of state of charge and operating conditions. This is supplemented with a shunt current model and a pumping loss model to estimate actual system efficiency. The operating parameters such as power density, flow rates and design parameters such as electrode aspect ratio and flow frame channel dimensions are adjusted to maximize efficiency and minimize capital costs. Detailed cost estimates are obtained from various vendors to calculate cost estimates for present, near-term and optimistic scenarios. The most cost-effective chemistries with optimum operating conditions for power or energy intensive applications are determined, providing a roadmap for battery management systems development for redox flow batteries. The main drivers for cost reduction for various chemistries are identified as a function of the energy to power ratio of the storage system. Levelized cost analysis further guide suitability of various chemistries for different applications.

Performance of a vanadium redox flow battery with tubular cell design

NASA Astrophysics Data System (ADS)

Ressel, Simon; Laube, Armin; Fischer, Simon; Chica, Antonio; Flower, Thomas; Struckmann, Thorsten

2017-07-01

We present a vanadium redox flow battery with a tubular cell design which shall lead to a reduction of cell manufacturing costs and the realization of cell stacks with reduced shunt current losses. Charge/discharge cycling and polarization curve measurements are performed to characterize the single test cell performance. A maximum current density of 70 mAcm-2 and power density of 142 Wl-1 (per cell volume) is achieved and Ohmic overpotential is identified as the dominant portion of the total cell overpotential. Cycling displays Coulomb efficiencies of ≈95% and energy efficiencies of ≈55%. During 113 h of operation a stable Ohmic cell resistance is observed.

Characterization and Electrical Response to Humidity of Sintered Polymeric Electrospun Fibers of Vanadium Oxide-({TiO}_{{2}} /{WO}_{{3}} )

NASA Astrophysics Data System (ADS)

Araújo, E. S.; Libardi, J.; Faia, P. M.; de Oliveira, H. P.

2018-02-01

Metal oxide composites have attracted much consideration due to their promising applications in humidity sensors in response to the physical and chemical property modifications of the resulting materials. This work focused on the preparation, microstructural characterization and analysis of humidity-dependent electrical properties of undoped and vanadium oxide (V2O5)-doped titanium oxide/tungsten oxide (TiO2/WO3) sintered ceramic films obtained by electrospinning. The electrical properties were investigated by impedance spectroscopy (400 Hz-40 MHz) as a function of relative humidity (RH). The results revealed a typical transition in the transport mechanisms controlled by the appropriated doping level of V2O5, which introduces important advantages to RH detection due to the atomic substitution of titanium by vanadium atoms in highly doped structures. These aspects are directly related to the microstructure modification and structure fabrication procedure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Xiaoliang; Nie, Zimin; Luo, Qingtao

Driven by the motivation of searching for low-cost membrane alternatives, a novel nanoporous polytetrafluoroethylene/silica composite separator has been prepared and evaluated for its use in all-vanadium mixed-acid redox flow battery. This separator consisting of silica particles enmeshed in a polytetrafluoroethylene fibril matrix has no ion exchange capacity and is featured with unique nanoporous structures, which function as the ion transport channels in redox flow battery operation, with an average pore size of 38nm and a porosity of 48%. This separator has produced excellent electrochemical performance in the all-vanadium mixed-acid system with energy efficiency delivery comparable to Nafion membrane and superiormore » rate capability and temperature tolerance. The separator also demonstrates an exceptional capacity retention capability over extended cycling, offering additional operational latitude towards conveniently mitigating the capacity decay that is inevitable for Nafion. Because of the inexpensive raw materials and simple preparation protocol, the separator is particularly low-cost, estimated to be at least an order of magnitude more inexpensive than Nafion. Plus the proven chemical stability due to the same backbone material as Nafion, this separator possesses a good combination of critical membrane requirements and shows great potential to promote market penetration of the all-vanadium redox flow battery by enabling significant reduction of capital and cycle costs.« less

Vanadium Redox Flow Batteries Using meta-Polybenzimidazole-Based Membranes of Different Thicknesses.

PubMed

Noh, Chanho; Jung, Mina; Henkensmeier, Dirk; Nam, Suk Woo; Kwon, Yongchai

2017-10-25

15, 25, and 35 μm thick meta-polybenzimidazole (PBI) membranes are doped with H 2 SO 4 and tested in a vanadium redox flow battery (VRFB). Their performances are compared with those of Nafion membranes. Immersed in 2 M H 2 SO 4 , PBI absorbs about 2 mol of H 2 SO 4 per mole of repeat unit. This results in low conductivity and low voltage efficiency (VE). In ex-situ tests, meta-PBI shows a negligible crossover of V 3+ and V 4+ ions, much lower than that of Nafion. This is due to electrostatic repulsive forces between vanadium cations and positively charged protonated PBI backbones, and the molecular sieving effect of PBI's nanosized pores. It turns out that charge efficiency (CE) of VRFBs using meta-PBI-based membranes is unaffected by or slightly increases with decreasing membrane thickness. Thick meta-PBI membranes require about 100 mV larger potentials to achieve the same charging current as thin meta-PBI membranes. This additional potential may increase side reactions or enable more vanadium ions to overcome the electrostatic energy barrier and to enter the membrane. On this basis, H 2 SO 4 -doped meta-PBI membranes should be thin to achieve high VE and CE. The energy efficiency of 15 μm thick PBI reaches 92%, exceeding that of Nafion 212 and 117 (N212 and N117) at 40 mA cm -2 .

In situ X-ray near-edge absorption spectroscopy investigation of the state of charge of all-vanadium redox flow batteries.

PubMed

Jia, Chuankun; Liu, Qi; Sun, Cheng-Jun; Yang, Fan; Ren, Yang; Heald, Steve M; Liu, Yadong; Li, Zhe-Fei; Lu, Wenquan; Xie, Jian

2014-10-22

Synchrotron-based in situ X-ray near-edge absorption spectroscopy (XANES) has been used to study the valence state evolution of the vanadium ion for both the catholyte and anolyte in all-vanadium redox flow batteries (VRB) under realistic cycling conditions. The results indicate that, when using the widely used charge-discharge profile during the first charge process (charging the VRB cell to 1.65 V under a constant current mode), the vanadium ion valence did not reach V(V) in the catholyte and did not reach V(II) in the anolyte. Consequently, the state of charge (SOC) for the VRB cell was only 82%, far below the desired 100% SOC. Thus, such incompletely charged mix electrolytes results in not only wasting the electrolytes but also decreasing the cell performance in the following cycles. On the basis of our study, we proposed a new charge-discharge profile (first charged at a constant current mode up to 1.65 V and then continuously charged at a constant voltage mode until the capacity was close to the theoretical value) for the first charge process that achieved 100% SOC after the initial charge process. Utilizing this new charge-discharge profile, the theoretical charge capacity and the full utilization of electrolytes has been achieved, thus having a significant impact on the cost reduction of the electrolytes in VRB.

Graphene‐Nanowall‐Decorated Carbon Felt with Excellent Electrochemical Activity Toward VO2 +/VO2+ Couple for All Vanadium Redox Flow Battery

PubMed Central

Li, Wenyue; Zhang, Zhenyu; Bian, Haidong; Ng, Tsz‐Wai

2015-01-01

3D graphene‐nanowall‐decorated carbon felts (CF) are synthesized via an in situ microwave plasma enhanced chemical vapor deposition method and used as positive electrode for vanadium redox flow battery (VRFB). The carbon fibers in CF are successfully wrapped by vertically grown graphene nanowalls, which not only increase the electrode specific area, but also expose a high density of sharp graphene edges with good catalytic activities to the vanadium ions. As a result, the VRFB with this novel electrode shows three times higher reaction rate toward VO2 +/VO2+ redox couple and 11% increased energy efficiency over VRFB with an unmodified CF electrode. Moreover, this designed architecture shows excellent stability in the battery operation. After 100 charging–discharging cycles, the electrode not only shows no observable morphology change, it can also be reused in another battery and practical with the same performance. It is believed that this novel structure including the synthesis procedure will provide a new developing direction for the VRFB electrode. PMID:27774399

Outstanding electrochemical performance of a graphene-modified graphite felt for vanadium redox flow battery application

NASA Astrophysics Data System (ADS)

González, Zoraida; Flox, Cristina; Blanco, Clara; Granda, Marcos; Morante, Juan R.; Menéndez, Rosa; Santamaría, Ricardo

2017-01-01

The development of more efficient electrode materials is essential to obtain vanadium redox flow batteries (VRFBs) with enhanced energy densities and to make these electrochemical energy storage devices more competitive. A graphene-modified graphite felt synthesized from a raw graphite felt and a graphene oxide water suspension by means of electrophoretic deposition (EPD) is investigated as a suitable electrode material in the positive side of a VRFB cell by means of cyclic voltammetry, impedance spectroscopy and charge/discharge experiments. The remarkably enhanced performance of the resultant hybrid material, in terms of electrochemical activity and kinetic reversibility towards the VO2+/VO2+, and mainly the markedly high energy efficiency of the VRFB cell (c.a. 95.8% at 25 mA cm-2) can be ascribed to the exceptional morphological and chemical characteristics of this tailored material. The 3D-architecture consisting of fibers interconnected by graphene-like sheets positively contributes to the proper development of the vanadium redox reactions and so represents a significant advance in the design of effective electrode materials.

Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Zhang, Bengui; Zhang, Shouhai; Weng, Zhihuan; Wang, Guosheng; Zhang, Enlei; Yu, Ping; Chen, Xiaomeng; Wang, Xinwei

2016-09-01

Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes (QADMPEK) are prepared and investigated for vanadium redox flow batteries (VRFB) application. The bulky, rigid and highly hydrophobic adamantane segment incorporated into the backbone of membrane material makes QADMPEK membranes have low water uptake and swelling ratio, and the as-prepared membranes display significantly lower permeability of vanadium ions than that of Nafion117 membrane. As a consequence, the VRFB cell with QADMPEK-3 membrane shows higher coulombic efficiency (99.4%) and energy efficiency (84.0%) than those for Nafion117 membrane (95.2% and 80.5%, respectively) at the current density of 80 mA cm-2. Furthermore, at a much higher current density of 140 mA cm-2, QADMPEK membrane still exhibits better coulombic efficiency and energy efficiency than Nafion117 membrane (coulombic efficiency 99.2% vs 96.5% and energy efficiency 76.0% vs 74.0%). Moreover, QADMPEK membranes show high stability in in-situ VRFB cycle test and ex-situ oxidation stability test. These results indicate that QADMPEK membranes are good candidates for VRFB applications.

First-principles study of adsorption-desorption kinetics of aqueous V2+/V3+ redox species on graphite in a vanadium redox flow battery.

PubMed

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2017-06-14

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (112[combining macron]0) graphite facets with water and aqueous V 2+ /V 3+ redox species at 300 K employing Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V 2+ /V 3+ species. The formation of V-O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

Graphene-Nanowall-Decorated Carbon Felt with Excellent Electrochemical Activity Toward VO2+/VO2+ Couple for All Vanadium Redox Flow Battery.

PubMed

Li, Wenyue; Zhang, Zhenyu; Tang, Yongbing; Bian, Haidong; Ng, Tsz-Wai; Zhang, Wenjun; Lee, Chun-Sing

2016-04-01

3D graphene-nanowall-decorated carbon felts (CF) are synthesized via an in situ microwave plasma enhanced chemical vapor deposition method and used as positive electrode for vanadium redox flow battery (VRFB). The carbon fibers in CF are successfully wrapped by vertically grown graphene nanowalls, which not only increase the electrode specific area, but also expose a high density of sharp graphene edges with good catalytic activities to the vanadium ions. As a result, the VRFB with this novel electrode shows three times higher reaction rate toward VO 2 + /VO 2+ redox couple and 11% increased energy efficiency over VRFB with an unmodified CF electrode. Moreover, this designed architecture shows excellent stability in the battery operation. After 100 charging-discharging cycles, the electrode not only shows no observable morphology change, it can also be reused in another battery and practical with the same performance. It is believed that this novel structure including the synthesis procedure will provide a new developing direction for the VRFB electrode.

Ion-exchange composite membranes pore-filled with sulfonated poly(ether ether ketone) and Engelhard titanosilicate-10 for improved performance of vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Kim, Jihoon; Lee, Yongkyu; Jeon, Jae-Deok; Kwak, Seung-Yeop

2018-04-01

A series of ion-exchange membranes for vanadium redox flow batteries (VRBs) are prepared by filling the pores of a poly(tetrafluoroethylene) (PTFE) substrate with sulfonated poly(ether ether ketone) (SPEEK) and microporous Engelhard titanosilicate-10 (ETS-10). The effects of ETS-10 incorporation and PTFE reinforcement on membrane properties and VRB single-cell performance are investigated using various characterization tools. The results show that these composite membranes exhibit improved mechanical properties and reduced vanadium-ion permeabilities owing to the interactions between ETS-10 and SPEEK, the suppressed swelling of PTFE, and the unique ETS-10 framework. The composite membrane with 3 wt% ETS-10 (referred to as "SE3/P") exhibits the best membrane properties and highest ion selectivity. The VRB system with the SE3/P membrane exhibits higher cell capacity, higher cell efficiency, and lower capacity decay than that with a Nafion membrane. These results indicate that this composite membrane has potential as an alternative to Nafion in VRB systems.

A Bunch-Like Tertiary Amine Grafted Polysulfone Membrane for VRFBs with Simultaneously High Proton Conductivity and Low Vanadium Ion Permeability.

PubMed

Tan, Qinglong; Lu, Shanfu; Si, Jiangju; Wang, Haining; Wu, Chunxiao; Li, Xianfeng; Xiang, Yan

2017-04-01

Novel polysulfone membranes with bunch-like tertiary amine groups are synthesized with high ion selectivity and outstanding chemical stability for vanadium redox flow batteries (VRFBs). The bunch-like tertiary amine groups simultaneously act as an ionic conductor for proton hopping and vanadium ion transport obstacles. The performance of the membrane is tuned via controlling the grafting degree of the chloromethylated polysulfone. The results show that membranes show increasing proton over vanadium ion (σ/p) selectivity with increasing functional tertiary groups. VRFBs assembled with the prepared membranes demonstrate an impressive Coulombic efficiency of 98.9% and energy efficiency of 90.9% at a current density of 50 mA cm -2 . Furthermore, the prepared membrane reported in this work shows excellent stability in 1 m VO 2 + solution at 35 °C over 240 h. Overall, the synthesized polymers provide a new insight into the design of high-performance membranes toward VRFB applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deposition and characterization of vanadium oxide based thin films for MOS device applications

NASA Astrophysics Data System (ADS)

Rakshit, Abhishek; Biswas, Debaleen; Chakraborty, Supratic

2018-04-01

Vanadium Oxide films are deposited on Si (100) substrate by reactive RF-sputtering of a pure Vanadium metallic target in an Argon-Oxygen plasma environment. The ratio of partial pressures of Argon to Oxygen in the sputtering-chamber is varied by controlling their respective flow rates and the resultant oxide films are obtained. MOS Capacitor based devices are then fabricated using the deposited oxide films. High frequency Capacitance-Voltage (C-V) and gate current-gate voltage (I-V) measurements reveal a significant dependence of electrical characteristics of the deposited films on their sputtering deposition parameters mainly, the relative content of Argon/Oxygen in the plasma chamber. A noteworthy change in the electrical properties is observed for the films deposited under higher relative oxygen content in the plasma atmosphere. Our results show that reactive sputtering serves as an indispensable deposition-setup for fabricating vanadium oxide based MOS devices tailor-made for Non-Volatile Memory (NVM) applications.

A high-performance dual-scale porous electrode for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zeng, Y. K.; Zhu, X. B.; Wei, L.; Zhao, T. S.

2016-09-01

In this work, we present a simple and cost-effective method to form a dual-scale porous electrode by KOH activation of the fibers of carbon papers. The large pores (∼10 μm), formed between carbon fibers, serve as the macroscopic pathways for high electrolyte flow rates, while the small pores (∼5 nm), formed on carbon fiber surfaces, act as active sites for rapid electrochemical reactions. It is shown that the Brunauer-Emmett-Teller specific surface area of the carbon paper is increased by a factor of 16 while maintaining the same hydraulic permeability as that of the original carbon paper electrode. We then apply the dual-scale electrode to a vanadium redox flow battery (VRFB) and demonstrate an energy efficiency ranging from 82% to 88% at current densities of 200-400 mA cm-2, which is record breaking as the highest performance of VRFB in the open literature.

Determination of dipyrone in pharmaceutical preparations based on the chemiluminescent reaction of the quinolinic hydrazide-H2O2-vanadium(IV) system and flow-injection analysis.

PubMed

Pradana Pérez, Juan A; Durand Alegría, Jesús S; Hernando, Pilar Fernández; Sierra, Adolfo Narros

2012-01-01

A rapid, economic and sensitive chemiluminescent method involving flow-injection analysis was developed for the determination of dipyrone in pharmaceutical preparations. The method is based on the chemiluminescent reaction between quinolinic hydrazide and hydrogen peroxide in a strongly alkaline medium, in which vanadium(IV) acts as a catalyst. Principal chemical and physical variables involved in the flow-injection system were optimized using a modified simplex method. The variations in the quantum yield observed when dipyrone was present in the reaction medium were used to determine the concentration of this compound. The proposed method requires no preconcentration steps and reliably quantifies dipyrone over the linear range 1-50 µg/mL. In addition, a sample throughput of 85 samples/h is possible. Copyright © 2011 John Wiley & Sons, Ltd.

Flow field design and optimization based on the mass transport polarization regulation in a flow-through type vanadium flow battery

NASA Astrophysics Data System (ADS)

Zheng, Qiong; Xing, Feng; Li, Xianfeng; Ning, Guiling; Zhang, Huamin

2016-08-01

Vanadium flow battery holds great promise for use in large scale energy storage applications. However, the power density is relatively low, leading to significant increase in the system cost. Apart from the kinetic and electronic conductivity improvement, the mass transport enhancement is also necessary to further increase the power density and reduce the system cost. To better understand the mass transport limitations, in the research, the space-varying and time-varying characteristic of the mass transport polarization is investigated based on the analysis of the flow velocity and reactant concentration in the bulk electrolyte by modeling. The result demonstrates that the varying characteristic of mass transport polarization is more obvious at high SoC or high current densities. To soften the adverse impact of the mass transport polarization, a new rectangular plug flow battery with a plug flow and short flow path is designed and optimized based on the mass transport polarization regulation (reducing the mass transport polarization and improving its uniformity of distribution). The regulation strategy of mass transport polarization is practical for the performance improvement in VFBs, especially for high power density VFBs. The findings in the research are also applicable for other flow batteries and instructive for practical use.

Vanadium

USGS Publications Warehouse

Kelley, Karen D.; Scott, Clinton T.; Polyak, Désirée E.; Kimball, Bryn E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Vanadium is used primarily in the production of steel alloys; as a catalyst for the chemical industry; in the making of ceramics, glasses, and pigments; and in vanadium redox-flow batteries (VRBs) for large-scale storage of electricity. World vanadium resources in 2012 were estimated to be 63 million metric tons, which include about 14 million metric tons of reserves. The majority of the vanadium produced in 2012 was from China, Russia, and South Africa.Vanadium is extracted from several different types of mineral deposits and from fossil fuels. These deposits include vanadiferous titanomagnetite (VTM) deposits, sandstone-hosted vanadium (with or without uranium) deposits (SSV deposits), and vanadium-rich black shales. VTM deposits are the principal source of vanadium and consist of magmatic accumulations of ilmenite and magnetite containing 0.2 to 1 weight percent vanadium pentoxide (V2O5). SSV deposits are another important source; these deposits have average ore grades that range from 0.1 to greater than 1 weight percent V2O5. The United States has been and is currently the main producer of vanadium from SSV deposits, particularly those on the Colorado Plateau. Vanadium-rich black shales occur in marine successions that were deposited in epeiric (inland) seas and on continental margins. Concentrations in these shales regularly exceed 0.18 weight percent V2O5 and can be as high as 1.7 weight percent V2O5. Small amounts of vanadium have been produced from the Alum Shale in Sweden and from ferrophosphorus slag generated during the reduction of phosphate to elemental phosphorus in ore from shales of the Phosphoria Formation in Idaho and Wyoming. Because vanadium enrichment occurs in beds that are typically only a few meters thick, most of the vanadiferous black shales are not currently economic, although they may become an important resource in the future. Significant amounts of vanadium are recovered as byproducts of petroleum refining, and processing of coal, tar sands, and oil shales may be important future sources.Vanadium occurs in one of four oxidation states in nature: +2, +3, +4, and +5. The V3+ ion has an octahedral radius that is almost identical to that of (Fe3+) and (Al3+) and, therefore, it substitutes in ferromagnesian minerals. During weathering, much of the vanadium may partition into newly formed clay minerals, and it either remains in the +3 valence state or oxidizes to the +4 valence state, both of which are relatively insoluble. If erosion is insignificant but chemical leaching is intense, the residual material may be enriched in vanadium, as are some bauxites and laterites. During the weathering of igneous, residual, or sedimentary rocks, some vanadium oxidizes to the +5 valence state, especially in the intensive oxidizing conditions that are characteristic of arid climates.The average contents of vanadium in the environment are as follows: soils [10 to 500 parts per million (ppm)]; streams and rivers [0.2 to 2.9 parts per billion (ppb)]; and coastal seawater (0.3 to 2.8 ppb). Concentrations of vanadium in soils (548 to 7,160 ppm) collected near vanadium mines in China, the Czech Republic, and South Africa are many times greater than natural concentrations in soils. Additionally, if deposits contain sulfide minerals such as chalcocite, pyrite, and sphalerite, high levels of acidity may be present if sulfide dissolution is not balanced by the presence of acid-neutralizing carbonate minerals. Some of the vanadium-bearing deposit types, particularly some SSV and black-shale deposits, contain appreciable amounts of carbonate minerals, which lowers the acid-generation potential.Vanadium is a micronutrient with a postulated requirement for humans of less than 10 micrograms per day, which can be met through dietary intake. Primary and secondary drinking water regulations for vanadium are not currently in place in the United States. Vanadium toxicity is thought to result from an intake of more than 10 to 20 milligrams per day. Vanadium is essential for some biological processes and organisms. For example, some nitrogen-fixing bacteria require vanadium for producing enzymes necessary to convert nitrogen from the atmosphere into ammonia, which is a more biologically accessible form of nitrogen.

Nanorod niobium oxide as powerful catalysts for an all vanadium redox flow battery.

PubMed

Li, Bin; Gu, Meng; Nie, Zimin; Wei, Xiaoliang; Wang, Chongmin; Sprenkle, Vincent; Wang, Wei

2014-01-08

A powerful low-cost electrocatalyst, nanorod Nb2O5, is synthesized using the hydrothermal method with monoclinic phases and simultaneously deposited on the surface of a graphite felt (GF) electrode in an all vanadium flow battery (VRB). Cyclic voltammetry (CV) study confirmed that Nb2O5 has catalytic effects toward redox couples of V(II)/V(III) at the negative side and V(IV)/V(V) at the positive side to facilitate the electrochemical kinetics of the vanadium redox reactions. Because of poor conductivity of Nb2O5, the performance of the Nb2O5 loaded electrodes is strongly dependent on the nanosize and uniform distribution of catalysts on GF surfaces. Accordingly, an optimal amount of W-doped Nb2O5 nanorods with minimum agglomeration and improved distribution on GF surfaces are established by adding water-soluble compounds containing tungsten (W) into the precursor solutions. The corresponding energy efficiency is enhanced by ∼10.7% at high current density (150 mA·cm(-2)) as compared with one without catalysts. Flow battery cyclic performance also demonstrates the excellent stability of the as prepared Nb2O5 catalyst enhanced electrode. These results suggest that Nb2O5-based nanorods, replacing expensive noble metals, uniformly decorating GFs holds great promise as high-performance electrodes for VRB applications.

Innovative model-based flow rate optimization for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

König, S.; Suriyah, M. R.; Leibfried, T.

2016-11-01

In this paper, an innovative approach is presented to optimize the flow rate of a 6-kW vanadium redox flow battery with realistic stack dimensions. Efficiency is derived using a multi-physics battery model and a newly proposed instantaneous efficiency determination technique. An optimization algorithm is applied to identify optimal flow rates for operation points defined by state-of-charge (SoC) and current. The proposed method is evaluated against the conventional approach of applying Faraday's first law of electrolysis, scaled to the so-called flow factor. To make a fair comparison, the flow factor is also optimized by simulating cycles with different charging/discharging currents. It is shown through the obtained results that the efficiency is increased by up to 1.2% points; in addition, discharge capacity is also increased by up to 1.0 kWh or 5.4%. Detailed loss analysis is carried out for the cycles with maximum and minimum charging/discharging currents. It is shown that the proposed method minimizes the sum of losses caused by concentration over-potential, pumping and diffusion. Furthermore, for the deployed Nafion 115 membrane, it is observed that diffusion losses increase with stack SoC. Therefore, to decrease stack SoC and lower diffusion losses, a higher flow rate during charging than during discharging is reasonable.

Effect of organic matter on nitrogenase metal cofactors homeostasis in Azotobacter vinelandii under diazotrophic conditions.

PubMed

Noumsi, Christelle Jouogo; Pourhassan, Nina; Darnajoux, Romain; Deicke, Michael; Wichard, Thomas; Burrus, Vincent; Bellenger, Jean-Philippe

2016-02-01

Biological nitrogen fixation can be catalysed by three isozymes of nitrogenase: molybdenum (Mo)-nitrogenase, vanadium (V)-nitrogenase and iron-only (Fe)-nitrogenase. The activity of these isozymes strongly depends on their metal cofactors, molybdenum, vanadium and iron, and their bioavailability in ecosystems. Here, we show how metal bioavailability can be affected by the presence of tannic acid (organic matter), and the subsequent consequences on diazotrophic growth of the soil bacterium Azotobacter vinelandii. In the presence of tannic acids, A. vinelandii produces a higher amount of metallophores, which coincides with an active, regulated and concomitant acquisition of molybdenum and vanadium under cellular conditions that are usually considered not molybdenum limiting. The associated nitrogenase genes exhibit decreased nifD expression and increased vnfD expression. Thus, in limiting bioavailable metal conditions, A. vinelandii takes advantage of its nitrogenase diversity to ensure optimal diazotrophic growth. © 2015 Society for Applied Microbiology and John Wiley & Sons Ltd.

ZrO2-Nanoparticle-Modified Graphite Felt: Bifunctional Effects on Vanadium Flow Batteries.

PubMed

Zhou, Haipeng; Shen, Yi; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

2016-06-22

To improve the electrochemical performance of graphite felt (GF) electrodes in vanadium flow batteries (VFBs), we synthesize a series of ZrO2-modified GF (ZrO2/GF) electrodes with varying ZrO2 contents via a facile immersion-precipitation approach. It is found that the uniform immobilization of ZrO2 nanoparticles on the GF not only significantly promotes the accessibility of vanadium electrolyte, but also provides more active sites for the redox reactions, thereby resulting in better electrochemical activity and reversibility toward the VO(2+)/VO2(+) and V(2+)/V(3+) redox reactions as compared with those of GF. In particular, The ZrO2/GF composite with 0.3 wt % ZrO2 displays the best electrochemical performance with voltage and energy efficiencies of 71.9% and 67.4%, respectively, which are much higher than those of 57.3% and 53.8% as obtained from the GF electrode at 200 mA cm(-2). The cycle life tests demonstrate that the ZrO2/GF electrodes exhibit outstanding stability. The ZrO2/GF-based VFB battery shows negligible activity decay after 200 cycles.

Low vanadium ion permeabilities of sulfonated poly(phthalazinone ether ketone)s provide high efficiency and stability for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Chen, Liyun; Zhang, Shouhai; Chen, Yuning; Jian, Xigao

2017-07-01

A series of novel sulfonated poly(phthalazinone ether ketone)s containing pendant phenyl moieties (SPPEK-Ps) are synthesized and thoroughly characterized. The chemical structures of the polymers are confirmed by 1H NMR and FTIR analysis. The physicochemical properties and single cell performance of SPPEK-P membranes are systematically evaluated, revealing that the membranes are thermally, chemically and mechanically stable. The area resistances of SPPEK-P-90 and SPPEK-P-100 are 0.75 Ω cm2 and 0.34 Ω cm2, respectively. SPPEK-P membranes are impermeable to the bulky hydrated VO2+ ion and exhibited low V3+ ion permeability (SPPEK-P-90, 2.53 × 10-5 cm min-1) (Nafion 115 membrane: 9.0 × 10-4 cm min-1). Tests of SPPEK-P-90 in vanadium redox flow batteries (VRFBs) demonstrate a comparable columbic efficiency (CE) and energy efficiency (EE) to that of Nafion 115, where the CE is 98% and the EE is 83% at 60 mA cm-2. Moreover, the SPPEK-P-90 membrane exhibits stable performance in cell over 100 charge-discharge cycles (∼450 h).

Novel sulfonated polyimide/zwitterionic polymer-functionalized graphene oxide hybrid membranes for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Cao, Li; Kong, Lei; Kong, Lingqian; Zhang, Xingxiang; Shi, Haifeng

2015-12-01

Hybrid membranes (SPI/ZGO) composed of sulfonated polyimide (SPI) and zwitterionic polymer-functionalized graphene oxide (ZGO) are fabricated via a solution-casting method for vanadium redox flow battery (VRB). Successful preparation of ZGO fillers and SPI/ZGO hybrid membranes are demonstrated by FT-IR, XPS and SEM, indicating that ZGO fillers is homogeneously dispersed into SPI matrix. Through controlling the interfacial interaction between SPI matrix and ZGO fillers, the physicochemical properties, e.g., vanadium ion barrier and proton transport pathway, of hybrid membranes are tuned via the zwitterionic acid-base interaction in the hybrid membrane, showing a high ion selectivity and good stability with the incorporated ZGO fillers. SPI/ZGO-4 hybrid membrane proves a higher cell efficiencies (CE: 92-98%, EE: 65-79%) than commercial Nafion 117 membrane (CE: 89-94%, EE: 59-70%) for VRB application at 30-80 mA cm-2. The assembled VRB with SPI/ZGO-4 membrane presents a stable cycling charge-discharge performance over 280 times, which demonstrates its excellent chemical stability under the strong acidic and oxidizing conditions. SPI/ZGO hybrid membranes show a brilliant perspective for VRB application.

Water-activated graphite felt as a high-performance electrode for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Kabtamu, Daniel Manaye; Chen, Jian-Yu; Chang, Yu-Chung; Wang, Chen-Hao

2017-02-01

A simple, green, novel, time-efficient, and potentially cost-effective water activation method was employed to enhance the electrochemical activity of graphite felt (GF) electrodes for vanadium redox flow batteries (VRFBs). The GF electrode prepared with a water vapor injection time of 5 min at 700 °C exhibits the highest electrochemical activity for the VO2+/VO2+ couple among all the tested electrodes. This is attributed to the small, controlled amount of water vapor that was introduced producing high contents of oxygen-containing functional groups, such as sbnd OH groups, on the surface of the GF fibers, which are known to be electrochemically active sites for vanadium redox reactions. Charge-discharge tests further confirm that only 5 min of GF water activation is required to improve the efficiency of the VRFB cell. The average coulombic efficiency, voltage efficiency, and energy efficiency are 95.06%, 87.42%, and 83.10%, respectively, at a current density of 50 mA cm-2. These voltage and energy efficiencies are determined to be considerably higher than those of VRFB cells assembled using heat-treated GF electrodes without water activation and pristine GF electrodes.

Removal of vanadium from industrial wastewater using iron sorbents in batch and continuous flow pilot systems.

PubMed

Leiviskä, Tiina; Khalid, Muhammad Kamran; Sarpola, Arja; Tanskanen, Juha

2017-04-01

This study investigated the removal of vanadium from real industrial wastewater by using six iron materials: commercial iron sorbent (CFH-12), commercial mineral sorbent (AQM), blast furnace sludge (BFS), steel converter sludge (SCS), ferrochrome slag (FeCr) and slag from a steel foundry (OKTO). Batch tests revealed that CFH-12 (ferric oxyhydroxide) removed vanadium most efficiently, which was explained by its high iron content and the amorphous form of the iron, and that the sorption followed the Langmuir isotherm. With a dosage of 10 g/l and an initial vanadium concentration of 58.2 mg/l, 91-94% removal rates for vanadium were achieved in the studied pH range (3-9). Other sorbents showed significantly lower efficiency than CFH-12, with the exception of BFS at acidic pH (93%). Based on the batch test results, CFH-12 was selected for a pilot study made on site. The pilot study demonstrated the feasibility of CFH-12 to remove vanadium at high temperature (80 °C) from concentrated industrial wastewater with fluctuating water quality (vanadium concentration varied from 51 to 83 mg/l, pH about 9 (at 25 °C)). Leaching of impurities (mainly S, Ca, Mg and K) into the effluent occurred during the first day, but subsequently good quality effluent was produced (e.g. <0.1 mg/l V). During the pilot study, the amorphous iron material of CFH-12 was crystallized into a hematite-like phase (Fe 1.67 H 0.99 O 3 ), and goethite (FeO(OH)) with a higher average pore diameter, probably due to the hot process conditions to which CFH-12 was exposed for over five days. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrochemical cell structure including an ionomeric barrier

DOEpatents

Lambert, Timothy N.; Hibbs, Michael

2017-06-20

An apparatus includes an electrochemical half-cell comprising: an electrolyte, an anode; and an ionomeric barrier positioned between the electrolyte and the anode. The anode may comprise a multi-electron vanadium phosphorous alloy, such as VP.sub.x, wherein x is 1-5. The electrochemical half-cell is configured to oxidize the vanadium and phosphorous alloy to release electrons. A method of mitigating corrosion in an electrochemical cell includes disposing an ionomeric barrier in a path of electrolyte or ion flow to an anode and mitigating anion accumulation on the surface of the anode.

Vanadium proton exchange membrane water electrolyser

NASA Astrophysics Data System (ADS)

Noack, Jens; Roznyatovskaya, Nataliya; Pinkwart, Karsten; Tübke, Jens

2017-05-01

In order to reverse the reactions of vanadium oxygen fuel cells and to regenerate vanadium redox flow battery electrolytes that have been oxidised by atmospheric oxygen, a vanadium proton exchange membrane water electrolyser was set up and investigated. Using an existing cell with a commercial and iridium-based catalyst coated membrane, it was possible to fully reduce V3.5+ and V3+ solutions to V2+ with the formation of oxygen and with coulomb efficiencies of over 96%. The cell achieved a maximum current density of 75 mA/cm2 during this process and was limited by the proximity of the V(III) reduction to the hydrogen evolution reaction. Due to the specific reaction mechanisms of V(IV) and V(III) ions, V(III) solutions were reduced with an energy efficiency of 61%, making this process nearly twice as energy efficient as the reduction of V(IV) to V(III). Polarisation curves and electrochemical impedance spectroscopy were used to further investigate the losses of half-cell reactions and to find ways of further increasing efficiency and performance levels.

A plug flow reactor model of a vanadium redox flow battery considering the conductive current collectors

NASA Astrophysics Data System (ADS)

König, S.; Suriyah, M. R.; Leibfried, T.

2017-08-01

A lumped-parameter model for vanadium redox flow batteries, which use metallic current collectors, is extended into a one-dimensional model using the plug flow reactor principle. Thus, the commonly used simplification of a perfectly mixed cell is no longer required. The resistances of the cell components are derived in the in-plane and through-plane directions. The copper current collector is the only component with a significant in-plane conductance, which allows for a simplified electrical network. The division of a full-scale flow cell into 10 layers in the direction of fluid flow represents a reasonable compromise between computational effort and accuracy. Due to the variations in the state of charge and thus the open circuit voltage of the electrolyte, the currents in the individual layers vary considerably. Hence, there are situations, in which the first layer, directly at the electrolyte input, carries a multiple of the last layer's current. The conventional model overestimates the cell performance. In the worst-case scenario, the more accurate 20-layer model yields a discharge capacity 9.4% smaller than that computed with the conventional model. The conductive current collector effectively eliminates the high over-potentials in the last layers of the plug flow reactor models that have been reported previously.

An Approach Toward Replacing Vanadium: A Single Organic Molecule for the Anode and Cathode of an Aqueous Redox-Flow Battery.

PubMed

Janoschka, Tobias; Friebe, Christian; Hager, Martin D; Martin, Norbert; Schubert, Ulrich S

2017-04-01

By combining a viologen unit and a 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) radical in one single combi-molecule, an artificial bipolar redox-active material, 1-(4-(((1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-1'-methyl-[4,4'-bipyridine]-1,1'-diium-chloride ( VIOTEMP ), was created that can serve as both the anode (-0.49 V) and cathode (0.67 V vs. Ag/AgCl) in a water-based redox-flow battery. While it mimics the redox states of flow battery metals like vanadium, the novel aqueous electrolyte does not require strongly acidic media and is best operated at pH 4. The electrochemical properties of VIOTEMP were investigated by using cyclic voltammetry, rotating disc electrode experiments, and spectroelectrochemical methods. A redox-flow battery was built and the suitability of the material for both electrodes was demonstrated through a polarity-inversion experiment. Thus, an organic aqueous electrolyte system being safe in case of cross contamination is presented.

Influence of oxygen flow rate on metal-insulator transition of vanadium oxide thin films grown by RF magnetron sputtering

NASA Astrophysics Data System (ADS)

Ma, Xu; Liu, Xinkun; Li, Haizhu; Zhang, Angran; Huang, Mingju

2017-03-01

High-quality vanadium oxide ( VO2) films have been fabricated on Si (111) substrates by radio frequency (RF) magnetron sputtering deposition method. The sheet resistance of VO2 has a significant change (close to 5 orders of magnitude) in the process of the metal-insulator phase transition (MIT). The field emission-scanning electron microscope (FE-SEM) results show the grain size of VO2 thin films is larger with the increase of oxygen flow. The X-ray diffraction (XRD) results indicate the thin films fabricated at different oxygen flow rates grow along the (011) crystalline orientation. As the oxygen flow rate increases from 3 sccm to 6 sccm, the phase transition temperature of the films reduces from 341 to 320 K, the width of the thermal hysteresis loop decreases from 32 to 9 K. The thin films fabricated in the condition of 5 sccm have a high temperature coefficient of resistance (TCR) -3.455%/K with a small resistivity of 2.795 ρ/Ω cm.

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery.

PubMed

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-02-06

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on.

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery

PubMed Central

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-01-01

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on. PMID:24500376

Optimized anion exchange membranes for vanadium redox flow batteries.

PubMed

Chen, Dongyang; Hickner, Michael A; Agar, Ertan; Kumbur, E Caglan

2013-08-14

In order to understand the properties of low vanadium permeability anion exchange membranes for vanadium redox flow batteries (VRFBs), quaternary ammonium functionalized Radel (QA-Radel) membranes with three ion exchange capacities (IECs) from 1.7 to 2.4 mequiv g(-1) were synthesized and 55-60 μm thick membrane samples were evaluated for their transport properties and in-cell battery performance. The ionic conductivity and vanadium permeability of the membranes were investigated and correlated to the battery performance through measurements of Coulombic efficiency, voltage efficiency and energy efficiency in single cell tests, and capacity fade during cycling. Increasing the IEC of the QA-Radel membranes increased both the ionic conductivity and VO(2+) permeability. The 1.7 mequiv g(-1) IEC QA-Radel had the highest Coulombic efficiency and best cycling capacity maintenance in the VRFB, while the cell's voltage efficiency was limited by the membrane's low ionic conductivity. Increasing the IEC resulted in higher voltage efficiency for the 2.0 and 2.4 mequiv g(-1) samples, but the cells with these membranes displayed reduced Coulombic efficiency and faster capacity fade. The QA-Radel with an IEC of 2.0 mequiv g(-1) had the best balance of ionic conductivity and VO(2+) permeability, achieving a maximum power density of 218 mW cm(-2) which was higher than the maximum power density of a VRFB assembled with a Nafion N212 membrane in our system. While anion exchange membranes are under study for a variety of VRFB applications, this work demonstrates that the material parameters must be optimized to obtain the maximum cell performance.

"Unexpected" behaviour of the internal resistance of a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Rudolph, S.; Schröder, U.; Bayanov, I. M.; Hage-Packhäuser, S.

2016-02-01

This article presents the results of experimental and theoretical studies of energy losses owing to the internal resistance of vanadium redox flow batteries (VRFBs). A dependence of the internal cell resistance (ICR) on the electric current was measured and calculated. During the cyclic operation of a test battery, the internal resistance was halved by increasing the electric current from 3 A to 9 A. This is due to a strongly non-linear dependence of an over-potential of the electrochemical reactions on the current density. However, the energy efficiency does not increase due to a squared dependence of the energy losses on the increasing electric current. The energy efficiency of the test battery versus the electric current was measured and simulated. The deviation between the simulation results and experimental data is less than ±3.5%.

High efficiency of CO2-activated graphite felt as electrode for vanadium redox flow battery application

NASA Astrophysics Data System (ADS)

Chang, Yu-Chung; Chen, Jian-Yu; Kabtamu, Daniel Manaye; Lin, Guan-Yi; Hsu, Ning-Yih; Chou, Yi-Sin; Wei, Hwa-Jou; Wang, Chen-Hao

2017-10-01

A simple method for preparing CO2-activated graphite felt as an electrode in a vanadium redox flow battery (VRFB) was employed by the direct treatment in a CO2 atmosphere at a high temperature for a short period. The CO2-activated graphite felt demonstrates excellent electrochemical activity and reversibility. The VRFB using the CO2-activated graphite felts in the electrodes has coulombic, voltage, and energy efficiencies of 94.52%, 88.97%, and 84.15%, respectively, which is much higher than VRFBs using the electrodes of untreated graphite felt and N2-activated graphite felt. The efficiency enhancement was attributed to the higher number of oxygen-containing functional groups on the graphite felt that are formed during the CO2-activation, leading to improving the electrochemical behaviour of the resultant VRFB.

High performance electrodes in vanadium redox flow batteries through oxygen-enriched thermal activation

NASA Astrophysics Data System (ADS)

Pezeshki, Alan M.; Clement, Jason T.; Veith, Gabriel M.; Zawodzinski, Thomas A.; Mench, Matthew M.

2015-10-01

The roundtrip electrochemical energy efficiency is improved from 63% to 76% at a current density of 200 mA cm-2 in an all-vanadium redox flow battery (VRFB) by utilizing modified carbon paper electrodes in the high-performance no-gap design. Heat treatment of the carbon paper electrodes in a 42% oxygen/58% nitrogen atmosphere increases the electrochemically wetted surface area from 0.24 to 51.22 m2 g-1, resulting in a 100-140 mV decrease in activation overpotential at operationally relevant current densities. An enriched oxygen environment decreases the amount of treatment time required to achieve high surface area. The increased efficiency and greater depth of discharge doubles the total usable energy stored in a fixed amount of electrolyte during operation at 200 mA cm-2.

Reduction of capacity decay in vanadium flow batteries by an electrolyte-reflow method

NASA Astrophysics Data System (ADS)

Wang, Ke; Liu, Le; Xi, Jingyu; Wu, Zenghua; Qiu, Xinping

2017-01-01

Electrolyte imbalance is a major issue with Vanadium flow batteries (VFBs) as it has a significant impact on electrolyte utilization and cycle life over extended charge-discharge cycling. This work seeks to reduce capacity decay and prolong cycle life of VFBs by adopting a novel electrolyte-reflow method. Different current density and various start-up time of the method are investigated in the charge-discharge tests. The results show that the capacity decay rate is reduced markedly and the cycle life is prolonged substantially by this method. In addition, the coulomb efficiency, voltage efficiency and energy efficiency remain stable during the whole cycle life test, which indicates this method has little impact on the long lifetime performance of the VFBs. The method is low-cost, simple, effective, and can be applied in industrial VFB productions.

Graphite furnace atomic absorption spectrometric detection of vanadium in water and food samples after solid phase extraction on multiwalled carbon nanotubes.

PubMed

Wadhwa, Sham Kumar; Tuzen, Mustafa; Gul Kazi, Tasneem; Soylak, Mustafa

2013-11-15

Vanadium(V) ions as 8-hydroxyquinoline chelates were loaded on multiwalled carbon nanotubes (MWNTs) in a mini chromatographic column. Vanadium was determined by graphite furnace atomic absorption spectrometry (GFAAS). Various analytical parameters including pH of the working solutions, amounts of 8-hydroxyquinoline, eluent type, sample volume, and flow rates were investigated. The effects of matrix ions and some transition metals were also studied. The column can be reused 250 times without any loss in its sorption properties. The preconcentration factor was found as 100. Detection limit (3 s) and limit of quantification (10 s) for the vanadium in the optimal conditions were observed to be 0.012 µg L(-1) and 0.040 μg L(-1), respectively. The capacity of adsorption was 9.6 mg g(-1). Relative standard deviation (RSD) was found to be 5%. The validation of the method was confirmed by using NIST SRM 1515 Apple leaves, NIST SRM 1570a Spinach leaves and GBW 07605 Tea certified reference materials. The procedure was applied to the determination of vanadium in tap water and bottled drinking water samples. The procedure was also successfully applied to microwave digested food samples including black tea, coffee, tomato, cabbage, zucchini, apple and chicken samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Green Chemistry Challenge: 2017 Small Business Award

EPA Pesticide Factsheets

Green Chemistry Challenge 2017 award winner, UniEnergy,improved a vanadium redox flow battery to double the energy density, have a broader operating temperature range, a smaller footprint, reduced chemical usage, and very little capacity degradation.

Versatile Organic Chemistry on Vanadium-Based Multi-Electron Reservoirs.

PubMed

Nachtigall, Olaf; Spandl, Johann

2018-02-21

We report the synthesis, post-functionalization, and redox behavior of two organically functionalized aggregates, [V 6 O 7 (OMe) 9 {(OCH 2 ) 3 C-CH 2 N 3 }] and [V 6 O 7 (OMe) 9 {(OCH 2 ) 3 C-NH 2 }]. All twelve μ 2 -oxo groups on the edges of the Lindqvist-type {V 6 O 19 } core were replaced by alkoxo ligands. The absence of a negative charge and the closed organic shell make these neutral mixed-valence compounds very stable towards hydrolysis and well soluble in almost all common organic solvents. These are important advantages over classical POMs. By post-functionalization through copper(I)-catalyzed Huisgen cycloaddition or imine formation, various organic moieties could be introduced. Even a well-soluble trimer composed of three hexanuclear vanadium units connected through an aromatic triimino core was synthesized and studied. The diverse redox behavior, the versatile reactivity, the good stability, and the excellent solubility make our vanadium compounds highly interesting for applications as building blocks in macromolecular chemistry as well as redox labels in biochemistry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The transfer behavior of different ions across anion and cation exchange membranes under vanadium flow battery medium

NASA Astrophysics Data System (ADS)

Sun, Jiawei; Li, Xianfeng; Xi, Xiaoli; Lai, Qinzhi; Liu, Tao; Zhang, Huamin

2014-12-01

The transfer behavior of different ions (V2+, V3+, VO2+, VO2+, H+, SO42-) across ion exchange membranes is investigated under vanadium flow battery (VFB) operating condition. VX-20 anion exchange membrane (AEM) and Nafion 115 cation exchange membrane (CEM) are selected to investigate the influence of fixed charged groups on the transfer behavior of different ions. The interaction between different ions and water is discussed in detail aiming to ascertain the variation of different ions in the charge-discharge process. Under the VFB medium, the transfer behavior and function of different ions are very different for the AEM and CEM. V2+ ions at the negative side accumulate when VFB is assembled with Nafion 115, while the VO2+ ions at the positive side accumulate for VX-20. The SO42- ions will transfer across Nafion 115 to balance the charges and the protons can balance the charges of VX-20. Finally the capacity fade mechanism of different membranes is investigated, showing that the capacity decay of VFB assembled with Nafion 115 mainly results from the cross mix of vanadium ions across the membrane, however, for VX-20, the side reactions can be the major reason. This paper provides important information about electrolyte for the application of VFB.

Mesoporous tungsten oxynitride as electrocatalyst for promoting redox reactions of vanadium redox couple and performance of vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Lee, Wonmi; Jo, Changshin; Youk, Sol; Shin, Hun Yong; Lee, Jinwoo; Chung, Yongjin; Kwon, Yongchai

2018-01-01

For enhancing the performance of vanadium redox flow battery (VRFB), a sluggish reaction rate issue of V2+/V3+ redox couple evaluated as the rate determining reaction should be addressed. For doing that, mesoporous tungsten oxide (m-WO3) and oxyniride (m-WON) structures are proposed as the novel catalysts, while m-WON is gained by NH3 heat treatment of m-WO3. Their specific surface area, crystal structure, surface morphology and component analysis are measured using BET, XRD, TEM and XPS, while their catalytic activity for V2+/V3+ redox reaction is electrochemically examined. As a result, the m-WON shows higher peak current, smaller peak potential difference, higher electron transfer rate constant and lower charge transfer resistance than other catalysts, like the m-WO3, WO3 nanoparticle and mesoporous carbon, proving that it is superior catalyst. Regarding the charge-discharge curve tests, the VRFB single cell employing the m-WON demonstrates high voltage and energy efficiencies, high specific capacity and low capacity loss rate. The excellent results of m-WON are due to the reasons like (i) reduced energy band gap, (ii) reaction familiar surface functional groups and (ii) greater electronegativity.

Bismuth nanoparticle decorating graphite felt as a high-performance electrode for an all-vanadium redox flow battery.

PubMed

Li, Bin; Gu, Meng; Nie, Zimin; Shao, Yuyan; Luo, Qingtao; Wei, Xiaoliang; Li, Xiaolin; Xiao, Jie; Wang, Chongmin; Sprenkle, Vincent; Wang, Wei

2013-03-13

Employing electrolytes containing Bi(3+), bismuth nanoparticles are synchronously electrodeposited onto the surface of a graphite felt electrode during operation of an all-vanadium redox flow battery (VRFB). The influence of the Bi nanoparticles on the electrochemical performance of the VRFB is thoroughly investigated. It is confirmed that Bi is only present at the negative electrode and facilitates the redox reaction between V(II) and V(III). However, the Bi nanoparticles significantly improve the electrochemical performance of VRFB cells by enhancing the kinetics of the sluggish V(II)/V(III) redox reaction, especially under high power operation. The energy efficiency is increased by 11% at high current density (150 mA·cm(-2)) owing to faster charge transfer as compared with one without Bi. The results suggest that using Bi nanoparticles in place of noble metals offers great promise as high-performance electrodes for VRFB application.

Hierarchical porous poly (ether sulfone) membranes with excellent capacity retention for vanadium flow battery application

NASA Astrophysics Data System (ADS)

Chen, Dongju; Li, Dandan; Li, Xianfeng

2017-06-01

A hierarchical poly (ether sulfone) (PES) porous membrane is facilely fabricated via a hard template method for vanadium flow battery (VFB) application. The construction of this hierarchical porous membrane is prepared via removing templates (phenolphthalein). The pore size can be well controlled by optimizing the template content in the cast solution, ensuring the membrane conductivity and selectively. The prepared hierarchical porous membrane can combine high ion selectivity with high proton conductivity, which renders a good electrochemical performance in a VFB. The optimized hierarchical porous membrane shows a columbic efficiency of 94.52% and energy efficiency of 81.66% along with a superior ability to maintain stable capacity over extended cycling at a current density of 80 mA cm-2. The characteristics of low cost, proven chemical stability and high electrochemical performance afford the hierarchical PES porous membrane great prospect in VFB application.

Graphite felt modified with bismuth nanoparticles as negative electrode in a vanadium redox flow battery.

PubMed

Suárez, David J; González, Zoraida; Blanco, Clara; Granda, Marcos; Menéndez, Rosa; Santamaría, Ricardo

2014-03-01

A graphite felt decorated with bismuth nanoparticles was studied as negative electrode in a vanadium redox flow battery (VRFB). The results confirm the excellent electrochemical performance of the bismuth modified electrode in terms of the reversibility of the V(3+) /V(2+) redox reactions and its long-term cycling performance. Moreover a mechanism that explains the role that Bi nanoparticles play in the redox reactions in this negative half-cell is proposed. Bi nanoparticles favor the formation of BiHx , an intermediate that reduces V(3+) to V(2+) and, therefore, inhibits the competitive irreversible reaction of hydrogen formation (responsible for the commonly observed loss of Coulombic efficiency of VRFBs). Thus, the total charge consumed during the cathodic sweep in this electrode is used to reduce V(3+) to V(2+) , resulting in a highly reversible and efficient process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ANIONIC EXCHANGE PROCESS FOR THE RECOVERY OF URANIUM AND VANADIUM FROM CARBONATE SOLUTIONS

DOEpatents

Bailes, R.H.; Ellis, D.A.; Long, R.S.

1958-12-16

Uranium and vanadium can be economically purified and recovered from non- salt roast carbonate leach liquors by adsorption on a strongly basic anionic exchange resin and subsequent selective elution by one of three alternative methods. Method 1 comprises selectively eluting uranium from the resin with an ammonium sulfate solution followed by eluting vanadium from the resin with either 5 M NaCl, saturated (NH/sub 4/)/sub 2/CO/sub 3/, saturated NaHCO/sub 3/, 1 M NaOH, or saturated S0/sub 2/ solutions. Method II comprises selectively eluting vanadium from the resin with either concentrated NaCl or S0/sub 2/ solutions subsequent to pretreatment of the column with either S0/sub 2/ gas, 1 N HCl, or 0.1 N H/sub 2/8O/sub 4/ followed by eluting uranium from the resin with solutions containing 0.9 M NH/sub 4/Cl or NaCl and 0.1 Cl. Method III comprises flowing the carbonate leac solutlon through a first column of a strongly basic anlonlc exchange resin untll vanadium breakthrough occurs, so that the effluent solution is enriched ln uranium content and the vanadium is chiefly retalned by the resln, absorbing the uranlum from the enriched effluent solution on a second column of a strongly basic anionic exchange resin, pretreating the first column with either 0.1 N HCl, 0.1 H/sub 2/SO/sub 4/, C0/sub 2/ gas, or ammonium sulfate, selectively eluting the vanadlum from the column with saturated S0/sub 2/ solution, pretreatlng the second column with either 0.1 N HCl or S0/sub 2/ gas, selectively eluting residual vanadium from the column with saturated S0/sub 2/ solution, and then eluting the uranium from the column with either 0.1 N HCl and 1 N NaCl orO.l N HCl and 1 N NH/sub 4/Cl.

An Approach Toward Replacing Vanadium: A Single Organic Molecule for the Anode and Cathode of an Aqueous Redox‐Flow Battery

PubMed Central

Janoschka, Tobias; Friebe, Christian; Hager, Martin D.; Martin, Norbert

2017-01-01

Abstract By combining a viologen unit and a 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO) radical in one single combi‐molecule, an artificial bipolar redox‐active material, 1‐(4‐(((1‐oxyl‐2,2,6,6‐tetramethylpiperidin‐4‐yl)oxy)carbonyl)benzyl)‐1′‐methyl‐[4,4′‐bipyridine]‐1,1′‐diium‐chloride (VIOTEMP), was created that can serve as both the anode (−0.49 V) and cathode (0.67 V vs. Ag/AgCl) in a water‐based redox‐flow battery. While it mimics the redox states of flow battery metals like vanadium, the novel aqueous electrolyte does not require strongly acidic media and is best operated at pH 4. The electrochemical properties of VIOTEMP were investigated by using cyclic voltammetry, rotating disc electrode experiments, and spectroelectrochemical methods. A redox‐flow battery was built and the suitability of the material for both electrodes was demonstrated through a polarity‐inversion experiment. Thus, an organic aqueous electrolyte system being safe in case of cross contamination is presented. PMID:28413754

Membrane development for vanadium redox flow batteries.

PubMed

Schwenzer, Birgit; Zhang, Jianlu; Kim, Soowhan; Li, Liyu; Liu, Jun; Yang, Zhenguo

2011-10-17

Large-scale energy storage has become the main bottleneck for increasing the percentage of renewable energy in our electricity grids. Redox flow batteries are considered to be among the best options for electricity storage in the megawatt range and large demonstration systems have already been installed. Although the full technological potential of these systems has not been reached yet, currently the main problem hindering more widespread commercialization is the high cost of redox flow batteries. Nafion, as the preferred membrane material, is responsible for about 11% of the overall cost of a 1 MW/8 MWh system. Therefore, in recent years two main membrane related research threads have emerged: 1) chemical and physical modification of Nafion membranes to optimize their properties with regard to vanadium redox flow battery (VRFB) application; and 2) replacement of the Nafion membranes with different, less expensive materials. This review summarizes the underlying basic scientific issues associated with membrane use in VRFBs and presents an overview of membrane-related research approaches aimed at improving the efficiency of VRFBs and making the technology cost-competitive. Promising research strategies and materials are identified and suggestions are provided on how materials issues could be overcome.

A comprehensive equivalent circuit model of all-vanadium redox flow battery for power system analysis

NASA Astrophysics Data System (ADS)

Zhang, Yu; Zhao, Jiyun; Wang, Peng; Skyllas-Kazacos, Maria; Xiong, Binyu; Badrinarayanan, Rajagopalan

2015-09-01

Electrical equivalent circuit models demonstrate excellent adaptability and simplicity in predicting the electrical dynamic response of the all-vanadium redox flow battery (VRB) system. However, only a few publications that focus on this topic are available. The paper presents a comprehensive equivalent circuit model of VRB for system level analysis. The least square method is used to identify both steady-state and dynamic characteristics of VRB. The inherent features of the flow battery such as shunt current, ion diffusion and pumping energy consumption are also considered. The proposed model consists of an open-circuit voltage source, two parasitic shunt bypass circuits, a 1st order resistor-capacitor network and a hydraulic circuit model. Validated with experimental data, the proposed model demonstrates excellent accuracy. The mean-error of terminal voltage and pump consumption are 0.09 V and 0.49 W respectively. Based on the proposed model, self-discharge and system efficiency are studied. An optimal flow rate which maximizes the system efficiency is identified. Finally, the dynamic responses of the proposed VRB model under step current profiles are presented. Variables such as SOC and stack terminal voltage can be provided.

Kinetic enhancement via passive deposition of carbon-based nanomaterials in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Aaron, Doug; Yeom, Sinchul; Kihm, Kenneth D.; Ashraf Gandomi, Yasser; Ertugrul, Tugrul; Mench, Matthew M.

2017-10-01

Addition of carbon-based nanomaterials to operating flow batteries accomplishes vanadium redox flow battery performance improvement. Initial efforts focus on addition of both pristine graphene and vacuum-filtered reduced graphene oxide (rGO) film on carbon paper supporting electrodes. While the former is unable to withstand convective flow through the porous electrode, the latter shows measurable kinetic improvement, particularly when laid on the polymer electrolyte membrane (PEM) side of the electrode; in contrast to the kinetic performance gain, a deleterious impact on mass transport is observed. Based on this tradeoff, further improvement is realized using perforated rGO films placed on the PEM side of the electrodes. Poor mass transport in the dense rGO film prompts identification of a more uniform, passive deposition method. A suspension of rGO flakes or Vulcan carbon black (XC-72R), both boasting two orders-of-magnitude greater specific surface area than that of common carbon electrodes, is added to the electrolyte reservoirs and allowed to passively deposit on the carbon paper or carbon felt supporting electrodes. For common carbon felt electrodes, addition of rGO flakes or XC-72R enables a tripling of current density at the same 80% voltage efficiency.

Design trade-offs among shunt current, pumping loss and compactness in the piping system of a multi-stack vanadium flow battery

NASA Astrophysics Data System (ADS)

Ye, Qiang; Hu, Jing; Cheng, Ping; Ma, Zhiqi

2015-11-01

Trade-off between shunt current loss and pumping loss is a major challenge in the design of the electrolyte piping network in a flow battery system. It is generally recognized that longer and thinner ducts are beneficial to reduce shunt current but detrimental to minimize pumping power. Base on the developed analog circuit model and the flow network model, we make case studies of multi-stack vanadium flow battery piping systems and demonstrate that both shunt current and electrolyte flow resistance can be simultaneously minimized by using longer and thicker ducts in the piping network. However, extremely long and/or thick ducts lead to a bulky system and may be prohibited by the stack structure. Accordingly, the intrinsic design trade-off is between system efficiency and compactness. Since multi-stack configurations bring both flexibility and complexity to the design process, we perform systematic comparisons among representative piping system designs to illustrate the complicated trade-offs among numerous parameters including stack number, intra-stack channel resistance and inter-stack pipe resistance. As the final design depends on various technical and economical requirements, this paper aims to provide guidelines rather than solutions for designers to locate the optimal trade-off points according to their specific cases.

HF/H2O2 treated graphite felt as the positive electrode for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

He, Zhangxing; Jiang, Yingqiao; Meng, Wei; Jiang, Fengyun; Zhou, Huizhu; Li, Yuehua; Zhu, Jing; Wang, Ling; Dai, Lei

2017-11-01

In order to improve the electrochemical performance of the positive graphite felt electrode in vanadium flow redox battery, a novel method is developed to effectively modify the graphite felt by combination of etching of HF and oxidation of H2O2. After the etching of HF for the graphite felt at ambient temperature, abundant oxygen-containing functional groups were further introduced on the surface of graphite felt by hydrothermal treatment using H2O2 as oxidant. Benefiting from the surface etching and introduction of functional groups, mass transfer and electrode process can be improved significantly on the surface of graphite felt. VO2+/VO2+ redox reaction on the graphite felt modified by HF and H2O2 jointly (denote: GF-HF/H2O2) exhibits superior electrochemical kinetics in comparison with the graphite felt modified by single HF or H2O2 treatment. The cell using GF-HF/H2O2 as the positive electrode was assembled and its electrochemical properties were evaluated. The increase of energy efficiency of 4.1% for GF-HF/H2O2 at a current density of 50 mA cm-2 was obtained compared with the pristine graphite felt. The cell using GF-HF/H2O2 also demonstrated higher discharge capacity. Our study revealed that HF/H2O2 treatment is an efficient method to enhance the electrochemical performance of graphite felt, further improving the comprehensive energy storage performance of the vanadium flow redox battery.

Inducing microstructural changes in Nafion by incorporating graphitic carbon nitride to enhance the vanadium-blocking effect.

PubMed

Wu, Chunxiao; Lu, Shanfu; Zhang, Jin; Xiang, Yan

2018-03-14

Two-dimensional graphitic carbon nitride (g-C 3 N 4 ) nanosheets are introduced into a Nafion matrix to prepare a 'vanadium-blocking' recast Nafion membrane for vanadium redox flow battery (VRFB) applications. After 0.2 wt% g-C 3 N 4 nanosheets are incorporated, the vanadium ion permeability of the composite membrane decreases from 3.3 × 10 -7 cm 2 min -1 to 3.8 × 10 -9 cm 2 min -1 , which is a reduction of two orders of magnitude in comparison to the pristine recast Nafion membrane. This satisfactory result contributes to the physical blocking effect as well as the Donnan effect from the 2D morphology and functional amino groups of g-C 3 N 4 nanosheets. Notably, this work reveals that the g-C 3 N 4 nanosheets can help reinforce the vanadium-blocking effect by changing the microstructure of Nafion in addition to the well-known effects mentioned above. The g-C 3 N 4 nanosheets induce shrinkage in the original spherical structure of the ion cluster and generate a new lamellar structure. Correspondingly, the amorphous phase of Nafion is interrupted, and the membrane crystallinity is reduced. The VRFB with an optimized composite membrane achieves a high coulombic efficiency of 97% and an energy efficiency of 83% at a current density of 160 mA cm -2 . Meanwhile, the battery exhibited excellent lifetime stability during a 100 charge-discharge cycling test.

Au doping effects on electrical and optical properties of vanadium dioxides

NASA Astrophysics Data System (ADS)

Zhu, YaBin; He, Fan; Na, Jie

2012-03-01

Vanadium dioxides were fabricated on normal glass substrates using reactive radio frequency (RF) magnetron sputtering. The oxygen flow volume and annealed temperatures as growth parameters are systematically investigated. The electrical and optical properties of VO2 and Au:VO2 thin films with different growth conditions are discussed. The semiconductor-metal phase transition temperature decreased by ˜10°C for the sample with Au doping compared to the sample without Au doping. However, the optical transmittance of Au:VO2 thin films is much lower than that of bare VO2. These results show that Au doping has a marked effect on the electrical and optical properties.

Influence of solvents on species crossover and capacity decay in non-aqueous vanadium redox flow batteries: Characterization of acetonitrile and 1, 3 dioxolane solvent mixture

NASA Astrophysics Data System (ADS)

Bamgbopa, Musbaudeen O.; Almheiri, Saif

2017-02-01

The importance of the choice of solvent in a non-aqueous redox flow battery (NARFB) cannot be overemphasized. Several studies demonstrated the influence of the solvent on electrolyte performance in terms of reaction rates, energy/power densities, and efficiencies. In this work, we investigate capacity decay as a direct consequence of varying reactant crossover rates through membranes in different solvent environments. Specifically, we demonstrate the superiority of an 84/16 vol% acetonitrile/1,3 dioxolane solvent mixture over pure acetonitrile in terms of energy efficiency (up to 89%) and capacity retention for vanadium NARFBs - while incorporating a Nafion 115 membrane. The permeability of Nafion to the vanadium acetylacetonate active species is an order of magnitude lower when pure acetonitrile is replaced by the solvent mixture. A method to estimate relative membrane permeability is formulated from numerical analysis of self-discharge experimental data. Furthermore, tests on a modified Nafion/SiO2 membrane, which generally offered low species permeability, also show that different solvents alter membrane permeability. Elemental and morphological analyses of cycled Nafion and NafionSi membranes in different solvent environments indicate that different crossover rates induced by the choice of solvent during cycling are due to changes in the membrane microstructure, intrinsic permeability, swelling rates, and chemical stability.

Zirconium oxide nanotube-Nafion composite as high performance membrane for all vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Aziz, Md. Abdul; Shanmugam, Sangaraju

2017-01-01

A high-performance composite membrane for vanadium redox flow battery (VRB) consisting of ZrO2 nanotubes (ZrNT) and perfluorosulfonic acid (Nafion) was fabricated. The VRB operated with a composite (Nafion-ZrNT) membrane showed the improved ion-selectivity (ratio of proton conductivity to permeability), low self-discharge rate, high discharge capacity and high energy efficiency in comparison with a pristine commercial Nafion-117 membrane. The incorporation of zirconium oxide nanotubes in the Nafion matrix exhibits high proton conductivity (95.2 mS cm-1) and high oxidative stability (99.9%). The Nafion-ZrNT composite membrane exhibited low vanadium ion permeability (3.2 × 10-9 cm2 min-1) and superior ion selectivity (2.95 × 107 S min cm-3). The VRB constructed with a Nafion-ZrNT composite membrane has lower self-discharge rate maintaining an open-circuit voltage of 1.3 V for 330 h relative to a pristine Nafion membrane (29 h). The discharge capacity of Nafion-ZrNT membrane (987 mAh) was 3.5-times higher than Nafion-117 membrane (280 mAh) after 100 charge-discharge cycles. These superior properties resulted in higher coulombic and voltage efficiencies with Nafion-ZrNT membranes compared to VRB with Nafion-117 membrane at a 40 mA cm-2 current density.

Highly active, bi-functional and metal-free B4C-nanoparticle-modified graphite felt electrodes for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Jiang, H. R.; Shyy, W.; Wu, M. C.; Wei, L.; Zhao, T. S.

2017-10-01

The potential of B4C as a metal-free catalyst for vanadium redox reactions is investigated by first-principles calculations. Results show that the central carbon atom of B4C can act as a highly active reaction site for redox reactions, due primarily to the abundant unpaired electrons around it. The catalytic effect is then verified experimentally by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests, both of which demonstrate that B4C nanoparticles can enhance the kinetics for both V2+/V3+ and VO2+/VO2+ redox reactions, indicating a bi-functional effect. The B4C-nanoparticle-modified graphite felt electrodes are finally prepared and tested in vanadium redox flow batteries (VRFBs). It is shown that the batteries with the prepared electrodes exhibit energy efficiencies of 88.9% and 80.0% at the current densities of 80 and 160 mA cm-2, which are 16.6% and 18.8% higher than those with the original graphite felt electrodes. With a further increase in current densities to 240 and 320 mA cm-2, the batteries can still maintain energy efficiencies of 72.0% and 63.8%, respectively. All these results show that the B4C-nanoparticle-modified graphite felt electrode outperforms existing metal-free catalyst modified electrodes, and thus can be promising electrodes for VRFBs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Soowhan; Thomsen, Edwin; Xia, Guanguang

This paper explores demonstration of an advanced vanadium redox flow battery (VRFB) using a mixed acid (sulfuric and hydrochloric acid) supporting electrolyte in a kW scale. The prototype VRFB is capable of delivering more than 1.1 kW in the whole operation range (15~85% state of charge) at 80 mA/cm2 with high energy efficiency of 82% and energy content of 1.4 kWh. The system has been operated stably without any precipitation even at elevated electrolyte temperatures of > 45°C, while the control tests with the conventional sulfuric acid electrolyte suffered from precipitation after 80 cycles. The mixed acid system enabled operationmore » at elevated temperature (> 40°C), providing unique advantages over the conventional pure sulfate system; 1) high stack energy efficiency due to better kinetics and low electrolyte resistance, 2) low viscosity, resulting in reduced pumping loss, 3) elimination of additional heat exchanger, 4) high system efficiency and 5) simple system design and operation.« less

Validating and improving a zero-dimensional stack voltage model of the Vanadium Redox Flow Battery

NASA Astrophysics Data System (ADS)

König, S.; Suriyah, M. R.; Leibfried, T.

2018-02-01

Simple, computationally efficient battery models can contribute significantly to the development of flow batteries. However, validation studies for these models on an industrial-scale stack level are rarely published. We first extensively present a simple stack voltage model for the Vanadium Redox Flow Battery. For modeling the concentration overpotential, we derive mass transfer coefficients from experimental results presented in the 1990s. The calculated mass transfer coefficient of the positive half-cell is 63% larger than of the negative half-cell, which is not considered in models published to date. Further, we advance the concentration overpotential model by introducing an apparent electrochemically active electrode surface which differs from the geometric electrode area. We use the apparent surface as fitting parameter for adapting the model to experimental results of a flow battery manufacturer. For adapting the model, we propose a method for determining the agreement between model and reality quantitatively. To protect the manufacturer's intellectual property, we introduce a normalization method for presenting the results. For the studied stack, the apparent electrochemically active surface of the electrode is 41% larger than its geometrical area. Hence, the current density in the diffusion layer is 29% smaller than previously reported for a zero-dimensional model.

Modeling the effect of shunt current on the charge transfer efficiency of an all-vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Chen, Yong-Song; Ho, Sze-Yuan; Chou, Han-Wen; Wei, Hwa-Jou

2018-06-01

In an all-vanadium redox flow battery (VRFB), a shunt current is inevitable owing to the electrically conductive electrolyte that fills the flow channels and manifolds connecting cells. The shunt current decreases the performance of a VRFB stack as well as the energy conversion efficiency of a VRFB system. To understand the shunt-current loss in a VRFB stack with various designs and operating conditions, a mathematical model is developed to investigate the effects of the shunt current on battery performance. The model is calibrated with experimental data under the same operating conditions. The effects of the battery design, including the number of cells, state of charge (SOC), operating current, and equivalent resistance of the electrolytes in the flow channels and manifolds, on the shunt current are analyzed and discussed. The charge-transfer efficiency is calculated to investigate the effects of the battery design parameters on the shunt current. When the cell number is increased from 5 to 40, the charge transfer efficiency is decreased from 0.99 to a range between 0.76 and 0.88, depending on operating current density. The charge transfer efficiency can be maintained at higher than 0.9 by limiting the cell number to less than 20.

Thermal hydraulic behavior and efficiency analysis of an all-vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Xiong, Binyu; Zhao, Jiyun; Tseng, K. J.; Skyllas-Kazacos, Maria; Lim, Tuti Mariana; Zhang, Yu

2013-11-01

Vanadium redox flow batteries (VRBs) are very competitive for large-capacity energy storage in power grids and in smart buildings due to low maintenance costs, high design flexibility, and long cycle life. Thermal hydraulic modeling of VRB energy storage systems is an important issue and temperature has remarkable impacts on the battery efficiency, the lifetime of material and the stability of the electrolytes. In this paper, a lumped model including auxiliary pump effect is developed to investigate the VRB temperature responses under different operating and surrounding environmental conditions. The impact of electrolyte flow rate and temperature on the battery electrical characteristics and efficiencies are also investigated. A one kilowatt VRB system is selected to conduct numerical simulations. The thermal hydraulic model is benchmarked with experimental data and good agreement is found. Simulation results show that pump power is sensitive to hydraulic design and flow rates. The temperature in the stack and tanks rises up about 10 °C under normal operating conditions for the stack design and electrolyte volume selected. An optimal flow rate of around 90 cm3 s-1 is obtained for the proposed battery configuration to maximize battery efficiency. The models developed in this paper can also be used for the development of a battery control strategy to achieve satisfactory thermal hydraulic performance and maximize energy efficiency.

Conjugated dynamic modeling on vanadium redox flow battery with non-constant variance for renewable power plant applications

NASA Astrophysics Data System (ADS)

Siddiquee, Abu Nayem Md. Asraf

A parametric modeling study has been carried out to assess the impact of change in operating parameters on the performance of Vanadium Redox Flow Battery (VRFB). The objective of this research is to develop a computer program to predict the dynamic behavior of VRFB combining fluid mechanics, reaction kinetics, and electric circuit. The computer program was developed using Maple 2015 and calculations were made at different operating parameters. Modeling results show that the discharging time increases from 2.2 hours to 6.7 hours when the concentration of V2+ in electrolytes increases from 1M to 3M. The operation time during the charging cycle decreases from 6.9 hours to 3.3 hours with the increase of applied current from 1.85A to 3.85A. The modeling results represent that the charging and discharging time were found to increase from 4.5 hours to 8.2 hours with the increase in tank to cell ratio from 5:1 to 10:1.

Highly catalytic and stabilized titanium nitride nanowire array-decorated graphite felt electrodes for all vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Wei, L.; Zhao, T. S.; Zeng, L.; Zeng, Y. K.; Jiang, H. R.

2017-02-01

In this work, we prepare a highly catalytic and stabilized titanium nitride (TiN) nanowire array-decorated graphite felt electrode for all vanadium redox flow batteries (VRFBs). Free-standing TiN nanowires are synthesized by a two-step process, in which TiO2 nanowires are first grown onto the surface of graphite felt via a seed-assisted hydrothermal method and then converted to TiN through nitridation reaction. When applied to VRFBs, the prepared electrode enables the electrolyte utilization and energy efficiency to be 73.9% and 77.4% at a high current density of 300 mA cm-2, which are correspondingly 43.3% and 15.4% higher than that of battery assembled with a pristine electrode. More impressively, the present battery exhibits good stability and high capacity retention during the cycle test. The superior performance is ascribed to the significant improvement in the electrochemical kinetics and enlarged active sites toward V3+/V2+ redox reaction.

A new strategy for integrating abundant oxygen functional groups into carbon felt electrode for vanadium redox flow batteries

PubMed Central

Kim, Ki Jae; Lee, Seung-Wook; Yim, Taeeun; Kim, Jae-Geun; Choi, Jang Wook; Kim, Jung Ho; Park, Min-Sik; Kim, Young-Jun

2014-01-01

The effects of surface treatment combining corona discharge and hydrogen peroxide (H2O2) on the electrochemical performance of carbon felt electrodes for vanadium redox flow batteries (VRFBs) have been thoroughly investigated. A high concentration of oxygen functional groups has been successfully introduced onto the surface of the carbon felt electrodes by a specially designed surface treatment, which is mainly responsible for improving the energy efficiency of VRFBs. In addition, the wettability of the carbon felt electrodes also can be significantly improved. The energy efficiency of the VRFB cell employing the surface modified carbon felt electrodes is improved by 7% at high current density (148 mA cm−2). Such improvement is attributed to the faster charge transfer and better wettability allowed by surface-active oxygen functional groups. Moreover, this method is much more competitive than other surface treatments in terms of processing time, production costs, and electrochemical performance. PMID:25366060

Synergistic effect of carbon nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance all-vanadium redox flow battery.

PubMed

Park, Minjoon; Jung, Yang-jae; Kim, Jungyun; Lee, Ho il; Cho, Jeaphil

2013-10-09

Carbon nanofiber/nanotube (CNF/CNT) composite catalysts grown on carbon felt (CF), prepared from a simple way involving the thermal decomposition of acetylene gas over Ni catalysts, are studied as electrode materials in a vanadium redox flow battery. The electrode with the composite catalyst prepared at 700 °C (denoted as CNF/CNT-700) demonstrates the best electrocatalytic properties toward the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples among the samples prepared at 500, 600, 700, and 800 °C. Moreover, this composite electrode in the full cell exhibits substantially improved discharge capacity and energy efficiency by ~64% and by ~25% at 40 mA·cm(-2) and 100 mA·cm(-2), respectively, compared to untreated CF electrode. This outstanding performance is due to the enhanced surface defect sites of exposed edge plane in CNF and a fast electron transfer rate of in-plane side wall of the CNT.

Performance evaluation of thermally treated graphite felt electrodes for vanadium redox flow battery and their four-point single cell characterization

NASA Astrophysics Data System (ADS)

Mazúr, P.; Mrlík, J.; Beneš, J.; Pocedič, J.; Vrána, J.; Dundálek, J.; Kosek, J.

2018-03-01

In our contribution we study the electrocatalytic effect of oxygen functionalization of thermally treated graphite felt on kinetics of electrode reactions of vanadium redox flow battery. Chemical and morphological changes of the felts are analysed by standard physico-chemical characterization techniques. A complex method four-point method is developed and employed for characterization of the felts in a laboratory single-cell. The method is based on electrochemical impedance spectroscopy and load curves measurements of positive and negative half-cells using platinum wire pseudo-reference electrodes. The distribution of ohmic and faradaic losses within a single-cell is evaluated for both symmetric and asymmetric electrode set-up with respect to the treatment conditions. Positive effect of oxygen functionalization is observed only for negative electrode, whereas kinetics of positive electrode reaction is almost unaffected by the treatment. This is in a contradiction to the results of typically employed cyclovoltammetric characterization which indicate that both electrodes are enhanced by the treatment to a similar extent. The developed four-point characterization method can be further used e.g., for the component screening and in-situ durability studies on single-cell scale redox flow batteries of various chemistries.

Degradation of all-vanadium redox flow batteries (VRFB) investigated by electrochemical impedance and X-ray photoelectron spectroscopy: Part 2 electrochemical degradation

NASA Astrophysics Data System (ADS)

Derr, Igor; Bruns, Michael; Langner, Joachim; Fetyan, Abdulmonem; Melke, Julia; Roth, Christina

2016-09-01

Electrochemical degradation (ED) of carbon felt electrodes was investigated by cycling of a flow through all-vanadium redox flow battery (VRFB) and conducting half-cell measurements with two reference electrodes inside the test bench. ED was detected using half-cell and full-cell electrochemical impedance spectroscopy (EIS) at different states of charge (SOC). Reversing the polarity of the battery to recover cell performance was performed with little success. Renewing the electrolyte after a certain amount of cycles restored the capacity of the battery. X-ray photoelectron spectroscopy (XPS) reveals that the amount of surface functional increases by more than a factor of 3 for the negative side as well as for the positive side. Scanning electron microscope (SEM) images show a peeling of the fiber surface after cycling the felts, which leads to a loss of electrochemically active surface area (ECSA). Long term cycling shows that ED has a stronger impact on the negative half-cell [V(II)/V(III)] than the positive half-cell [V(IV)/V(V)] and that the negative half-cell is the rate-determining half-cell for the VRFB.

Speciation of vanadium in Chinese cabbage (Brassica rapa L.) and soils in response to different levels of vanadium in soils and cabbage growth.

PubMed

Tian, Liyan; Yang, Jinyan; Alewell, Christine; Huang, Jen-How

2014-09-01

This study highlights the accumulation and speciation of vanadium in Chinese cabbage (Brassica rapa L.) in relation to the speciation of soil vanadium with pot experiments at 122-622mgVkg(-1) by spiking NH4VO3. Cabbage planting decreased the bioavailable and residual vanadium based on sequential extraction, leading to enrichment of oxalate-extractable vanadium in soils. The biomass production increased with increasing concentrations of soil vanadium from 122 to 372mgVkg(-1), probably due to the increasing nitrogen availability and low vanadium availability in our soils with a consequent low vanadium toxicity. Although the concentrations of root vanadium (14.4-24.9mgVkg(-1)) related positively with soil vanadium, the bio-dilution alleviated the increase of leaf vanadium (2.1-2.7mgVkg(-1)). The predominance of vanadium(IV) in leaves (∼60-80% of total vanadium) indicates bio-reduction of vanadium in Chinese cabbage, since the mobile vanadium in oxic soils was usually pentavalent. Approximately 15-20% of the leaf vanadium was associated with recalcitrant leaf tissues. The majority of leaf vanadium was water and ethanol extractable, which is considered mobile and may cause more toxic effects on Chinese cabbage. Copyright © 2014 Elsevier Ltd. All rights reserved.

A Pulsed Power System Design Using Lithium-ion Batteries and One Charger per Battery

DTIC Science & Technology

2009-12-01

zinc-bromine and vanadium redox batteries • NAS: high-temperature sodium batteries • EDLC: Electric Double-Layer Capacitors • SMES...terminology used in this figure. • Conventional: lead-acid, nickel-cadmium, and nickel-metal hydride batteries . • Lithium: lithium ion batteries . • Flow ...than the second stage due to less current flowing to the battery [5], [7], [8], [9]. Figure 4 shows typical current, voltage, and capacity curves

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, David M.; Thomsen, Edwin C.; Wang, Wei

Three Nafion membranes of similar composition but different thicknesses were operated in a 3-cell 1kW class all vanadium mixed acid redox flow battery. The influence of current density on the charge/discharge characteristics, coulombic and energy efficiency, capacity fade, operating temperature and pressure drop in the flow circuit will be discussed and correlated to the Nafion membrane thickness. Material costs associated with the Nafion membranes, ease of handling the membranes, and performance impacts will also be discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujimoto, Cy H.; Kim, Soowhan; Stains, Ronald

Sulfonated Diels Alder poly(phenylene) (SDAPP) was examined for vanadium redox flow battery (VRFB) use. The ion exchange capacity (IEC) was varied from 1.4, 1.6 and 2.0 meq/g in order to tune the proton conductivity and vanadium permeability. Coulombic efficiencies between 92 to 99% were observed, depending on IEC (lower IEC, higher coulombic efficiencies). In all cases the SDAPP displayed comparable energy efficiencies (88 - 90%) to Nafion 117 (88%) at 50mA/cm2. Membrane durability also was dependent on IEC; SDAPP with the highest IEC lasted slightly over 50 cycles while SDAPP with the lowest IEC lasted over 400 cycles and testingmore » was discontinued only due to time constraints. Accelerated vanadium lifetime studies were initialed with SDAPP, by soaking films in a 0.1 M V5+ and 5.0 M total SO4-2 solution. The rate of degradation was also proportional with IEC; the 2 meq/g sample dissolved within 376 hours, the 1.6 meq/g sample dissolved after 860 hours, while the 1.4 meq/g sample broke apart after 1527 hours.« less

CTAB-Aided Synthesis of Stacked V2O5 Nanosheets: Morphology, Electrochemical Features and Asymmetric Device Performance

NASA Astrophysics Data System (ADS)

Saravanakumar, B.; Maruthamuthu, S.; Umadevi, V.; Saravanan, V.

To accomplish superior performance in supercapacitors, a fresh class of electrode materials with advantageous structures is essential. Owing to its rich electrochemical activity, vanadium oxides are considered to be an attractive electrode material for energy storing devices. In this work, vanadium pentoxide (V2O5) nanostructures were prepared using surfactant (CTAB)-assisted hydrothermal route. Stacked V2O5 sheets enable additional channels for electrolyte ion intercalation. These stacked V2O5 nanosheets show highest specific capacitance of 466Fg-1 at 0.5Ag-1. In addition, it exhibits good rate capacity, lower value of charge transfer resistance and good stability when used as an electrode material for supercapacitors. Further, an asymmetric supercapacitor device was assembled utilizing the stacked V2O5 sheets and activated carbon as electrodes. The electrochemical features of the device are also discussed.

Thermal Instability Induced Oriented 2D Pores for Enhanced Sodium Storage.

PubMed

Kong, Lingjun; Xie, Chen-Chao; Gu, Haichen; Wang, Chao-Peng; Zhou, Xianlong; Liu, Jian; Zhou, Zhen; Li, Zhao-Yang; Zhu, Jian; Bu, Xian-He

2018-04-19

Hierarchical porous structures are highly desired for various applications. However, it is still challenging to obtain such materials with tunable architectures. Here, this paper reports hierarchical nanomaterials with oriented 2D pores by taking advantages of thermally instable bonds in vanadium-based metal-organic frameworks (MOFs). High-temperature calcination of these MOFs accompanied by the loss of coordinated water molecules and other components enables the formation of orderly slit-like 2D pores in vanadium oxide/porous carbon nanorods (VO x /PCs). This unique combination leads to an increase of the reactive surface area. In addition, optimized VO x /PCs demonstrate high-rate capability and ultralong cycling life for sodium storage. The assembled full cells also show high capacity and cycling stability. This report provides an effective strategy for producing MOFs-derived composites with hierarchical porous architectures for energy storage. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave assisted growth of nanorods vanadium dioxide VO2 (R): structural and electrical properties

NASA Astrophysics Data System (ADS)

Derkaoui, I.; Khenfouch, M.; Mothudi, B. M.; Moloi, S. J.; Zorkani, I.; Jorio, A.; Maaza, M.

2018-03-01

Nanostructured metal oxides have attracted a lot of attention recently owning to their unique structural advantages and demonstrated promising chemical and physical properties for various applications. In this study, we report the structural and electrical properties of vanadium dioxide VO2 (R) prepared via a single reaction microwave (SRC) synthesis. Our results are revealing that the components of VO2 (R) films have a rod-like shape with a uniform size distribution. The nanorods with very smooth and flat surfaces have a typical length of up to 2μm and a width of about several nanometers. The structural investigations reveal the high crystallinity of VO2 (R) ensuring good electrical contact and showing a high conductivity as a function of temperature. This synthesis method provides a new simple route to fabricate one-dimensional nanostructured metal oxides which is suitable for a large field of applications especially for smart windows.

Energy Storage for the Power Grid

ScienceCinema

Imhoff, Carl; Vaishnav, Dave; Wang, Wei

2018-05-30

The iron vanadium redox flow battery was developed by researchers at Pacific Northwest National Laboratory as a solution to large-scale energy storage for the power grid. This technology provides the energy industry and the nation with a reliable, stable, safe, and low-cost storage alternative for a cleaner, efficient energy future.

Hydrophobic asymmetric ultrafiltration PVDF membranes: an alternative separator for VFB with excellent stability.

PubMed

Wei, Wenping; Zhang, Huamin; Li, Xianfeng; Zhang, Hongzhang; Li, Yun; Vankelecom, Ivo

2013-02-14

Polyvinylidene fluoride (PVDF) ultrafiltration membranes were investigated for the first time in vanadium redox flow battery (VFB) applications. Surprisingly, PVDF ultrafiltration membranes with hydrophobic pore walls and relatively large pore sizes of several tens of nanometers proved able to separate vanadium ions and protons efficiently, thus being suitable as a VFB separator. The ion selectivity of this new type of VFB membrane could be tuned readily by controlling the membrane morphology via changes in the composition of the membrane casting solution, and the casting thickness. The results showed that the PVDF membranes offered good performances and excellent stability in VFB applications, where it could, performance-wise, truly substitute Nafion in VFB applications, but at a much lower cost.

Characterization of vanadium ion uptake in sulfonated diels alder poly(phenylene) membranes

DOE PAGES

Lawton, Jamie; Jones, Amanda; Tang, Zhijiang; ...

2015-11-28

Sulfonated diels alder poly(phenylene) (SDAPP), alternative aromatic hydrocarbon membranes for vanadium redox flow batteries (VRFBs) are characterized using electron paramagnetic resonance (EPR). Membranes soaked in sulfuric acid and vanadyl sulfate are analyzed to determine the membrane environment in which the vanadyl ion (VO 2+) diffuses in the membranes. These results are compared to Nafion 117 membranes. In contrast to Nafion, the VO 2+ in SDAPP membranes exists in two different environments. The results of analysis of rotational diffusion determined from fits the EPR spectral lineshapes in comparison with previously reported permeation studies and measurements of partitioning functions reported here suggestmore » that the diffusion pathways in SDAPP are very different than in Nafion.« less

Influence of dissolved organic matter on dissolved vanadium speciation in the Churchill River estuary (Manitoba, Canada).

PubMed

Shi, Yong Xiang; Mangal, Vaughn; Guéguen, Céline

2016-07-01

Diffusive gradients in thin films (DGT) devices were used to investigate the temporal and spatial changes in vanadium (V) speciation in the Churchill estuary system (Manitoba). Thirty-six DGT sets and 95 discrete water samples were collected at 8 river and 3 estuary sites during spring freshet and summer base flow. Dissolved V concentration in the Churchill River at summer base flow was approximately 5 times higher than those during the spring high flow (27.3 ± 18.9 nM vs 4.8 ± 3.5 nM). DGT-labile V showed an opposite trend with greater values found during the spring high flow (2.6 ± 1.8 nM vs 1.4 ± 0.3 nM). Parallel factor analysis (PARAFAC) conducted on 95 excitation-emission matrix spectra validated four humic-like (C1C4) and one protein-like (C5) fluorescent components. Significant positive relationship was found between protein-like DOM and DGT-labile V (r = 0.53, p < 0.05), indicating that protein-like DOM possibly affected the DGT-labile V concentration in Churchill River. Sediment leachates were enriched in DGT-labile V and protein-like DOM, which can be readily released when river sediment began to thaw during spring freshet. Copyright © 2016 Elsevier Ltd. All rights reserved.

A highly permeable and enhanced surface area carbon-cloth electrode for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zhao, T. S.; Zeng, Y. K.; An, L.; Wei, L.

2016-10-01

In this work, a high-performance porous electrode, made of KOH-activated carbon-cloth, is developed for vanadium redox flow batteries (VRFBs). The macro-scale porous structure in the carbon cloth formed by weaving the carbon fibers in an ordered manner offers a low tortuosity (∼1.1) and a broad pore distribution from 5 μm to 100 μm, rendering the electrode a high hydraulic permeability and high effective ionic conductivity, which are beneficial for the electrolyte flow and ion transport through the porous electrode. The use of KOH activation method to create nano-scale pores on the carbon-fiber surfaces leads to a significant increase in the surface area for redox reactions from 2.39 m2 g-1 to 15.4 m2 g-1. The battery assembled with the present electrode delivers an energy efficiency of 80.1% and an electrolyte utilization of 74.6% at a current density of 400 mA cm-2, as opposed to an electrolyte utilization of 61.1% achieved by using a conventional carbon-paper electrode. Such a high performance is mainly attributed to the combination of the excellent mass/ion transport properties and the high surface area rendered by the present electrode. It is suggested that the KOH-activated carbon-cloth electrode is a promising candidate in redox flow batteries.

Pore-scale study of multiphase reactive transport in fibrous electrodes of vanadium redox flow batteries

DOE PAGES

Chen, Li; He, YaLing; Tao, Wen -Quan; ...

2017-07-21

The electrode of a vanadium redox flow battery generally is a carbon fibre-based porous medium, in which important physicochemical processes occur. In this work, pore-scale simulations are performed to study complex multiphase flow and reactive transport in the electrode by using the lattice Boltzmann method (LBM). Four hundred fibrous electrodes with different fibre diameters and porosities are reconstructed. Both the permeability and diffusivity of the reconstructed electrodes are predicted and compared with empirical relationships in the literature. Reactive surface area of the electrodes is also evaluated and it is found that existing empirical relationship overestimates the reactive surface under lowermore » porosities. Further, a pore-scale electrochemical reaction model is developed to study the effects of fibre diameter and porosity on electrolyte flow, V II/V III transport, and electrochemical reaction at the electrolyte-fibre surface. Finally, evolution of bubble cluster generated by the side reaction is studied by adopting a LB multiphase flow model. Effects of porosity, fibre diameter, gas saturation and solid surface wettability on average bubble diameter and reduction of reactive surface area due to coverage of bubbles on solid surface are investigated in detail. It is found that gas coverage ratio is always lower than that adopted in the continuum model in the literature. Furthermore, the current pore-scale studies successfully reveal the complex multiphase flow and reactive transport processes in the electrode, and the simulation results can be further upscaled to improve the accuracy of the current continuum-scale models.« less

Vanadium Respiration by Geobacter metallireducens: Novel Strategy for In Situ Removal of Vanadium from Groundwater

PubMed Central

Ortiz-Bernad, Irene; Anderson, Robert T.; Vrionis, Helen A.; Lovley, Derek R.

2004-01-01

Vanadium can be an important contaminant in groundwaters impacted by mining activities. In order to determine if microorganisms of the Geobacteraceae, the predominant dissimilatory metal reducers in many subsurface environments, were capable of reducing vanadium(V), Geobacter metallireducens was inoculated into a medium in which acetate was the electron donor and vanadium(V) was the sole electron acceptor. Reduction of vanadium(V) resulted in the production of vanadium(IV), which subsequently precipitated. Reduction of vanadium(V) was associated with cell growth with a generation time of 15 h. No vanadium(V) was reduced and no precipitate was formed in heat-killed or abiotic controls. Acetate was the most effective of all the electron donors evaluated. When acetate was injected into the subsurface to enhance the growth and activity of Geobacteraceae in an aquifer contaminated with uranium and vanadium, vanadium was removed from the groundwater even more effectively than uranium. These studies demonstrate that G. metallireducens can grow via vanadium(V) respiration and that stimulating the activity of Geobacteraceae, and hence vanadium(V) reduction, can be an effective strategy for in situ immobilization of vanadium in contaminated subsurface environments. PMID:15128571

Temperature-dependent mechanical behavior of silicon dioxide, gold and gold-vanadium thin films for VLSI integrated circuits and MicroElectroMechanical systems (MEMs)

NASA Astrophysics Data System (ADS)

Lin, Ming-Tzer

The Semiconductor Industry has grown rapidly in the last twenty years. The national technology roadmap for semiconductors plans for developing the complexity and packing density of semiconductor devices into the next decade, allowing ever smaller and more densely packed structures to be fabricated. Recently, MEMS (Micro-Electro-Mechanical Systems) have become important in modern technology. The goal of MEMs is to integrate many types of miniature devices on a single chip, creating a new micro-world. The oxidation of silicon is one of the most important processes in semiconductor technology. Producing high-quality IC's and MEMS devices requires an understanding of the basic oxidation mechanism. In addition, for the reliability of IC's and MEMS devices, the mechanical properties of the oxide play a critical role. There has been an apparent convergence of opinion on the relevant mechanism leading to the "standard computational model" for stress effects on silicon oxidation. This model has recently become suspect. Most of the reasonably direct experimental data on the flow properties of SiO 2 thin film do not support a stress-dependent viscosity of the sort envisioned by the model. Gold and gold vanadium alloys are used in electrical interconnections and in radio frequency switch contacts for the semiconductor industry, MEMs sensors for the aerospace industry and also in brain probes by the bioelectronics mechanical industry. Despite the strong potential usage of gold and gold vanadium thin films at the small scale, very little is known about their mechanical properties. Our goal was to experimentally investigate stress and its influence on SiO2 thin films and the mechanical properties of gold and gold vanadium thin films at room temperature and at elevated temperature of different vanadium concentration. We found that the application of relatively small amounts of bending to an oxidizing silicon substrate leads to significant decreases in oxide thickness in the ultrathin oxide regime. Both tensile and compressive bending retard oxide growth, although compressive bending results in somewhat thinner oxides than does tensile bending. We also determined the modulus of gold and gold vanadium, and discovered that there is some evidence for a vanadium concentration dependence of the mechanical properties.

A transient electrochemical model incorporating the Donnan effect for all-vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Lei, Y.; Zhang, B. W.; Bai, B. F.; Zhao, T. S.

2015-12-01

In a typical all-vanadium redox flow battery (VRFB), the ion exchange membrane is directly exposed in the bulk electrolyte. Consequently, the Donnan effect occurs at the membrane/electrolyte (M/E) interfaces, which is critical for modeling of ion transport through the membrane and the prediction of cell performance. However, unrealistic assumptions in previous VRFB models, such as electroneutrality and discontinuities of ionic potential and ion concentrations at the M/E interfaces, lead to simulated results inconsistent with the theoretical analysis of ion adsorption in the membrane. To address this issue, this work proposes a continuous-Donnan effect-model using the Poisson equation coupled with the Nernst-Planck equation to describe variable distributions at the M/E interfaces. A one-dimensional transient VRFB model incorporating the Donnan effect is developed. It is demonstrated that the present model enables (i) a more realistic simulation of continuous distributions of ion concentrations and ionic potential throughout the membrane and (ii) a more comprehensive estimation for the effect of the fixed charge concentration on species crossover across the membrane and cell performance.

Effect of degree of sulfonation and casting solvent on sulfonated poly(ether ether ketone) membrane for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Xi, Jingyu; Li, Zhaohua; Yu, Lihong; Yin, Bibo; Wang, Lei; Liu, Le; Qiu, Xinping; Chen, Liquan

2015-07-01

The properties of sulfonated poly(ether ether ketone) (SPEEK) membranes with various degree of sulfonation (DS) and casting solvent are investigated for vanadium redox flow battery (VRFB). The optimum DS of SPEEK membrane is firstly confirmed by various characterizations such as physicochemical properties, ion selectivity, and VRFB single-cell performance. Subsequently the optimum casting solvent is selected for the optimum DS SPEEK membrane within N,N‧-dimethylformamide (DMF), N,N‧-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and dimethylsulfoxide (DMSO). The different performance of SPEEK membranes prepared with various casting solvents can be attributed to the different interaction between solvent and -SO3H group of SPEEK. In the VRFB single-cell test, the optimum SPEEK membrane with DS of 67% and casting solvent of DMF (S67-DMF membrane) exhibits higher VRFB efficiencies and better cycle-life performance at 80 mA cm-2. The investigation of various DS and casting solvent will be effective guidance on the selection and modification of SPEEK membrane towards VRFB application.

Hydrogen-Treated Rutile TiO2 Shell in Graphite-Core Structure as a Negative Electrode for High-Performance Vanadium Redox Flow Batteries.

PubMed

Vázquez-Galván, Javier; Flox, Cristina; Fàbrega, Cristian; Ventosa, Edgar; Parra, Andres; Andreu, Teresa; Morante, Joan Ramón

2017-05-09

Hydrogen-treated TiO 2 as an electrocatalyst has shown to boost the capacity of high-performance all-vanadium redox flow batteries (VRFBs) as a simple and eco-friendly strategy. The graphite felt-based GF@TiO 2 :H electrode is able to inhibit the hydrogen evolution reaction (HER), which is a critical barrier for operating at high rate for long-term cycling in VRFBs. Significant improvements in charge/discharge and electron-transfer processes for the V 3+ /V 2+ reaction on the surface of reduced TiO 2 were achieved as a consequence of the formation of oxygen functional groups and oxygen vacancies in the lattice structure. Key performance indicators of VRFB have been improved, such as high capability rates and electrolyte-utilization ratios (82 % at 200 mA cm -2 ). Additionally, high coulombic efficiencies (ca. 100 % up to the 96th cycle, afterwards >97 %) were obtained, demonstrating the feasibility of achieving long-term stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High surface area bio-waste based carbon as a superior electrode for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Maharjan, Makhan; Bhattarai, Arjun; Ulaganathan, Mani; Wai, Nyunt; Oo, Moe Ohnmar; Wang, Jing-Yuan; Lim, Tuti Mariana

2017-09-01

Activated carbon (AC) with high surface area (1901 m2 g-1) is synthesized from low cost bio-waste orange (Citrus sinensis) peel for vanadium redox flow battery (VRB). The composition, structure and electrochemical properties of orange peel derived AC (OP-AC) are characterized by elemental analyzer, field emission-scanning electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy. CV results show that OP-AC coated bipolar plate demonstrates improved electro-catalytic activity in both positive and negative side redox couples than the pristine bipolar plate electrode and this is ascribed to the high surface area of OP-AC which provides effective electrode area and better contact between the porous electrode and bipolar plate. Consequently, the performance of VRB in a static cell shows higher energy efficiency for OP-AC electrode than the pristine electrode at all current densities tested. The results suggest the OP-AC to be a promising electrode for VRB applications and can be incorporated into making conducting plastics electrode to lower the VRB cell stack weight and cost.

A novel branched side-chain-type sulfonated polyimide membrane with flexible sulfoalkyl pendants and trifluoromethyl groups for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Li, Jinchao; Liu, Suqin; He, Zhen; Zhou, Zhi

2017-04-01

A novel branched side-chain-type sulfonated polyimide (6F-s-bSPI) membrane with accessible branching agents of melamine, hydrophobic trifluoromethyl groups (sbnd CF3), and flexible sulfoalkyl pendants is prepared by a high-temperature polycondensation and post-sulfonation method for use in vanadium redox flow batteries (VRFBs). The chemical structure of the 6F-s-bSPI membrane is confirmed by ATR-FTIR and 1H NMR spectra. The physico-chemical properties of the as-prepared 6F-s-bSPI membrane are systematically investigated and found to be strongly related to the specially designed structure. The 6F-s-bSPI membrane offers a reduced cost and possesses a significantly lowered vanadium ion permeability (1.18 × 10-7 cm2 min-1) compared to the linear SPI (2.25 × 10-7 cm2 min-1) and commercial Nafion 115 (1.36 × 10-6 cm2 min-1) membranes, prolonging the self-discharge duration of the VRFBs. In addition, the VRFB assembled with a 6F-s-bSPI membrane shows higher coulombic (98.3%-99.7%) and energy efficiencies (88.4%-66.12%) than that with a SPI or Nafion 115 membrane under current densities ranging from 20 to 100 mA cm-2. Moreover, the VRFB with a 6F-s-bSPI membrane delivers a stable cycling performance over 100 cycles with no decline in coulombic and energy efficiencies. These results show that the branched side-chain-type structure is a promising design to prepare excellent proton conductive membranes.

Changes in lung function after exposure to vanadium compounds in fuel oil ash

PubMed Central

Lees, R E M

1980-01-01

ABSTRACT Seventeen men were studied during the cleaning of bottom ash from the boiler of an oil-fired electricity generating station. The men were exposed to a time weighted average respirable dust (<10 μ) of 523 μg/m3, containing 15·3% vanadium. Sixteen of the men wore respirators, subsequently found to have peak leakages of up to 9%, while one volunteer had a one-hour exposure wearing only a compressed paper oronasal mask. Symptoms experienced by the men were recorded, urine samples were collected for assessment of vanadium concentration 24 hours after the first exposure, and spirometry was performed daily for four days and on the eight day. Pronounced reductions in forced vital capacity (mean 0·5 l), forced expiratory volume (mean 0·5 l), and forced mid-expiratory flow (mean 1·16 l/s) had occurred within 24 hours of first exposure to the dust, and had not returned to pre-exposure levels by the eight day. Four weeks after exposure no residual deficits were present. A urinary vanadium concentration of 280 μg/l was found in the volunteer, but none of the others had concentrations above the test-threshold of 40 μg/l. Symptoms and signs of airway irritation were noted. The timing, duration, and quality of changes in lung function, however, indicated that the response could not be attributed solely to a reflex bronchial reaction to irritation by an inert dust. PMID:7426476

Memory Deficit Recovery after Chronic Vanadium Exposure in Mice

PubMed Central

Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

2016-01-01

Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal. PMID:26962395

Memory Deficit Recovery after Chronic Vanadium Exposure in Mice.

PubMed

Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

2016-01-01

Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal.

Assessment of total and organic vanadium levels and their bioaccumulation in edible sea cucumbers: tissues distribution, inter-species-specific, locational differences and seasonal variations.

PubMed

Liu, Yanjun; Zhou, Qingxin; Xu, Jie; Xue, Yong; Liu, Xiaofang; Wang, Jingfeng; Xue, Changhu

2016-02-01

The objective of this study is to investigate the levels, inter-species-specific, locational differences and seasonal variations of vanadium in sea cucumbers and to validate further several potential factors controlling the distribution of metals in sea cucumbers. Vanadium levels were evaluated in samples of edible sea cucumbers and were demonstrated exhibit differences in different seasons, species and sampling sites. High vanadium concentrations were measured in the sea cucumbers, and all of the vanadium detected was in an organic form. Mean vanadium concentrations were considerably higher in the blood (sea cucumber) than in the other studied tissues. The highest concentration of vanadium (2.56 μg g(-1)), as well as a higher degree of organic vanadium (85.5 %), was observed in the Holothuria scabra samples compared with all other samples. Vanadium levels in Apostichopus japonicus from Bohai Bay and Yellow Sea have marked seasonal variations. Average values of 1.09 μg g(-1) of total vanadium and 0.79 μg g(-1) of organic vanadium were obtained in various species of sea cucumbers. Significant positive correlations between vanadium in the seawater and V org in the sea cucumber (r = 81.67 %, p = 0.00), as well as between vanadium in the sediment and V org in the sea cucumber (r = 77.98 %, p = 0.00), were observed. Vanadium concentrations depend on the seasons (salinity, temperature), species, sampling sites and seawater environment (seawater, sediment). Given the adverse toxicological effects of inorganic vanadium and positive roles in controlling the development of diabetes in humans, a regular monitoring programme of vanadium content in edible sea cucumbers can be recommended.

Leaching characteristics of vanadium in mine tailings and soils near a vanadium titanomagnetite mining site.

PubMed

Yang, Jinyan; Tang, Ya; Yang, Kai; Rouff, Ashaki A; Elzinga, Evert J; Huang, Jen-How

2014-01-15

A series of column leaching experiments were performed to understand the leaching behaviour and the potential environmental risk of vanadium in a Panzhihua soil and vanadium titanomagnetite mine tailings. Results from sequential extraction experiments indicated that the mobility of vanadium in both the soil and the mine tailings was low, with <1% of the total vanadium readily mobilised. Column experiments revealed that only <0.1% of vanadium in the soil and mine tailing was leachable. The vanadium concentrations in the soil leachates did not vary considerably, but decreased with the leachate volume in the mine tailing leachates. This suggests that there was a smaller pool of leachable vanadium in the mine tailings compared to that in the soil. Drought and rewetting increased the vanadium concentrations in the soil and mine tailing leachates from 20μgL(-1) to 50-90μgL(-1), indicating the potential for high vanadium release following periods of drought. Experiments with soil columns overlain with 4, 8 and 20% volume mine tailings/volume soil exhibited very similar vanadium leaching behaviour. These results suggest that the transport of vanadium to the subsurface is controlled primarily by the leaching processes occurring in soils. Copyright © 2013 Elsevier B.V. All rights reserved.

Direct growth of vanadium nitride nanosheets on carbon nanotube fibers as novel negative electrodes for high-energy-density wearable fiber-shaped asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Guo, Jiabin; Zhang, Qichong; Sun, Juan; Li, Chaowei; Zhao, Jingxin; Zhou, Zhenyu; He, Bing; Wang, Xiaona; Man, Ping; Li, Qiulong; Zhang, Jun; Xie, Liyan; Li, Mingxing; Yao, Yagang

2018-04-01

Significant efforts have been recently devoted to constructing high-performance fiber-shaped asymmetric supercapacitors. However, it is still a paramount challenge to develop high-energy-density fiber-shaped asymmetric supercapacitors for practical applications in portable and wearable electronics. This work reports a simple and efficient method to directly grow vanadium nitride nanosheets on carbon nanotube fibers as advanced negative electrodes with a high specific capacitance of 188 F/cm3 (564 mF/cm2). Taking advantage of their attractive structure, we successfully fabricated a fiber-shaped asymmetric supercapacitor device with a maximum operating voltage of 1.6 V by assembling the vanadium nitride/carbon nanotube fiber negative electrode with the Zinc-Nickel-Cobalt ternary oxides nanowire arrays positive electrode. Due to the excellent synergistic effects between positive and negative electrodes, a remarkable specific capacitance of 50 F/cm3 (150 mF/cm2) and an outstanding energy density of 17.78 mWh/cm3 (53.33 μWh/cm2) for our fiber-shaped asymmetric supercapacitor can be achieved. Furthermore, the as-assembled fiber-shaped asymmetric supercapacitor device has excellent mechanical flexibility in that 91% of the capacitance retained after bending 90° for 3000 times. Thus, this work exploits a pathway to construct high-energy-density fiber-shaped asymmetric supercapacitor for next-generation portable and wearable electronics.

Mixed addenda polyoxometalate "solutions" for stationary energy storage.

PubMed

Pratt, Harry D; Anderson, Travis M

2013-11-28

A series of redox flow batteries utilizing mixed addenda (vanadium and tungsten), phosphorus-based polyoxometalates (A-α-PV3W9O40(6-), B-α-PV3W9O40(6-), and P2V3W15O62(9-)) were prepared and tested. Cyclic voltammetry and bulk electrolysis experiments on the Keggin compounds (A-α-PV3W9O40(6-) and B-α-PV3W9O40(6-)) established that the vanadium centers of these compounds could be used as the positive electrode (PV(IV)3W(VI)9O40(9-)/PV(V)3W(VI)9O40(6-)), and the tungsten centers could be used as the negative electrode (PV(IV)3W(VI)9O40(9-)/PV(IV)3W(V)3W(VI)6O40(12-)) since these electrochemical processes are separated by about 1 V. The results showed that A-α-PV3W9O40(6-) (where A indicates adjacent, corner-sharing vanadium atoms) had coulombic efficiencies (charge in divided by charge out) above 80%, while the coulombic efficiency of B-α-PV3W9O40(6-) (where B indicates adjacent edge-sharing vanadium atoms) fluctuated between 50% and 70% during cycling. The electrochemical yield, a measurement of the actual charge or discharge observed in comparison with the theoretical charge, was between 40% and 50% for A-α-PV3W9O40(6-), and (31)P NMR showed small amounts of PV2W10O40(5-) and PVW11O40(4-) formed with cycling. The electrochemical yield for B-α-PV3W9O40(6-) decreased from 90% to around 60% due to precipitation of the compound on the electrode, but there were no decomposition products detected in the solution by (31)P NMR, and infrared data on the electrode suggested that the cluster remained intact. Testing of P2V3W15O62(9-) (Wells-Dawson structure) suggested higher charge density clusters were not as suitable as the Keggin structures for a redox flow battery due to the poor stability and inaccessibility of the highly reduced materials.

[Oxidative Stress Level of Vanadium-exposed Workers].

PubMed

Wei, Teng-da; Li, Shun-pin; Liu, Yun-xing; Tan, Chun-ping; Li, Juan; Zhang, Zu-hui; Lan, Ya-jia; Zhang, Qin

2015-11-01

To determine the oxidative stress level in peripheral blood of vanadium-exposed workers, as an indication of population health effect of vanadium on human neurobehavioral system. 86 vanadium-exposed workers and 65 non-exposed workers were recruited by cluster sampling. A questionnaire was administered to collect demographic and occupational exposure information. Serum activity of superoxide dismutase (SOD), inducible nitric oxide synthase (iNOS) and malonaldehyde (MDA) contents were detected by kit assay. The differences in oxidative stress level between vanadium-exposed and non-exposed workers were compared. Vanadium-exposed workers had higher levels of MDA contents than the controls. The total superoxide dismutase(T-SOD) activity in vanadium-exposed workers was significantly lower than that in the controls, which was associated with lowered levels of manganese superoxide dismutase (Mn-SOD) activity. No changes in serum levels of cupro-zinc superoxide dismutase (CuZn-SOD) was found in vanadium-exposed workers. No difference in iNOS activity was found between vanadium-exposed workers and controls. Vanadium exposure increases free radical production in serum and reduces antioxidant capacity. But the relationship between vanadium exposure and iNOS damage remains uncertain.

The presence of vanadium in groundwater of southeastern extreme the pampean region Argentina Relationship with other chemical elements.

PubMed

Fiorentino, Carmen E; Paoloni, Juan D; Sequeira, Mario E; Arosteguy, Pedro

2007-08-15

Changes in the quality of groundwater resources are related to the presence and concentration of contaminants, especially trace elements such as arsenic, boron, fluoride and vanadium. Vanadium is a rare element naturally abundant, generally found in combination with other elements. Vanadium pentoxide is known to have aneugenic effects. Thus, a study was carried out to assess the presence of vanadium in the groundwater of the southeastern pampean region of Argentina, which constitutes the main water supply for the local population. Statistical and correlational analyses were applied to identify possible interrelationships between vanadium and another chemical elements. Vanadium was found in all groundwater samples. The minimum and maximum vanadium concentrations found were 0.05 mg/l and 2.47 mg/l, respectively. Vanadium is significantly correlated with other trace elements such as arsenic, fluoride and boron. The interrelationship between vanadium and the presence of volcanic glass in sediments is not significant as expected.

Bioaccumulation of Vanadium by Vanadium-Resistant Bacteria Isolated from the Intestine of Ascidia sydneiensis samea.

PubMed

Romaidi; Ueki, Tatsuya

2016-06-01

Isolation of naturally occurring bacterial strains from metal-rich environments has gained popularity due to the growing need for bioremediation technologies. In this study, we found that the vanadium concentration in the intestine of the vanadium-rich ascidian Ascidia sydneiensis samea could reach 0.67 mM, and thus, we isolated vanadium-resistant bacteria from the intestinal contents and determined the ability of each bacterial strain to accumulate vanadium and other heavy metals. Nine strains of vanadium-resistant bacteria were successfully isolated, of which two strains, V-RA-4 and S-RA-6, accumulated vanadium at a higher rate than did the other strains. The maximum vanadium absorption by these bacteria was achieved at pH 3, and intracellular accumulation was the predominant mechanism. Each strain strongly accumulated copper and cobalt ions, but accumulation of nickel and molybdate ions was relatively low. These bacterial strains can be applied to protocols for bioremediation of vanadium and heavy metal toxicity.

Sodium vanadium titanium phosphate electrode for symmetric sodium-ion batteries with high power and long lifespan

PubMed Central

Wang, Dongxue; Bie, Xiaofei; Fu, Qiang; Dixon, Ditty; Bramnik, Natalia; Hu, Yong-Sheng; Fauth, Francois; Wei, Yingjin; Ehrenberg, Helmut; Chen, Gang; Du, Fei

2017-01-01

Sodium-ion batteries operating at ambient temperature hold great promise for use in grid energy storage owing to their significant cost advantages. However, challenges remain in the development of suitable electrode materials to enable long lifespan and high rate capability. Here we report a sodium super-ionic conductor structured electrode, sodium vanadium titanium phosphate, which delivers a high specific capacity of 147 mA h g−1 at a rate of 0.1 C and excellent capacity retentions at high rates. A symmetric sodium-ion full cell demonstrates a superior rate capability with a specific capacity of about 49 mA h g−1 at 20 C rate and ultralong lifetime over 10,000 cycles. Furthermore, in situ synchrotron diffraction and X-ray absorption spectroscopy measurement are carried out to unravel the underlying sodium storage mechanism and charge compensation behaviour. Our results suggest the potential application of symmetric batteries for electrochemical energy storage given the superior rate capability and long cycle life. PMID:28660877

Sodium vanadium titanium phosphate electrode for symmetric sodium-ion batteries with high power and long lifespan.

PubMed

Wang, Dongxue; Bie, Xiaofei; Fu, Qiang; Dixon, Ditty; Bramnik, Natalia; Hu, Yong-Sheng; Fauth, Francois; Wei, Yingjin; Ehrenberg, Helmut; Chen, Gang; Du, Fei

2017-06-29

Sodium-ion batteries operating at ambient temperature hold great promise for use in grid energy storage owing to their significant cost advantages. However, challenges remain in the development of suitable electrode materials to enable long lifespan and high rate capability. Here we report a sodium super-ionic conductor structured electrode, sodium vanadium titanium phosphate, which delivers a high specific capacity of 147 mA h g -1 at a rate of 0.1 C and excellent capacity retentions at high rates. A symmetric sodium-ion full cell demonstrates a superior rate capability with a specific capacity of about 49 mA h g -1 at 20 C rate and ultralong lifetime over 10,000 cycles. Furthermore, in situ synchrotron diffraction and X-ray absorption spectroscopy measurement are carried out to unravel the underlying sodium storage mechanism and charge compensation behaviour. Our results suggest the potential application of symmetric batteries for electrochemical energy storage given the superior rate capability and long cycle life.

Release kinetics of vanadium from vanadium (III, IV and V) oxides: Effect of pH, temperature and oxide dose.

PubMed

Hu, Xingyun; Yue, Yuyan; Peng, Xianjia

2018-05-01

Batch experiments were performed to derive the rate laws for the proton-promoted dissolution of the main vanadium (III, IV and V) oxides at pH 3.1-10.0. The release rates of vanadium are closely related to the aqueous pH, and several obvious differences were observed in the release behavior of vanadium from the dissolution of V 2 O 5 and vanadium(III, IV) oxides. In the first 2hr, the release rates of vanadium from V 2 O 3 were r=1.14·([H + ]) 0.269 at pH 3.0-6.0 and r=0.016·([H + ]) -0.048 at pH 6.0-10.0; the release rates from VO 2 were r=0.362·([H + ]) 0.129 at pH 3.0-6.0 and r=0.017·([H + ]) -0.097 at pH 6.0-10.0; and the release rates from V 2 O 5 were r=0.131·([H + ]) -0.104 at pH 3.1-10.0. The release rates of vanadium from the three oxides increased with increasing temperature, and the effect of temperature was different at pH 3.8, pH 6.0 and pH 7.7. The activation energies of vanadium (III, IV and V) oxides (33.4-87.5kJ/mol) were determined at pH 3.8, pH6.0 and pH 7.7, showing that the release of vanadium from dissolution of vanadium oxides follows a surface-controlled reaction mechanism. The release rates of vanadium increased with increasing vanadium oxides dose, albeit not proportionally. This study, as part of a broader study of the release behavior of vanadium, can help to elucidate the pollution problem of vanadium and to clarify the fate of vanadium in the environment. Copyright © 2017. Published by Elsevier B.V.

Methods for making lithium vanadium oxide electrode materials

DOEpatents

Schutts, Scott M.; Kinney, Robert J.

2000-01-01

A method of making vanadium oxide formulations is presented. In one method of preparing lithium vanadium oxide for use as an electrode material, the method involves: admixing a particulate form of a lithium compound and a particulate form of a vanadium compound; jet milling the particulate admixture of the lithium and vanadium compounds; and heating the jet milled particulate admixture at a temperature below the melting temperature of the admixture to form lithium vanadium oxide.

THE COLORIMETRIC DETERMINATION OF VANADIUM IN NIOBIUM-VANADIUM ALLOYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Articolo, O.J.

1959-06-26

A procedure is described for the analysis of vanadium in niobium-- vanadium alloys in the range >0.1% vanadium with an accuracy of better than 3%. The method was applied to the analysis of niobium alloys in which the nominal per cent vanadium varied between 0.3 to 4.6%. The sample is dissolved in a mixture of nitric and hydrofluoric acid and then evaporated to fumes with sulfuric acid. The niobium is hydrolyzed with sulfurous acid and separated from the vanadium by filtration. Hydrogen peroxide is added to the filtrate to form a reddish brown complex with the vanadium. The optical densitymore » of the resulting solution is obtained at 450 m mu on a model B Beckman spectrophotometer. (auth)« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan

In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm 2.« less

Structure, hydrolysis, and diffusion of aqueous vanadium ions from Car-Parrinello molecular dynamics

NASA Astrophysics Data System (ADS)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2016-09-01

A molecular level understanding of the properties of electroactive vanadium species in aqueous solution is crucial for enhancing the performance of vanadium redox flow batteries. Here, we employ Car-Parrinello molecular dynamics simulations based on density functional theory to investigate the hydration structures, first hydrolysis reaction, and diffusion of aqueous V2+, V3+, VO2+, and VO 2+ ions at 300 K. The results indicate that the first hydration shell of both V2+ and V3+ contains six water molecules, while VO2+ is coordinated to five and VO 2+ to three water ligands. The first acidity constants (pKa) estimated using metadynamics simulations are 2.47, 3.06, and 5.38 for aqueous V3+, VO 2+ , and VO2+, respectively, while V2+ is predicted to be a fairly weak acid in aqueous solution with a pKa value of 6.22. We also show that the presence of chloride ions in the first coordination sphere of the aqueous VO 2+ ion has a significant impact on water hydrolysis leading to a much higher pKa value of 4.8. This should result in a lower propensity of aqueous VO 2+ for oxide precipitation reaction in agreement with experimental observations for chloride-based electrolyte solutions. The computed diffusion coefficients of vanadium species in water at room temperature are found to increase as V 3 + < VO 2 + < V O 2 + < V 2 + and thus correlate with the simulated hydrolysis constants, namely, the higher the pKa value, the greater the diffusion coefficient.

Nanoporous polysulfone membranes via a degradable block copolymer precursor for redox flow batteries

DOE PAGES

Gindt, Brandon P.; Abebe, Daniel G.; Tang, Zhijiang J.; ...

2016-02-16

In this study, nanoporous polysulfone (PSU) membranes were fabricated via post-hydrolysis of polylactide (PLA) from PLA–PSU–PLA triblock copolymer membranes. The PSU scaffold was thermally crosslinked before sacrificing PLA blocks. The resulting nanopore surface was chemically modified with sulfonic acid moieties. The membranes were analyzed and evaluated as separators for vanadium redox flow batteries. Nanoporous PSU membranes prepared by this new method and further chemically modified to a slight degree exhibited unique behavior with respect to their ionic conductivity when exposed to solutions of increasing acid concentration.

DNA damage induction in human cells exposed to vanadium oxides in vitro.

PubMed

Rodríguez-Mercado, Juan J; Mateos-Nava, Rodrigo A; Altamirano-Lozano, Mario A

2011-12-01

Vanadium and vanadium salts cause genotoxicity and elicit variable biological effects depending on several factors. In the present study, we analyzed and compared the DNA damage and repair processes induced by vanadium in three oxidation states. We used human blood leukocytes in vitro and in a single cell gel electrophoresis assay at two pH values. We observed that vanadium(III) trioxide and vanadium(V) pentoxide produced DNA single-strand breaks at all of the concentrations (1, 2, 4, or 8 μg/ml) and treatment times (2, 4, or 6 h) tested. Vanadium(IV) tetraoxide treatment significantly increased DNA damage at all concentrations for 4 or 6 h of treatment but not for 2 h of treatment. The DNA repair kinetics indicated that most of the cells exposed to vanadium III and V for 4 h recovered within the repair incubation time of 90 min; however, those exposed to vanadium(IV) repaired their DNA within 120 min. The data at pH 9 indicated that vanadium(IV) tetraoxide induced DNA double-strand breaks. Our results show that the genotoxic effect of vanadium can be produced by any of its three oxidation states. However, vanadium(IV) induces double-strand breaks, and it is known that these lesions are linked with forming structural chromosomal aberrations. Copyright © 2011 Elsevier Ltd. All rights reserved.

Effects of dietary vanadium in mallard ducks

USGS Publications Warehouse

White, D.H.; Dieter, M.P.

1978-01-01

Adult mallard ducks fed 0, 1, 10, or 100 ppm vanadyl sulfate in the diet were sacrificed after 12 wk on treatment; tissues were analyzed for vanadium. No birds died during the study and body weights did not change. Vanadium accumulated to higher concentrations in the bone and liver than in other tissues. Concentrations in bones of hens were five times those in bones of drakes, suggesting an interaction between vanadium and calcium mobilization in laying hens. Vanadium concentrations in most tissues were significantly correlated and increased with treatment level. Lipid metabolism was altered in laying hens fed 100 ppm vanadium. Very little vanadium accumulated in the eggs of laying hens.

Characterization of Metal-Insulator-Transition (MIT) Phase Change Materials (PCM) for Reconfigurable Components, Circuits, and Systems

DTIC Science & Technology

2013-03-01

materials have been introduced as dopants: Vanadium (V), Chromium (Cr), Manganese (Mn), Lead (Pb), and Iron (Fe) [41, 42, 43, 44]. While these...value reported in literature, 188°C, due to the samples being heated on an open air hot plate in a laminar flow fume hood. The average resistivity of

Vanadium accumulation in carbonaceous rocks: A review of geochemical controls during deposition and diagenesis

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1991-01-01

Published data relevant to the geochemistry of vanadium were used to evaluate processes and conditions that control vanadium accumulation in carbonaceous rocks. Reduction, adsorption, and complexation of dissolved vanadium favor addition of vanadium to sediments rich in organic carbon. Dissolved vanadate (V(V)) species predominate in oxic seawater and are reduced to vanadyl ion (V(IV)) by organic compounds or H2S. Vanadyl ion readily adsorbs to particle surfaces and is added to the sediment as the particles settle. The large vanadium concentrations of rocks deposited in marine as compared to lacustrine environments are the result of the relatively large amount of vanadium provided by circulating ocean water compared to terrestrial runoff. Vanadium-rich carbonaceous rocks typically have high contents of organically bound sulfur and are stratigraphically associated with phosphate-rich units. A correspondence between vanadium content and organically bound sulfur is consistent with high activities of H2S during sediment deposition. Excess H2S exited the sediment into bottom waters and favored reduction of dissolved V(V) to V(IV) or possibly V(III). The stratigraphic association of vanadiferous and phosphatic rocks reflects temporal and spatial shifts in bottom water chemistry from suboxic (phosphate concentrated) to more reducing (euxinic?) conditions that favor vanadium accumulation. During diagenesis some vanadium-organic complexes migrate with petroleum out of carbonaceous rocks, but significant amounts of vanadium are retained in refractory organic matter or clay minerals. As carbon in the rock evolves toward graphite during metamorphism, vanadium is incorporated into silicate minerals. ?? 1991.

Efficient Separation and Extraction of Vanadium and Chromium in High Chromium Vanadium Slag by Selective Two-Stage Roasting-Leaching

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Xu, Yingzhe; Liu, Jiayi; Xue, Xiangxin

2018-06-01

Vanadium and chromium are important rare metals, leading to a focus on high chromium vanadium slag (HCVS) as a potential raw material to extract vanadium and chromium in China. In this work, a novel method based on selective two-stage roasting-leaching was proposed to separate and extract vanadium and chromium efficiently in HCVS. XRD, FT-IR, and SEM were utilized to analyze the phase evolutions and microstructure during the whole process. Calcification roasting, which can calcify vanadium selectively using thermodynamics, was carried out in the first roasting stage to transfer vanadium into acid-soluble vanadate and leave chromium in the leaching residue as (Fe0.6Cr0.4)2O3 after H2SO4 leaching. When HCVS and CaO were mixed in the molar ratio CaO/V2O3 (n(CaO)/n(V2O3)) of 0.5 to 1.25, around 90 pct vanadium and less than 1 pct chromium were extracted in the first leaching liquid, thus achieving the separation of vanadium and chromium. In the second roasting stage, sodium salt, which combines with chromium easily, was added to the first leaching residue to extract chromium and 95.16 pct chromium was extracted under the optimal conditions. The total vanadium and chromium leaching rates were above 95 pct, achieving the efficient separation and extraction of vanadium and chromium. The established method provides a new technique to separate vanadium and chromium during roasting rather than in the liquid form, which is useful for the comprehensive application of HCVS.

Efficient Separation and Extraction of Vanadium and Chromium in High Chromium Vanadium Slag by Selective Two-Stage Roasting-Leaching

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Xu, Yingzhe; Liu, Jiayi; Xue, Xiangxin

2018-04-01

Vanadium and chromium are important rare metals, leading to a focus on high chromium vanadium slag (HCVS) as a potential raw material to extract vanadium and chromium in China. In this work, a novel method based on selective two-stage roasting-leaching was proposed to separate and extract vanadium and chromium efficiently in HCVS. XRD, FT-IR, and SEM were utilized to analyze the phase evolutions and microstructure during the whole process. Calcification roasting, which can calcify vanadium selectively using thermodynamics, was carried out in the first roasting stage to transfer vanadium into acid-soluble vanadate and leave chromium in the leaching residue as (Fe0.6Cr0.4)2O3 after H2SO4 leaching. When HCVS and CaO were mixed in the molar ratio CaO/V2O3 (n(CaO)/n(V2O3)) of 0.5 to 1.25, around 90 pct vanadium and less than 1 pct chromium were extracted in the first leaching liquid, thus achieving the separation of vanadium and chromium. In the second roasting stage, sodium salt, which combines with chromium easily, was added to the first leaching residue to extract chromium and 95.16 pct chromium was extracted under the optimal conditions. The total vanadium and chromium leaching rates were above 95 pct, achieving the efficient separation and extraction of vanadium and chromium. The established method provides a new technique to separate vanadium and chromium during roasting rather than in the liquid form, which is useful for the comprehensive application of HCVS.

Surface properties and graphitization of polyacrylonitrile based fiber electrodes affecting the negative half-cell reaction in vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Langner, J.; Bruns, M.; Dixon, D.; Nefedov, A.; Wöll, Ch.; Scheiba, F.; Ehrenberg, H.; Roth, C.; Melke, J.

2016-07-01

Carbon felt electrodes for vanadium redox flow batteries are obtained by the graphitization of polyacrylonitrile based felts at different temperatures. Subsequently, the surface of the felts is modified via thermal oxidation at various temperatures. A single-cell experiment shows that the voltage efficiency is increased by this treatment. Electrode potentials measured with reference electrode setup show that this voltage efficiency increase is caused mainly by a reduction of the overpotential of the negative half-cell reaction. Consequently, this reaction is investigated further by cyclic voltammetry and the electrode activity is correlated with structural and surface chemical properties of the carbon fibers. By Raman, X-ray photoelectron and near edge X-ray absorption fine structure spectroscopy the role of edge sites and oxygen containing functional groups (OCFs) for the electrochemical activity are elucidated. A significant activity increase is observed in correlation with these two characteristics. The amount of OCFs is correlated with structural defects (e.g. edge sites) of the carbon fibers and therefore decreases with an increasing graphitization degree. Thus, for the same thermal oxidation temperature carbon fibers graphitized at a lower temperature show higher activities than those graphitized at a higher temperature.

Tunable Oxygen Functional Groups as Electrocatalysts on Graphite Felt Surfaces for All-Vanadium Flow Batteries.

PubMed

Estevez, Luis; Reed, David; Nie, Zimin; Schwarz, Ashleigh M; Nandasiri, Manjula I; Kizewski, James P; Wang, Wei; Thomsen, Edwin; Liu, Jun; Zhang, Ji-Guang; Sprenkle, Vincent; Li, Bin

2016-06-22

A dual oxidative approach using O2 plasma followed by treatment with H2 O2 to impart oxygen functional groups onto the surface of a graphite felt electrode. When used as electrodes for an all-vanadium redox flow battery (VRB) system, the energy efficiency of the cell is enhanced by 8.2 % at a current density of 150 mA cm(-2) compared with one oxidized by thermal treatment in air. More importantly, by varying the oxidative techniques, the amount and type of oxygen groups was tailored and their effects were elucidated. It was found that O-C=O groups improve the cells performance whereas the C-O and C=O groups degrade it. The reason for the increased performance was found to be a reduction in the cell overpotential after functionalization of the graphite felt electrode. This work reveals a route for functionalizing carbon electrodes to improve the performance of VRB cells. This approach can lower the cost of VRB cells and pave the way for more commercially viable stationary energy storage systems that can be used for intermittent renewable energy storage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adaptive estimation of state of charge and capacity with online identified battery model for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wei, Zhongbao; Tseng, King Jet; Wai, Nyunt; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2016-11-01

Reliable state estimate depends largely on an accurate battery model. However, the parameters of battery model are time varying with operating condition variation and battery aging. The existing co-estimation methods address the model uncertainty by integrating the online model identification with state estimate and have shown improved accuracy. However, the cross interference may arise from the integrated framework to compromise numerical stability and accuracy. Thus this paper proposes the decoupling of model identification and state estimate to eliminate the possibility of cross interference. The model parameters are online adapted with the recursive least squares (RLS) method, based on which a novel joint estimator based on extended Kalman Filter (EKF) is formulated to estimate the state of charge (SOC) and capacity concurrently. The proposed joint estimator effectively compresses the filter order which leads to substantial improvement in the computational efficiency and numerical stability. Lab scale experiment on vanadium redox flow battery shows that the proposed method is highly authentic with good robustness to varying operating conditions and battery aging. The proposed method is further compared with some existing methods and shown to be superior in terms of accuracy, convergence speed, and computational cost.

Investigation of iron(III) reduction and trace metal interferences in the determination of dissolved iron in seawater using flow injection with luminol chemiluminescence detection.

PubMed

Ussher, Simon J; Milne, Angela; Landing, William M; Attiq-ur-Rehman, Kakar; Séguret, Marie J M; Holland, Toby; Achterberg, Eric P; Nabi, Abdul; Worsfold, Paul J

2009-10-12

A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II)+Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100microM concentrations of sulphite a reduction time of 4h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.

Effect of tea polyphenols on production performance, egg quality, and hepatic antioxidant status of laying hens in vanadium-containing diets.

PubMed

Yuan, Z H; Zhang, K Y; Ding, X M; Luo, Y H; Bai, S P; Zeng, Q F; Wang, J P

2016-07-01

This study was conducted to determine the effect of tea polyphenols (TP) on production performance, egg quality, and hepatic-antioxidant status of laying hens in vanadium-containing diets. A total of 300 Lohman laying hens (67 wk old) were used in a 1 plus 3 × 3 experiment design in which hens were given either a diet without vanadium and TP supplementation (control) or diets supplemented with 5, 10, or 15 mg V/kg and TP (0, 600, 1,000 mg/kg) diets for 8 wk, which included 2 phases: a 5-wk accumulation phase and a 3-wk depletion phase. During the accumulation phase, dietary vanadium addition decreased (linear, P < 0.01) albumen height and Haugh unit (HU), and TP supplementation mitigated (linear effect, P < 0.01) this reduction effect induced by vanadium. Eggshell thickness (linear, P < 0.01), redness (linear and quadratic, P < 0.05), and yellowness (linear and quadratic, P < 0.05) were decreased by vanadium and increased by the effect of TP when a vanadium-containing diet was fed. In the depletion phase, the bleaching effect on eggshells induced by vanadium disappeared one wk after vanadium withdrawal. Eggshell thickness, eggshell strength, albumen height, and HU were lower (P < 0.05) in the 15 mg/kg vanadium group compared with the control diet until 2 wk post vanadium challenge, but hens fed 15 mg/kg vanadium and 600 mg/kg TP showed no difference from the control diet only after 1 wk withdrawal. In the liver, the activity of glutathione S-transferases and glutathione peroxidase was increased (linear, P < 0.01) with the TP addition at 5 wk in the accumulation phase in the vanadium-containing diet; the malondialdehyde content increased (linear effect, P = 0.02) with the addition of vanadium. The results indicate that supplementation of 10 and 15 mg/kg vanadium resulted in reduced albumen quality, bleaching effect on eggshell color, and antioxidant stress in the liver. The effect of TP addition can prevent laying hens from the adverse effect of vanadium on egg quality, liver antioxidant stress and shorten the recovery time. © 2016 Poultry Science Association Inc.

Vanadium distribution in rats and DNA cleavage by vanadyl complex: implication for vanadium toxicity and biological effects.

PubMed Central

Sakurai, H

1994-01-01

Vanadium ion is toxic to animals. However, vanadium is also an agent used for chemoprotection against cancers in animals. To understand both the toxic and beneficial effects we studied vanadium distribution in rats. Accumulation of vanadium in the liver nuclei of rats given low doses of compounds in the +4 or +5 oxidation state was greater than in the liver nuclei of rats given high doses of vanadium compounds or the vanadate (+5 oxidation state) compound. Vanadium was incorporated exclusively in the vanadyl (+4 oxidation state) form. We also investigated the reactions of vanadyl ion and found that incubation of DNA with vanadyl ion and hydrogen peroxide (H2O2) led to intense DNA cleavage. ESR spin trapping demonstrated that hydroxyl radicals are generated during the reactions of vanadyl ion and H2O2. Thus, we propose that the mechanism for vanadium-dependent toxicity and antineoplastic action is due to DNA cleavage by hydroxyl radicals generated in living systems. PMID:7843133

Aqueous vanadium ion dynamics relevant to bioinorganic chemistry: A review.

PubMed

Kustin, Kenneth

2015-06-01

Aqueous solutions of the four highest vanadium oxidation states exhibit four diverse colors, which only hint at the diverse reactions that these ions can undergo. Cationic vanadium ions form complexes with ligands; anionic vanadium ions form complexes with ligands and self-react to form isopolyanions. All vanadium species undergo oxidation-reduction reactions. With a few exceptions, elucidation of the dynamics of these reactions awaited the development of fast reaction techniques before the kinetics of elementary ligation, condensation, reduction, and oxidation of the aqueous vanadium ions could be investigated. As the biological roles played by endogenous and therapeutic vanadium expand, it is appropriate to bring the results of the diverse kinetics studies under one umbrella. To achieve this goal this review presents a systematic examination of elementary aqueous vanadium ion dynamics. Copyright © 2014 Elsevier Inc. All rights reserved.

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

Vanadium Recovery from Oil Fly Ash by Carbon Removal and Roast-Leach Process

NASA Astrophysics Data System (ADS)

Jung, Myungwon; Mishra, Brajendra

2018-02-01

This research mainly focuses on the recovery of vanadium from oil fly ash by carbon removal and the roast-leach process. The oil fly ash contained about 85% unburned carbon and 2.2% vanadium by weight. A vanadium-enriched product was obtained after carbon removal, and the vanadium content of this product was 19% by weight. Next, the vanadium-enriched product was roasted with sodium carbonate to convert vanadium oxides to water-soluble sodium metavanadate. The roasted sample was leached with water at 60°C, and the extraction percentage of vanadium was about 92% by weight. Several analytical techniques, such as inductively coupled plasma atomic emission spectroscopy (ICP-AES), x-ray fluorescence (XRF), and thermogravimetric and differential thermal analysis (TG-DTA), were utilized for sample analyses. Thermodynamic modeling was also conducted with HSC chemistry software to explain the experimental results.

Ion conducting membranes for aqueous flow battery systems.

PubMed

Yuan, Zhizhang; Zhang, Huamin; Li, Xianfeng

2018-06-07

Flow batteries, aqueous flow batteries in particular, are the most promising candidates for stationary energy storage to realize the wide utilization of renewable energy sources. To meet the requirement of large-scale energy storage, there has been a growing interest in aqueous flow batteries, especially in novel redox couples and flow-type systems. However, the development of aqueous flow battery technologies is at an early stage and their performance can be further improved. As a key component of a flow battery, the membrane has a significant effect on battery performance. Currently, the membranes used in aqueous flow battery technologies are very limited. In this feature article, we first cover the application of porous membranes in vanadium flow battery technology, and then the membranes in most recently reported aqueous flow battery systems. Meanwhile, we hope that this feature article will inspire more efforts to design and prepare membranes with outstanding performance and stability, and then accelerate the development of flow batteries for large scale energy storage applications.

Thirty years through vanadium chemistry.

PubMed

Costa Pessoa, J

2015-06-01

The relevance of vanadium in biological systems is known for many years and vanadium-based catalysts have important industrial applications, however, till the beginning of the 80s research on vanadium chemistry and biochemistry did not receive much attention from the scientific community. The understanding of the broad bioinorganic implications resulting from the similarities between phosphate and vanadate(V) and the discovery of vanadium dependent enzymes gave rise to an enormous increase in interest in the chemistry and biological relevance of vanadium. Thereupon the last 30years corresponded to a period of enormous research effort in these fields, as well as in medicinal applications of vanadium and in the development of catalysts for use in fine-chemical synthesis, some of these inspired by enzymatic active sites. Since the 80s my group in collaboration with others made contributions, described throughout this text, namely in the understanding of the speciation of vanadium compounds in aqueous solution and in biological fluids, and to the transport of vanadium compounds in blood plasma and their uptake by cells. Several new types of vanadium compounds were also synthesized and characterized, with applications either as prospective therapeutic drugs or as homogeneous or heterogenized catalysts for the production of fine chemicals. The developments made are described also considering the international context of the evolution of the knowledge in the chemistry and bioinorganic chemistry of vanadium compounds during the last 30years. This article was compiled based on the Vanadis Award presentation at the 9th International Vanadium Symposium. Copyright © 2015 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, M.; Luo, Qingtao; Lloyd, Ralph

The microstructure of the perfluorinated sulfonic acid proton exchange membranes such as Nafion significantly affects their transport properties and performance in a vanadium redox flow battery (VRB). In this work, Nafion membranes with various equivalent weights (EW) ranging from 1000 to 1500 are prepared and the structure-property-performance relationship is investigated. Nuclear magnetic resonance (NMR) and small-angle X-ray scattering (SAXS) studies revealed their composition and morphology variances, which lead to major differences in key transport properties related to proton conduction and vanadium ion permeation. Their performances are further characterized as VRB membranes. Based on those understanding, a new perfluorosulfonic acid membranemore » is designed with optimal pore geometry and thickness, leading to higher ion selectivity and lower cost compared with the widely used Nafion® 115. Excellent VRB single-cell performance (89.3% energy efficiency at 50mA∙cm-2) was achieved along with a stable cyclical capacity over prolonged cycling.« less

[The vanadium compounds: chemistry, synthesis, insulinomimetic properties].

PubMed

Fedorova, E V; Buriakina, A V; Vorob'eva, N M; Baranova, N I

2014-01-01

The review considers the biological role of vanadium, its participation in various processes in humans and other mammals, and the anti-diabetic effect of its compounds. Vanadium salts have persistent hypoglycemic and antihyperlipidemic effects and reduce the probability of secondary complications in animals with experimental diabetes. The review contains a detailed description of all major synthesized vanadium complexes having antidiabetic activity. Currently, vanadium complexes with organic ligands are more effective and safer than the inorganic salts. Despite the proven efficacy of these compounds as the anti-diabetic agents in animal models, only one organic complex of vanadium is currently under the second phase of clinical trials. All of the considered data suggest that vanadium compound are a new promising class of drugs in modern pharmacotherapy of diabetes.

Bioleaching of vanadium from barren stone coal and its effect on the transition of vanadium speciation and mineral phase

NASA Astrophysics Data System (ADS)

Wang, Xin; Lin, Hai; Dong, Ying-bo; Li, Gan-yu

2018-03-01

This study determined the optimal conditions required to obtain maximum vanadium extraction and examined the transition of mineral phases and vanadium speciation during the bioleaching process. Parameters including the initial pH value, initial Fe2+ concentration, solid load, and inoculum quantity were examined. The results revealed that 48.92wt% of the vanadium was extracted through bioleaching under optimal conditions. Comparatively, the chemical leaching yield (H2SO4, pH 2.0) showed a slower and milder increase in vanadium yield. The vanadium bioleaching yield was 35.11wt% greater than the chemical leaching yield. The Community Bureau of Reference (BCR) sequential extraction results revealed that 88.62wt% of vanadium existed in the residual fraction. The bacteria substantially changed the distribution of the vanadium speciation during the leaching process, and the residual fraction decreased to 48.44wt%. The X-ray diffraction (XRD) and Fourier transform infrared (FTIR) results provided evidence that the crystal lattice structure of muscovite was destroyed by the bacteria.

Why Antidiabetic Vanadium Complexes are Not in the Pipeline of "Big Pharma" Drug Research? A Critical Review.

PubMed

Scior, Thomas; Guevara-Garcia, Jose Antonio; Do, Quoc-Tuan; Bernard, Philippe; Laufer, Stefan

2016-01-01

Public academic research sites, private institutions as well as small companies have made substantial contributions to the ongoing development of antidiabetic vanadium compounds. But why is this endeavor not echoed by the globally operating pharmaceutical companies, also known as "Big Pharma"? Intriguingly, today's clinical practice is in great need to improve or replace insulin treatment against Diabetes Mellitus (DM). Insulin is the mainstay therapeutically and economically. So, why do those companies develop potential antidiabetic drug candidates without vanadium (vanadium- free)? We gathered information about physicochemical and pharmacological properties of known vanadium-containing antidiabetic compounds from the specialized literature, and converted the data into explanations (arguments, the "pros and cons") about the underpinnings of antidiabetic vanadium. Some discoveries were embedded in chronological order while seminal reviews of the last decade about the Medicinal chemistry of vanadium and its history were also listed for further understanding. In particular, the concepts of so-called "noncomplexed or free" vanadium species (i.e. inorganic oxido-coordinated species) and "biogenic speciation" of antidiabetic vanadium complexes were found critical and subsequently documented in more details to answer the question.

Physiological and anthocyanin biosynthesis genes response induced by vanadium stress in mustard genotypes with distinct photosynthetic activity.

PubMed

Imtiaz, Muhammad; Mushtaq, Muhammad Adnan; Nawaz, Muhammad Amjad; Ashraf, Muhammad; Rizwan, Muhammad Shahid; Mehmood, Sajid; Aziz, Omar; Rizwan, Muhammad; Virk, Muhammad Safiullah; Shakeel, Qaiser; Ijaz, Raina; Androutsopoulos, Vasilis P; Tsatsakis, Aristides M; Coleman, Michael D

2018-06-13

The present study aimed to elucidate the photosynthetic performance, antioxidant enzyme activities, anthocyanin contents, anthocyanin biosynthetic gene expression, and vanadium uptake in mustard genotypes (purple and green) that differ in photosynthetic capacity under vanadium stress. The results indicated that vanadium significantly reduced photosynthetic activity in both genotypes. The activities of the antioxidant enzymes were increased significantly in response to vanadium in both genotypes, although the purple exhibited higher. The anthocyanin contents were also reduced under vanadium stress. The anthocyanin biosynthetic genes were highly expressed in the purple genotype, notably the genes TT8, F3H, and MYBL2 under vanadium stress. The results indicate that induction of TT8, F3H, and MYBL2 genes was associated with upregulation of the biosynthetic genes required for higher anthocyanin biosynthesis in purple compared with the green mustard. The roots accumulated higher vanadium than shoots in both mustard genotypes. The results indicate that the purple mustard had higher vanadium tolerance. Copyright © 2018 Elsevier B.V. All rights reserved.

Commercialization of the Chevron FCC vanadium trap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, J.V.; Kuehler, C.W.; Krishna, A.S.

1995-09-01

Vanadium, present to varying degrees in FCC feed, deposits on the catalyst virtually quantitatively in the cracking process. In resid operations, vanadium levels on catalyst can reach 10,000 ppm at typical catalyst make-up rates. Once on the catalyst, vanadium destroys the zeolite and restricts access to active sites. This reduces catalyst activity. A vanadium trap is a material that when introduced into the catalyst inventory selectively reacts with migrating vanadium, thus protecting the zeolite and other active components of the catalyst. The trap may be incorporated into the catalyst, or introduced as a separate particle. Only a limited amount ofmore » trap can be incorporated into the catalyst without limiting the amount of zeolite that can be included. Gulf began development of a vanadium trap during the early 1980`s. The work produced a variety of promising materials whose use as vanadium traps was subsequently patented. The work ultimately led to a formulation with a phase very active for trapping vanadium while still quite sulfur tolerant. Based on these results, an extensive pilot plant evaluation was undertaken by Chevron after the Chevron-Gulf merger to better simulate commercial operation. The paper describes pilot plant tests as well as 3 commercial tests of this vanadium trap.« less

Spatial distribution of vanadium and microbial community responses in surface soil of Panzhihua mining and smelting area, China.

PubMed

Cao, Xuelong; Diao, Muhe; Zhang, Baogang; Liu, Hui; Wang, Song; Yang, Meng

2017-09-01

Spatial distribution of vanadium in surface soils from different processing stages of vanadium-bearing titanomagnetite in Panzhihua mining and smelting area (China) as well as responses of microbial communities including bacteria and fungi to vanadium were investigated by fieldwork and laboratory incubation experiment. The vanadium contents in this region ranged from 149.3 to 4793.6 mg kg -1 , exceeding the soil background value of vanadium in China (82 mg kg -1 ) largely. High-throughput DNA sequencing results showed bacterial communities from different manufacturing locations were quite diverse, but Bacteroidetes and Proteobacteria were abundant in all samples. The contents of organic matter, available P, available S and vanadium had great influences on the structures of bacterial communities in soils. Bacterial communities converged to similar structure after long-term (240 d) cultivation with vanadium containing medium, dominating by bacteria which can tolerate or reduce toxicities of heavy metals. Fungal diversities decreased after cultivation, but Ascomycota and Ciliophora were still the most abundant phyla as in the original soil samples. Results in this study emphasize the urgency of investigating vanadium contaminations in soils and provide valuable information on how vanadium contamination influences bacterial and fungal communities. Copyright © 2017 Elsevier Ltd. All rights reserved.

Controlled coordination in vanadium(V) dimethylhydrazido compounds.

PubMed

Sakuramoto, Takashi; Moriuchi, Toshiyuki; Hirao, Toshikazu

2016-11-01

The vanadium(V) dimethylhydrazido compounds were structurally characterized to elucidate the effect of the alkoxide ligands in the coordination environment of vanadium(V) hydrazido center. The single-crystal X-ray structure determination of the vanadium(V) dimethylhydrazido compound with isopropoxide ligands revealed a dimeric structure with the V(1)-N(1) distance of 1.680(5)Å, in which each vanadium atom is coordinated in a distorted trigonal-bipyramidal geometry (τ 5 =0.81) with the hydrazido and bridging isopropoxide ligands in the apical positions. On the contrary, nearly tetrahedral arrangement around the vanadium metal center (τ 4 =0.06) with the V(1)-N(1) distance of 1.660(2)Å was observed in the vanadium(V) dimethylhydrazido compound with tert-butoxide ligands. The introduction of the 2,2',2″-nitrilotriethoxide ligand led to a pseudo-trigonal-bipyramidal geometry (τ 5 =0.92) at the vanadium center with the V(1)-N(1) distance of 1.691(5)Å, wherein vanadium atom is pulled out of the plane formed by the nitrilotriethoxide oxygen atoms in the direction of the hydrazido nitrogen. The coordination from the apical ligand in the vanadium(V) dimethylhydrazido compound was found to result in the longer V(1)-N(1) distance. Copyright © 2016 Elsevier Inc. All rights reserved.

The toxicity of vanadium on gastrointestinal, urinary and reproductive system, and its influence on fertility and fetuses malformations.

PubMed

Wilk, Aleksandra; Szypulska-Koziarska, Dagmara; Wiszniewska, Barbara

2017-09-25

Vanadium is a transition metal that has a unique and beneficial effect on both humans and animals. For many years, studies have suggested that vanadium is an essential trace element. Its biological properties are of interest due to its therapeutic potential, including in the treatment of diabetes mellitus. Vanadium deficiencies can lead to a range of pathologies. However, excessive concentration of this metal can cause irreversible damage to various tissues and organs. Vanadium toxicity mainly manifests in gastrointestinal symptoms, including diarrhea, vomiting, and weight reduction. Vanadium also exhibits hepatotoxic and nephrotoxic properties, including glomerulonephritis and pyelonephritis. Vanadium compounds may also lead to partial degeneration of the seminiferous epithelium of the seminiferous tubules in the testes and can affect male fertility. This paper describes the harmful effects of vanadium on the morphology and physiology of both animal and human tissues, including the digestive system, the urinary tract, and the reproductive system. What is more, the following study includes data concerning the correlation between the above-mentioned metal and its influence on fertility and fetus malformations. Additionally, this research identifies the doses of vanadium which lead to pathological alterations becoming visible within tissues. Moreover, this study includes information about the protective efficacy of some substances in view of the toxicity of vanadium.

Study of flow behavior in all-vanadium redox flow battery using spatially resolved voltage distribution

NASA Astrophysics Data System (ADS)

Bhattarai, Arjun; Wai, Nyunt; Schweiss, Rüdiger; Whitehead, Adam; Scherer, Günther G.; Ghimire, Purna C.; Nguyen, Tam D.; Hng, Huey Hoon

2017-08-01

Uniform flow distribution through the porous electrodes in a flow battery cell is very important for reducing Ohmic and mass transport polarization. A segmented cell approach can be used to obtain in-situ information on flow behaviour, through the local voltage or current mapping. Lateral flow of current within the thick felts in the flow battery can hamper the interpretation of the data. In this study, a new method of segmenting a conventional flow cell is introduced, which for the first time, splits up both the porous felt as well as the current collector. This dual segmentation results in higher resolution and distinct separation of voltages between flow inlet to outlet. To study the flow behavior for an undivided felt, monitoring the OCV is found to be a reliable method, instead of voltage or current mapping during charging and discharging. Our approach to segmentation is simple and applicable to any size of the cell.

Assessment of Dephosphorization During Vanadium Extraction Process in Converter

NASA Astrophysics Data System (ADS)

Chen, Lian; Diao, Jiang; Wang, Guang; Xie, Bing

2018-06-01

Dephosphorization during the vanadium extraction process in the converter was studied. The effects of the slag basicity and FeO content on the dephosphorization and the mineral phases in the phosphorus-containing vanadium slag are discussed. The results show that removal of phosphorus from the hot metal during the vanadium extraction process can be achieved by adding lime into the vanadium extraction converter. The highest dephosphorization rate was obtained at slag basicity of 1.93. The phosphorus distribution ratio increased with increasing FeO content up to 16-18% but decreased thereafter. Vanadium was present in the slag only as spinels rather than calcium vanadate. Phosphorus was still present in the form of calcium phosphate eutectic in calcium silicate. The present work proves that the vanadium extraction and dephosphorization processes are nonconflicting reactions.

Synthesis, Characterization, Antioxidant Status, and Toxicity Study of Vanadium-Rutin Complex in Balb/c Mice.

PubMed

Roy, Souvik; Majumdar, Sumana; Singh, Amit Kumar; Ghosh, Balaram; Ghosh, Nilanjan; Manna, Subhadip; Chakraborty, Tania; Mallick, Sougato

2015-08-01

A new trend was developed for the formation of a complex between vanadium and flavonoid derivatives in order to increase the intestinal absorption and to reduce the toxicity of vanadium compounds. The vanadium-rutin complex was characterized by several spectroscopic techniques like ultraviolet (UV)-visible, Fourier transform infrared (FTIR), NMR, mass spectrometry, and microscopic evaluation by scanning electron microscopy. The mononuclear complex was formed by the interaction between vanadium and rutin with 1:2 metal to ligand stoichiometry. Antioxidant activity of the complex was evaluated by 1,1-diphenyl-2 picrylhydrazyl, ferric-reducing power, and 2,2'-azin-obis 3-ethylbenzothiazoline-6-sulphonic acid methods. It was shown that radical scavenging activity and ferric-reducing potential of free rutin was lower as compared with vanadium-rutin complex. The study was also investigated for oral acute toxicity and 28 days repeated oral subacute toxicity study of vanadium-rutin complex in balb/c mice. The vanadium-rutin complex showed mortality at a dose of 120 mg/kg in the balb/c mice. In 28 days repeated oral toxicity study, vanadium-rutin complex was administered to both sex of balb/c mice at dose levels of 90, 45, and 20 ppm, respectively. In addition, subacute toxicity study of vanadium-rutin complex (at 90 ppm dose level) showed increase levels of white blood cell (WBC), total bilirubin, alanine aminotransferase (ALT), alkaline phosphatase (ALP), aspartate aminotransferase (AST), creatinine, and blood urea nitrogen and decrease level of total protein (TP) as compared with control group. Histopathological study of vanadium-rutin showed structural alteration in the liver, kidney, and stomach at 90 ppm dose level. No observed toxic level of vanadium-rutin complex at 20 ppm dose level could be good for further study.

Vanadium exposure-induced striatal learning and memory alterations in rats.

PubMed

Sun, Liping; Wang, Keyue; Li, Yan; Fan, Qiyuan; Zheng, Wei; Li, Hong

2017-09-01

Occupational and environmental exposure to vanadium has been associated with toxicities in reproductive, respiratory, and cardiovascular systems. The knowledge on whether and how vanadium exposure caused neurobehavioral changes remains incomplete. This study was designed to investigate the changes in learning and memory following drinking water exposure to vanadium, and to conduct the preliminary study on underlying mechanisms. Male Sprague-Dawley rats were exposed to vanadium dissolved in drinking water at the concentration of 0.0, 0.5, 1.0 and 2.0g/L, as the control, low-, medium-, and high- dose groups, respectively, for 12 weeks. The results by the Morris water maze test showed that the time for the testing animal to find the platform in the high exposed group was increased by 82.9% and 49.7%, as compared to animals in control and low-dose groups (p<0.05). There were significantly fewer rats in the medium- and high- dose groups than in the control group who were capable of crossing the platform (p<0.05). Quantitation of vanadium by atomic absorption spectrophotometry revealed a significant dose-dependent accumulation of vanadium in striatum (r=0.931, p<0.01). Histopathological examination further demonstrated a degenerative damage in vanadium-exposed striatum. Interestingly, with the increase of the dose of vanadium, the contents of neurotransmitter ACh, 5-HT and GABA in the striatum increased; however, the levels of Syn1 was significantly reduced in the exposed groups compared with controls (p<0.05). These data suggest that vanadium exposure apparently reduces the animals' learning ability. This could be due partly to vanadium's accumulation in striatum and the ensuing toxicity to striatal structure and synaptic plasticity. Further research is warranted for mechanistic understanding of vanadium-induced neurotoxicity. Copyright © 2017 Elsevier B.V. All rights reserved.

Enhanced magnetization in VxFe3-xO4 nanoparticles

NASA Astrophysics Data System (ADS)

Pool, V. L.; Kleb, M. T.; Chorney, C. L.; Arenholz, E.; Idzerda, Y. U.

2015-12-01

Nanoparticles of VxFe3-xO4 with up to 33% vanadium doping (x=0 to 1) and a 9 nm diameter are investigated in order to determine the site preference of the vanadium and the magnetic behavior of the nanoparticles. The iron and vanadium L23-edge X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (MCD) spectra are used to identify that vanadium initially substitutes into the tetrahedral iron site as V3+ and that the average iron moment is observed to increase with vanadium concentration up to 12.5% (x=.375). When the vanadium incorporation exceeds 12.5%, the XAS and MCD show that the vanadium begins substituting as V2+ in the octahedral coordination. This coincides with a rapid reduction of the average moment to zero by 25% (x=.75). The frequency-dependent alternating-current magnetic susceptibility (ACMS) displays a substantial increase in blocking temperature with vanadium concentration and indicated substantial variation in the strength of inter-particle interactions.

Investigation on the fates of vanadium and nickel during co-gasification of petroleum coke with biomass.

PubMed

Li, Jiazhou; Wang, Xiaoyu; Wang, Bing; Zhao, Jiantao; Fang, Yitian

2018-06-01

This study investigates the volatilization behaviors and mineral transformation of vanadium and nickel during co-gasification of petroleum coke with biomass. Moreover, the evolution of occurrence modes of vanadium and nickel was also determined by the method of sequential chemical extraction. The results show that the volatilities of vanadium and nickel in petroleum coke have a certain level of growth with an increase in the temperature. With the addition of biomass, their volatilities both show an obvious decrease. Organic matter and stable forms are the dominant chemical forms of vanadium and nickel. After gasification, organic-bound vanadium and nickel decompose completely and convert into other chemical forms. The crystalline phases of vanadium trioxide, coulsonite, nickel sulfide, and elemental nickel are clearly present in petroleum coke and biomass gasification ashes. When the addition of biomass reaches 60 wt%, the diffraction peaks of orthovanadate are found while that of vanadium trioxide disappear. Copyright © 2018 Elsevier Ltd. All rights reserved.

Comparison of Ultrasound-Assisted and Regular Leaching of Vanadium and Chromium from Roasted High Chromium Vanadium Slag

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Gao, Huiyang; Liu, Yajing; Zheng, Xiaole; Xue, Xiangxin

2018-02-01

Ultrasound-assisted leaching (UAL) was used for vanadium and chromium leaching from roasted material obtained by the calcification roasting of high-chromium-vanadium slag. UAL was compared with regular leaching. The effect of the leaching time and temperature, acid concentration, and liquid-solid ratio on the vanadium and chromium leaching behaviors was investigated. The UAL mechanism was determined from particle-size-distribution and microstructure analyses. UAL decreased the reaction time and leaching temperature significantly. Furthermore, 96.67% vanadium and less than 1% chromium were leached at 60°C for 60 min with 20% H2SO4 at a liquid-solid ratio of 8, which was higher than the maximum vanadium leaching rate of 90.89% obtained using regular leaching at 80°C for 120 min. Ultrasonic waves broke and dispersed the solid sample because of ultrasonic cavitation, which increased the contact area of the roasted sample and the leaching medium, the solid-liquid mass transfer, and the vanadium leaching rate.

Spectrophotometric determination of vanadium in rutile and in mafic igneous rocks

USGS Publications Warehouse

Marinenko, John; Mei, Leung

1974-01-01

Minor and major levels of vanadium in rutile are separated from titanium and iron by sample fusion with sodium carbonate followed by water leach and filtration. The filtrate is then acidified with hydrochloric acid. Silicates are decomposed with a mixture of hydrofluoric and hydrochloric acids, and iron is separated by extraction of its chloride with diethyl ether. Sample vanadium in hydrochloric acid is then quantitatively reduced to vanadium(IV) with sulfurous acid. The remaining sulfur dioxide is expelled by heating. Vanadium (IV) then is reacted with excess of iron(III) at reduced acidity (pH 5) in the presence of 1,10-phenanthroline to yield the orange-red iron(II) 1,10-phenanthroline complex. Iron(II) generated by vanadium(IV) is a measure of total vanadium in the sample. The proposed method is free from elemental interferences because the color development cannot take place without the two redox reactions described above, and these are, under the outlined experimental conditions, quantitative only for vanadium.

High–energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane

PubMed Central

Jia, Chuankun; Pan, Feng; Zhu, Yun Guang; Huang, Qizhao; Lu, Li; Wang, Qing

2015-01-01

Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage. PMID:26702440

High-energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane.

PubMed

Jia, Chuankun; Pan, Feng; Zhu, Yun Guang; Huang, Qizhao; Lu, Li; Wang, Qing

2015-11-01

Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage.

Protective effects of Sesamum indicum extract against oxidative stress induced by vanadium on isolated rat hepatocytes.

PubMed

Hosseini, Mir-Jamal; Shahraki, Jafar; Tafreshian, Saman; Salimi, Ahmad; Kamalinejad, Mohammad; Pourahmad, Jalal

2016-08-01

Vanadium toxicity is a challenging problem to human and animal health with no entirely understanding cytotoxic mechanisms. Previous studies in vanadium toxicity showed involvement of oxidative stress in isolated liver hepatocytes and mitochondria via increasing of ROS formation, release of cytochrome c and ATP depletion after incubation with different concentrations (25-200 µM). Therefore, we aimed to investigate the protective effects of Sesamum indicum seed extract (100-300 μg/mL) against oxidative stress induced by vanadium on isolated rat hepatocytes. Our results showed that quite similar to Alpha-tocopherol (100 µM), different concentrations of extract (100-300 μg/mL) protected the isolated hepatocyte against all oxidative stress/cytotoxicity markers induced by vanadium in including cell lysis, ROS generation, mitochondrial membrane potential decrease and lysosomal membrane damage. Besides, vanadium induced mitochondrial/lysosomal toxic interaction and vanadium reductive activation mediated by glutathione in vanadium toxicity was significantly (P < 0.05) ameliorated by Sesamum indicum extracts. These findings suggested a hepato-protective role for extracts against liver injury resulted from vanadium toxicity. © 2015 Wiley Periodicals, Inc. Environ Toxicol 31: 979-985, 2016. © 2015 Wiley Periodicals, Inc.

Why Antidiabetic Vanadium Complexes are Not in the Pipeline of “Big Pharma” Drug Research? A Critical Review

PubMed Central

Scior, Thomas; Guevara-Garcia, Jose Antonio; Do, Quoc-Tuan; Bernard, Philippe; Laufer, Stefan

2016-01-01

Public academic research sites, private institutions as well as small companies have made substantial contributions to the ongoing development of antidiabetic vanadium compounds. But why is this endeavor not echoed by the globally operating pharmaceutical companies, also known as “Big Pharma”? Intriguingly, today’s clinical practice is in great need to improve or replace insulin treatment against Diabetes Mellitus (DM). Insulin is the mainstay therapeutically and economically. So, why do those companies develop potential antidiabetic drug candidates without vanadium (vanadium-free)? We gathered information about physicochemical and pharmacological properties of known vanadium-containing antidiabetic compounds from the specialized literature, and converted the data into explanations (arguments, the “pros and cons”) about the underpinnings of antidiabetic vanadium. Some discoveries were embedded in chronological order while seminal reviews of the last decade about the Medicinal chemistry of vanadium and its history were also listed for further understanding. In particular, the concepts of so-called “noncomplexed or free” vanadium species (i.e. inorganic oxido-coordinated species) and “biogenic speciation” of antidiabetic vanadium complexes were found critical and subsequently documented in more details to answer the question. PMID:26997154

Investigation of performance and durability of polymer electrolytes for electrochemical energy storage and conversion technologies

NASA Astrophysics Data System (ADS)

Jung, Min-Suk

Polymeric ion exchange membranes are integral components of electrochemical conversion/storage devices such as fuel cells, water electrolyzers, and redox flow batteries. There has been dramatic progress in the research and development of cation exchange membranes (CEM). NafionRTM (perfluorosulfonic acid membranes) is one example of a state-of-the-art CEM and has been successfully demonstrated in various electrochemical energy devices. Unlike CEMs, anion exchange membranes (AEMs) have been of limited utility to date due to their drawbacks, including poor chemical/mechanical stability and low ionic conductivity. However, alkaline environments result in better activity for electrochemical reactions and afford the possibility of using non-platinum group metal (PGM) electrocatalysts. AEMs, therefore, are still being studied in order to resolve existing challenges in terms of conductivity and stability in alkaline media and in strongly oxidizing solutions. In this work, AEMs derived from different types of polymer backbones were prepared, and their chemical stability and electrochemical property were investigated. Polysulfone (PSF) AEMs were prepared by first chloromethylating polysulfone, then by functionalizing chloromethylated polysulfone (CMPSF) with different base reagents. PSF-trimethylamine (TMA) AEMs showed a 40-fold reduction in vanadium (IV) ion (VO2+) permeability when compared to a NafionRTM membrane and exceptional oxidative stability after exposure to a 1.5 M vanadium (V) ion (VO2+) solution for 90 days. PSF-TMA AEMs were successfully demonstrated in the all-vanadium redox flow battery. Excellent energy efficiencies (>75 %) were attained and sustained over 75 charge-discharge cycles for a vanadium redox flow battery prepared using the PSF-TMA separator. Crosslinking of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) AEMs using diamine was tried with intentions to improve the mechanical stability and electrochemical property of PPO AEM. Crosslinked PPO AEMs (30 +/- 4 % at 25 °C) showed less liquid water uptake than non-crosslinked PPO AEMs (46 +/- 5% at 25 °C) while maintaining comparable ionic conductivities (hydroxide ion conductivity of 45 mS/cm at 60 °C). Crosslinked PPO AEMs maintained mechanical integrity and still showed some mechanical stability (ultimate tensile strength of 3˜4 MPa and elongation at break of 13˜17 %) after exposure to 1 M KOH at 60 °C for 14 days, while non-crosslinked PPO AEMs completely lost their mechanical durability. Finally, this dissertation presents research related to perfluorinated AEMs prepared using a Grignard reagent. These membranes exhibited 0.7 mmol/g of Cl- ion exchange capacity (IEC), 20 mS/cm of hydroxide ion conductivity at 20 °C, and 10 % of water uptake at room temperature. The membranes also maintained 90 % of their initial conductivity after an exposure to 1.5 M VO2+ in 3 M H2SO4 solution for seven days.

Enhancing the Performance of Vanadium Redox Flow Batteries using Quinones

NASA Astrophysics Data System (ADS)

Mulcahy, James W., III

The global dependence on fossil fuels continues to increase while the supply diminishes, causing the proliferation in demand for renewable energy sources. Intermittent renewable energy sources such as wind and solar, require electrochemical storage devices in order to transfer stored energy to the power grid at a constant output. Redox flow batteries (RFB) have been studied extensively due to improvements in scalability, cyclability and efficiency over conventional batteries. Vanadium redox flow batteries (VRFB) provide one of the most comprehensive solutions to energy storage in relation to other RFBs by alleviating the problem of cross-contamination. Quinones are a class of organic compounds that have been extensively used in chemistry, biochemistry and pharmacology due to their catalytic properties, fast proton-coupled electron transfer, good chemical stability and low cost. Anthraquinones are a subcategory of quinones and have been utilized in several battery systems. Anthraquinone-2, 6-disulfonic acid (AQDS) was added to a VRFB in order to study its effects on cyclical performance. This study utilized carbon paper electrodes and a Nafion 117 ion exchange membrane for the membrane-electrode assembly (MEA). The cycling performance was investigated over multiple charge and discharge cycles and the addition of AQDS was found to increase capacity efficiency by an average of 7.6% over the standard VRFB, while decreasing the overall cycle duration by approximately 18%. It is thus reported that the addition of AQDS to a VRFB electrolyte has the potential to increase the activity and capacity with minimal increases in costs.

The Influence of Vanadium Microalloying on the Production of Thin Slab Casting and Direct Rolled Steel Strip

NASA Astrophysics Data System (ADS)

Li, Yu; Milbourn, David

Vanadium microalloying is highly effective in high strength strip steels produced by thin slab casting and direct rolled process. Because of the high solubility of V(C,N) in austenite, vanadium is likely to remain in solution during casting, equalisation and rolling. Vanadium microalloyed steels have better hot ductility and are less prone to transverse cracking than niobium containing steels. Despite a coarse as-cast austenite grain size before rolling, significant grain refinement can be achieved in vanadium microalloyed steels by repeated recrystallization during rolling, resulting in a fine uniform ferrite microstructure in final strip. Almost all vanadium present in microalloyed steels is available to precipitate in ferrite as very fine particles, contributing to precipitation strengthening. Vanadium microalloyed steels show less sensitivity to rolling process variables and exhibit excellent combination of strength and toughness.

Photo-driven nanoactuators based on carbon nanocoils and vanadium dioxide bimorphs.

PubMed

Ma, He; Zhang, Xinping; Cui, Ruixue; Liu, Feifei; Wang, Meng; Huang, Cuiying; Hou, Jiwei; Wang, Guang; Wei, Yang; Jiang, Kaili; Pan, Lujun; Liu, Kai

2018-06-06

Photo-driven actuators are highly desirable in various smart systems owing to the advantages of wireless control and possible actuation by solar energy. Miniaturization of photo-driven actuators is particularly essential in micro-robotics and micro-/nano-electro-mechanical systems. However, it remains a great challenge to build up nano-scale photo-driven actuators with competitive performance in amplitude, response speed, and lifetime. In this work, we developed photo-driven nanoactuators based on bimorph structures of vanadium dioxides (VO2) and carbon nanocoils (CNCs). Activated by the huge structural phase transition of VO2, the photo-driven VO2/CNC nanoactuators deliver a giant amplitude, a fast response up to 9400 Hz, and a long lifetime more than 10 000 000 actuation cycles. Both experimental and simulation results show that the helical structure of CNCs enables a low photo-driven threshold of VO2/CNC nanoactuators, which provides an effective method to construct photo-driven nanoactuators with low power consumption. Our photo-driven VO2/CNC nanoactuators would find potential applications in nano-scale electrical/optical switches and other smart devices.

Pharmacokinetics of vanadium in humans after intravenous administration of a vanadium containing albumin solution

PubMed Central

Heinemann, Günter; Fichtl, Burckhard; Vogt, Wolfgang

2003-01-01

Aims Vanadium is currently undergoing clinical trials as an oral drug in patients with noninsulin-dependent diabetes mellitus. Furthermore, vanadium occurs in elevated concentrations in the blood of patients receiving intravenous albumin solutions containing large amounts of the metal ion as an impurity. The present study was performed to examine the pharmacokinetics of vanadium in humans following a single intravenous (i.v.) dose of a commercial albumin solution containing a high amount of vanadium. Methods The study was conducted in five healthy volunteer subjects who received intravenously 90 ml of a commercial 20% albumin infusion solution containing 47.6 µg vanadium as an impurity. Vanadium concentrations in serum and urine were determined by electrothermal atomic absorption spectrometry. Results Vanadium serum concentrations after i.v. administration were measured for 31 days. The data could be fitted by a triexponential function corresponding formally to a three-compartment model. There was an initial rapid decrease in serum concentrations with half-lives of 1.2 and 26 h. This was followed by a long-terminal half-life time of 10 days. The terminal phase accounted for about 80% of the total area under the serum concentration-time curve (AUC). The mean apparent volume of distribution of the central compartment was found to be 10 l. The volume of distribution at steady state was 54 l, and total clearance was 0.15 l h−1. Vanadium was mainly excreted by the kidneys. About 52% of the dose was recovered in the urine after 12 days. Conclusions This study provides data on vanadium pharmacokinetics in healthy humans. PMID:12630973

Effect of vanadium contamination on the framework and micropore structure of ultra stable Y-zeolite.

PubMed

Etim, U J; Xu, B; Ullah, Rooh; Yan, Z

2016-02-01

Y-zeolites are the main component of fluid catalytic cracking (FCC) catalyst for conversion of crude petroleum to products of high demand including transportation fuel. We investigated effects of vanadium which is present as one of the impurities in FCC feedstock on the framework and micropore structure of ultra-stable (US) Y-zeolite. The zeolite samples were prepared and characterized using standard techniques including: (1) X-ray diffraction, (2) N2 adsorption employing non local density functional theory method, NLDFT, (3) Transmittance and Pyridine FTIR, (4) Transmittance electron microscopy (TEM), and (5) (27)Al and (29)Si MAS-NMR. Results revealed that in the presence of steam, vanadium caused excessive evolution of non inter-crystalline mesopores and structural damage. The evolved mesopore size averaged about 25.0nm at 0.5wt.% vanadium loading, far larger than mesopore size in zeolitic materials with improved hydrothermal stability and performance for FCC catalyst. A mechanism of mesopore formation based on accelerated dealumination has been proposed and discussed. Vanadium immobilization experiments conducted to mitigate vanadium migration into the framework clearly showed vanadium is mobile at reaction conditions. From the results, interaction of vanadium with the passivator limits and decreases mobility and activity of vanadium into inner cavities of the zeolite capable of causing huge structure breakdown and acid sites destruction. This study therefore deepens insight into the causes of alteration in activity and selectivity of vanadium contaminated catalyst and hints on a possible mechanism of passivation in vanadium passivated FCC catalyst. Copyright © 2015 Elsevier Inc. All rights reserved.

NREL, American Vanadium Demonstrate First-of-Its-Kind Battery Management

Science.gov Websites

System | Energy Systems Integration Facility | NREL American Vanadium NREL, American Vanadium Demonstrate First-of-Its-Kind Battery Management System NREL researchers are collaborating with American Vanadium, an integrated energy storage company, to evaluate and demonstrate the first North American

76 FR 78888 - Final Results of Expedited Sunset Review: Ferrovanadium and Nitrided Vanadium From Russia

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-20

... Sunset Review: Ferrovanadium and Nitrided Vanadium From Russia AGENCY: Import Administration... and nitrided vanadium from the Russian Federation (Russia), pursuant to section 751(c) of the Tariff... vanadium from Russia, pursuant to section 751(c) of the Act. See Initiation of Five-Year (``Sunset...

77 FR 51825 - Ferrovanadium and Nitrided Vanadium From Russia

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-27

... Nitrided Vanadium From Russia Determination On the basis of the record \\1\\ developed in the subject five... order on ferrovanadium and nitrided vanadium from Russia would not be likely to lead to continuation or... in USITC Publication 4345 (August 2012), entitled Ferrovanadium and Nitrided Vanadium from Russia...

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the vanadium ore...

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the vanadium ore...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... uranium, radium and vanadium ores subcategory. 440.30 Section 440.30 Protection of Environment... SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.30 Applicability; description of the uranium, radium and vanadium ores subcategory. The provisions of this subpart C are applicable to...

Consolidation and fabrication techniques for vanadium-20 w/o titanium /TV-20/

NASA Technical Reports Server (NTRS)

Burt, W. R.; Karasek, F. J.; Kramer, W. C.; Mayfield, R. M.; Mc Gowan, R. D.

1968-01-01

Tests of the mechanical properties, fuel compatibility, sodium corrosion and irradiation behavior were made for vanadium and vanadium alloy. Improved methods for consolidation and fabrication of bar, rod, sheet, and high-quality, small diameter, thin-wall tubing of vanadium-20 without titanium are reported.

Mineralogy and geochemistry of vanadium in the Colorado Plateau

USGS Publications Warehouse

Weeks, A.D.

1961-01-01

The chief domestic source of vanadium is uraniferous sandstone in the Colorado Plateau. Vanadium is 3-, 4-, or 5-valent in nature and, as oxides or combined with other elements, it forms more than 40 minerals in the Plateau ores. These ores have been studied with regard to the relative amounts of vanadium silicates and oxide-vanadates, uranium-vanadium ratios, the progressive oxidation of black low-valent ores to high-valent carnotite-type ores, and theories of origin. ?? 1961.

CATALYTIC PROMOTION OF THE ADSORPTION OF VANADIUM ON AN ANIONIC EXCHANGE RESIN

DOEpatents

Bailes, R.H.; Ellis, D.A.

1958-08-26

An improvement in the process for the recovery of vanadium from acidic phosphatic solutions is presented. In this process the vanadium is first oxidized to the pentavaleat state, and is then separated by contacting such solutions with an anion exchange resin whereby adsorption of the complexed pentavalent vanadium is effected. The improvement lies in the fact that adsorp tion of the vanadium complex by the anion exchange resin is promoted and improved by providing fiuoride ions in solution to be contacted.

Exploring electrolyte preference of vanadium nitride supercapacitor electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Bo; Chen, Zhaohui; Lu, Gang

Highlights: • Hierarchical VN nanostructures were prepared on graphite foam. • Electrolyte preference of VN supercapacitor electrodes was explored. • VN showed better capacitive property in organic and alkaline electrolytes than LiCl. - Abstract: Vanadium nitride hierarchical nanostructures were prepared through an ammonia annealing procedure utilizing vanadium pentoxide nanostructures grown on graphite foam. The electrochemical properties of hierarchical vanadium nitride was tested in aqueous and organic electrolytes. As a result, the vanadium nitride showed better capacitive energy storage property in organic and alkaline electrolytes. This work provides insight into the charge storage process of vanadium nitride and our findings canmore » shed light on other transition metal nitride-based electrochemical energy storage systems.« less

An alternative low-loss stack topology for vanadium redox flow battery: Comparative assessment

NASA Astrophysics Data System (ADS)

Moro, Federico; Trovò, Andrea; Bortolin, Stefano; Del, Davide, , Col; Guarnieri, Massimo

2017-02-01

Two vanadium redox flow battery topologies have been compared. In the conventional series stack, bipolar plates connect cells electrically in series and hydraulically in parallel. The alternative topology consists of cells connected in parallel inside stacks by means of monopolar plates in order to reduce shunt currents along channels and manifolds. Channelled and flat current collectors interposed between cells were considered in both topologies. In order to compute the stack losses, an equivalent circuit model of a VRFB cell was built from a 2D FEM multiphysics numerical model based on Comsol®, accounting for coupled electrical, electrochemical, and charge and mass transport phenomena. Shunt currents were computed inside the cells with 3D FEM models and in the piping and manifolds by means of equivalent circuits solved with Matlab®. Hydraulic losses were computed with analytical models in piping and manifolds and with 3D numerical analyses based on ANSYS Fluent® in the cell porous electrodes. Total losses in the alternative topology resulted one order of magnitude lower than in an equivalent conventional battery. The alternative topology with channelled current collectors exhibits the lowest shunt currents and hydraulic losses, with round-trip efficiency higher by about 10%, as compared to the conventional topology.

Enhanced vanadium redox flow battery performance using graphene nanoplatelets to decorate carbon electrodes

NASA Astrophysics Data System (ADS)

Sankar, Abhinandh; Michos, Ioannis; Dutta, Indrajit; Dong, Junhang; Angelopoulos, Anastasios P.

2018-05-01

Rotating Disk Electrode (RDE) measurements on model glassy carbon (GC) substrates and Cyclic Voltammetry on more practical commercial carbon supports are used to demonstrate that the kinetics of the positive VO2+/VO2+ redox reaction can be substantially enhanced by using electrostatic layer-by-layer assembly (LbL) to decorate their surface with graphene nanoplatelets (GNPs). An exchange current density, i0, is obtained that is more than two orders of magnitude greater than that observed with standard carbon supported Pt nanocatalyst with the deposition of only 20 GNP layers. Tafel slope analysis is compared to electron microscopy imaging to conclude that while faster redox kinetics is associated with an increase in the available active area, the prevalence of smaller GNPs and associated edge sites the can attenuate activity gains with increasing number of layers. Practical implementation to existing Vanadium Redox Flow Battery (VRFB) configurations was demonstrated through the application of a 370 nm (20 layer) LbL GNP coating on carbon felt (CF). The GNP coating yielded a 5% increase relative in voltage and overall efficiency of charge discharge curves obtained under typical VRFB cell operating conditions at 40 mA cm-2. Furthermore, a substantial increase in the discharge time is observed with this GNP coating on CF.

Fabrication of VO2 thin film by rapid thermal annealing in oxygen atmosphere and its metal—insulator phase transition properties

NASA Astrophysics Data System (ADS)

Liang, Ji-Ran; Wu, Mai-Jun; Hu, Ming; Liu, Jian; Zhu, Nai-Wei; Xia, Xiao-Xu; Chen, Hong-Da

2014-07-01

Vanadium dioxide thin films have been fabricated through sputtering vanadium thin films and rapid thermal annealing in oxygen. The microstructure and the metal—insulator transition properties of the vanadium dioxide thin films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and a spectrometer. It is found that the preferred orientation of the vanadium dioxide changes from (1¯11) to (011) with increasing thickness of the vanadium thin film after rapid thermal annealing. The vanadium dioxide thin films exhibit an obvious metal—insulator transition with increasing temperature, and the phase transition temperature decreases as the film thickness increases. The transition shows hysteretic behaviors, and the hysteresis width decreases as the film thickness increases due to the higher concentration carriers resulted from the uncompleted lattice. The fabrication of vanadium dioxide thin films with higher concentration carriers will facilitate the nature study of the metal—insulator transition.

Cellular uptake of titanium and vanadium from addition of salts or fretting corrosion in vitro

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maurer, A.M.; Merritt, K.; Brown, S.A.

1994-02-01

The use of titanium and titanium-6% aluminum-4% vanadium alloy for dental and orthopedic implants has increased in the last decade. The implants are presumed to be compatible because oseointegration, bony apposition, and cell attachment are known. However, the cellular association of titanium and vanadium have remained unknown. This study examined the uptake of salts or fretting corrosion products. Titanium was not observed to be toxic to the cells. Vanadium was toxic at levels greater than 10[mu]g/mL. The percentage of cellular association of titanium was shown to be about 10 times that of vanadium. The percentage of cellular association of eithermore » element was greater from fretting corrosion than from the addition of salts. The presence of vanadium did not affect the cellular uptake of titanium. The presence of titanium decreased the cell association of vanadium.« less

Low-temperature direct synthesis of mesoporous vanadium nitrides for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Lee, Hae-Min; Jeong, Gyoung Hwa; Kim, Sang-Wook; Kim, Chang-Koo

2017-04-01

Mesoporous vanadium nitrides are directly synthesized by a one-step chemical precipitation method at a low temperature (70 °C). Structural and morphological analyses reveal that vanadium nitride consist of long and slender nanowhiskers, and mesopores with diameters of 2-5 nm. Compositional analysis confirms the presence of vanadium in the VN structure, along with oxidized vanadium. The cyclic voltammetry and charge-discharge tests indicate that the obtained material stores charges via a combination of electric double-layer capacitance and pseudocapacitance mechanisms. The vanadium nitride electrode exhibits a specific capacitance of 598 F/g at a current density of 4 A/g. After 5000 charge-discharge cycles, the electrode has an equivalent series resistance of 1.42 Ω and retains 83% of its initial specific capacitance. This direct low-temperature synthesis of mesoporous vanadium nitrides is a simple and promising method to achieve high specific capacitance and low equivalent series resistance for electrochemical capacitor applications.

Vanadium in landscape components of western Transbaikalia

NASA Astrophysics Data System (ADS)

Kashin, V. K.

2017-10-01

Vanadium in soil-forming rocks, soils, and vegetation of forest-steppe, steppe, and dry-steppe landscapes of Transbaikalia has been studied. The mean element contents in rocks and soils are equal to its mean natural abundances (clarke values). The content of vanadium in soils is strictly determined by its content in parent materials; its dependence on the vanadium concentration in plants and on the soil pH and humus is less pronounced. With respect to the coefficient of biological uptake by plants, vanadium is assigned to the group of elements of slight accumulation (0.10-0.33) on mineral soils and of moderate accumulation (1.1-1.5) on peat bog soils. The mean vanadium concentration in steppe, meadow, and cultivated vegetation exceeds the norm for animals by 1.7-2.6 times but does not rich toxic levels. Vanadium uptake by plants is most intensive in meadow cenoses and is less intensive in dry-steppe cenoses.

Vanadium-uranium extraction from Wyoming vanadiferoud silicates. Report of investigations/1983

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayashi, M.; Nichols, I.L.; Huiatt, J.L.

1983-11-01

The Bureau of Mines conducted laboratory studies on low-grade vanadiferous silicates from the Pumpkin Buttes and Nine Mile Lake deposits of Wyoming to examine techniques for extracting vanadium and uranium. Recovery from low-grade sources such as these could contribute to future vanadium production and reduce reliance on vanadium imports.

77 FR 54897 - Ferrovanadium and Nitrided Vanadium from the Russian Federation: Revocation of Antidumping Duty...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-06

... nitrided vanadium from the Russian Federation (Russia) would not be likely to lead to continuation or... the antidumping duty order on ferrovanadium and nitrided vanadium from Russia. \\1\\ See Ferrovanadium and Nitrided Vanadium From Russia, 77 FR 51825 (August 27, 2012) (ITC Final). DATES: Effective Date...

76 FR 69736 - Draft Toxicological Review of Vanadium Pentoxide: In Support of Summary Information on the...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-09

... Toxicological Review of Vanadium Pentoxide: In Support of Summary Information on the Integrated Risk Information..., ``Toxicological Review of Vanadium Pentoxide: In Support of Summary Information on the Integrated Risk Information... Vanadium Pentoxide: In Support of Summary Information on the Integrated Risk Information System (IRIS)'' is...

Essentiality and toxicity of vanadium supplements in health and pathology.

PubMed

Gruzewska, K; Michno, A; Pawelczyk, T; Bielarczyk, H

2014-10-01

The biological properties of vanadium complexes have become an object of interest due to their therapeutic potential in several diseases. However, the mechanisms of action of vanadium salts are still poorly understood. Vanadium complexes are cofactors for several enzymes and also exhibit insulin-mimetic properties. Thus, they are involved in the regulation of glucose metabolism, including in patients with diabetes. In addition, vanadium salts may also normalize blood pressure and play a key role in the metabolism of the thyroid and of iron as well as in the regulation of total cholesterol, cholesterol HDL and triglyceride (TG) levels in blood. Moreover, in cases of hypoxia, vanadium compounds may improve cardiomyocytes function. They may also exhibit both carcinogenic and anti-cancer properties. These include dose- and exposure-time-dependent induction and inhibition of the proliferation and survival of cancer cells. On the other hand, the balance between vanadium's therapeutic properties and its side effects has not yet been determined. Therefore, any studies on the potential use of vanadium compounds as supplements to support the treatment of a number of diseases must be strictly monitored for adverse effects.

Electronic structure of lead telluride-based alloys, doped with vanadium

NASA Astrophysics Data System (ADS)

Skipetrov, E. P.; Golovanov, A. N.; Slynko, E. I.; Slynko, V. E.

2013-01-01

The crystal structure, composition, galvanomagnetic properties in low magnetic fields (4.2 K ≤ T ≤ 300 K, B ≤ 0.07 T), and the Shubnikov-de Haas effect (T = 4.2 K, B ≤ 7 T) are studied in Pb1-x-ySnxVyTe (x = 0, 0.05-0.18) alloys synthesized by the Bridgman technique with variable vanadium impurity concentrations. It is shown that increasing the vanadium content leads to the formation of regions enriched in vanadium and of microscopic inclusions of compounds with compositions close to V3Te4. In Pb1-yVyTe stabilization of the Fermi level by a deep vanadium level, an insulator-metal transition, and a rise in the free electron concentration are observed as the vanadium content is increased. The variation in the free charge carrier concentration with increasing vanadium concentration in Pb1-yVyTe and Pb1-x-ySnxVyTe (x = 0.05-0.18) alloys is compared. Possible models for rearrangement of the electronic structure in Pb1-x-ySnxVyTe alloys with vanadium doping are discussed.

Kinetic model of whole-body vanadium metabolism: studies in sheep

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patterson, B.W.; Hansard, S.L. II; Ammerman, C.B.

1986-08-01

A compartmental model for vanadium metabolism in sheep has been proposed. The model is consistent with data obtained from sheep fed a control diet (2.6 ppm vanadium) containing 0 or 200 ppm supplemental vanadium. Sheep were administered UYV dioxovanadium either orally or intravenously. Blood feces, and urine radioactivity were monitored for 6 days postdosing. Several new insights regarding vanadium metabolism are suggested and tested against the data using the model. Some of these include 1) significant absorption of UYV occurs from the upper gastrointestinal tract; 2) an in vivo process is necessary in order for UYV dioxovanadium to be convertedmore » into a more biologically reactive species; 3) at steady state the upper and lower gastrointestinal tracts contain at least 10- and 100-fold more mass of vanadium, respectively, than does blood. No statistically significant differences in transport rate constants were found between animals receiving 0 and 200 ppm supplemental dietary vanadium. The availability of a model will enable the refinement of future studies regarding vanadium metabolism in the ruminant.« less

Cottonseed meal, dehydrated grass and ascorbic acid as dietary factors preventing toxicity of vanadium for the chick

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, L.R.; Lawrence, W.W.

1971-01-01

Studies have been conducted which show that the replacement of 5% sucrose in a sucrose-fish meal diet for chicks with degossypolized cottonseed meal prevents the toxicity of 20 ppm added vanadium. The addition of 5% dehydrated grass to the same ration markedly reduced the toxicity symptoms. No such reduction in vanadium toxicity resulted when soybean meal, corn gluten meal, meat meal, fish meal, casein, isolated soybean protein, zein or wheat gluten were added to the ration. No evidence was found that the gossypol remaining in the cottonseed meal was the detoxifying agent. The addition of 0.25 to 0.50% ascorbic acidmore » to the sucrose-fish meal basal ration prevented the toxic symptoms resulting from the addition of 20 ppm vanadium derived from HN/sub 4/VO/sub 3/. The vanadium derived from VOSO/sub 4/ and VOCl/sub 2/ (vanadium valence 4) was as toxic as vanadium derived from HN/sub 4/VO/sub 3/ (V = valence 5). This leads one to question that the action of ascorbic acid in reducing vanadium toxicity is through its property of a reducing agent which might change the vanadium in VH/sub 4/VO/sub 3/ to a lower valence, presumably less toxic.« less

Vanadium bioavailability and toxicity to soil microorganisms and plants.

PubMed

Larsson, Maja A; Baken, Stijn; Gustafsson, Jon Petter; Hadialhejazi, Golshid; Smolders, Erik

2013-10-01

Vanadium, V, is a redox-sensitive metal that in solution, under aerobic conditions, prevails as the oxyanion vanadate(V). There is little known regarding vanadium toxicity to soil biota, and the present study was set up to determine the toxicity of added vanadate to soil organisms and to investigate the relationship between toxicity and vanadium sorption in soils. Five soils with contrasting properties were spiked with 7 different doses (3.2-3200 mg V kg(-1)) of dissolved vanadate, and toxicity was measured with 2 microbial and 3 plant assays. The median effective concentration (EC50) thresholds of the microbial assays ranged from 28 mg added V kg(-1) to 690 mg added V kg(-1), and the EC50s in the plant assays ranged from 18 mg added V kg(-1) to 510 mg added V kg(-1). The lower thresholds were in the concentration range of the background vanadium in the untreated control soils (15-58 mg V kg(-1)). The vanadium toxicity to plants decreased with a stronger soil vanadium sorption strength. The EC50 values for plants expressed on a soil solution basis ranged from 0.8 mg V L(-1) to 15 mg V L(-1) and were less variable among soils than corresponding values based on total vanadium in soil. It is concluded that sorption decreases the toxicity of added vanadate and that soil solution vanadium is a more robust measure to determine critical vanadium concentrations across soils. © 2013 SETAC.

Vanadium exposure-induced striatal learning and memory alterations in rats

PubMed Central

Sun, Liping; Wang, Keyue; Li, Yan; Fan, Qiyuan; Zheng, Wei; Li, Hong

2017-01-01

Occupational and environmental exposure to vanadium has been associated with toxicities in reproductive, respiratory, and cardiovascular systems. The knowledge on whether and how vanadium exposure caused neurobehavioral changes remains incomplete. This study was designed to investigate the changes in learning and memory following drinking water exposure to vanadium, and to conduct the preliminary study on underlying mechanisms. Male Sprague-Dawley rats were exposed to vanadium dissolved in drinking water at the concentration of 0.0, 0.5, 1.0 and 2.0 g/L, as the control, low-, medium-, and high- dose groups, respectively, for 12 weeks. The results by the Morris water maze test showed that the time for the testing animal to find the platform in the high exposed group was increased by 82.9% and 49.7%, as compared to animals in control and low-dose groups (p <0.05). There were significantly fewer rats in the medium- and high- dose groups than in the control group who were capable of crossing the platform (p <0.05). Quantitation of vanadium by atomic absorption spectrophotometry revealed a significant dose-dependent accumulation of vanadium in striatum (r = 0.931, p <0.01). Histopathological examination further demonstrated a degenerative damage in vanadium-exposed striatum. Interestingly, with the increase of the dose of vanadium, the contents of neurotransmitter ACh, 5-HT and GABA in the striatum increased; however, the levels of Syn1 was significantly reduced in the exposed groups compared with controls (p <0.05). These data suggest that vanadium exposure apparently reduces the animals’ learning ability. This could be due partly to vanadium’s accumulation in striatum and the ensuing toxicity to striatal structure and synaptic plasticity. Further research is warranted for mechanistic understanding of vanadium-induced neurotoxicity. PMID:28625925

Influence of vanadium on serum lipid and lipoprotein profiles: a population-based study among vanadium exposed workers

PubMed Central

2014-01-01

Background Some experimental animal studies reported that vanadium had beneficial effects on blood total cholesterol (TC) and triglyceride (TG). However, the relationship between vanadium exposure and lipid, lipoprotein profiles in human subjects remains uncertain. This study aimed to compare the serum lipid and lipoprotein profiles of occupational vanadium exposed and non-exposed workers, and to provide human evidence on serum lipid, lipoprotein profiles and atherogenic indexes changes in relation to vanadium exposure. Methods This cross-sectional study recruited 533 vanadium exposed workers and 241 non-exposed workers from a Steel and Iron Group in Sichuan, China. Demographic characteristics and occupational information were collected through questionnaires. Serum lipid and lipoprotein levels were measured for all participants. The ratios of total cholesterol to high-density lipoprotein cholesterol (HDL-C), low-density lipoprotein cholesterol (LDL-C) to HDL-C and apoB to apoA-I were used as atherogenic indexes. A general linear model was applied to compare outcomes of the two groups while controlling possible confounders and multivariate logistic regression was performed to evaluate the relationship between low HDL-C level, abnormal atherogenic index and vanadium exposure. Results Higher levels of HDL-C and apoA-I could be observed in the vanadium exposed group compared with the control group (P < 0.05). Furthermore, atherogenic indexes (TC/HDL-C, LDL-C/HDL-C, and apoB/apoA-I ratios) were found statistically lower in the vanadium exposed workers (P < 0.05). Changes in HDL-C, TC/HDL-C, and LDL-C/HDL-C were more pronounced in male workers than that in female workers. In male workers, after adjusting for potential confounding variables as age, habits of smoking and drinking, occupational vanadium exposure was still associated with lower HDL-C (OR 0.41; 95% CI, 0.27-0.62) and abnormal atherogenic index (OR 0.38; 95% CI, 0.20-0.70). Conclusion Occupational vanadium exposure appears to be associated with increased HDL-C and apoA-I levels and decreased atherogenic indexes. Among male workers, a significantly negative association existed between low HDL-C level, abnormal atherogenic index and occupational vanadium exposure. This suggests vanadium has beneficial effects on blood levels of HDL-C and apoA-I. PMID:24558984

Redox flow batteries based on supporting solutions containing chloride

DOEpatents

Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Xia, Guanguang

2014-01-14

Redox flow battery systems having a supporting solution that contains Cl.sup.- ions can exhibit improved performance and characteristics. Furthermore, a supporting solution having mixed SO.sub.4.sup.2- and Cl.sup.- ions can provide increased energy density and improved stability and solubility of one or more of the ionic species in the catholyte and/or anolyte. According to one example, a vanadium-based redox flow battery system is characterized by an anolyte having V.sup.2+ and V.sup.3+ in a supporting solution and a catholyte having V.sup.4+ and V.sup.5+ in a supporting solution. The supporting solution can contain Cl.sup.- ions or a mixture of SO.sub.4.sup.2- and Cl.sup.- ions.

Redox flow batteries based on supporting solutions containing chloride

DOEpatents

Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Nie, Zimin; Chen, Baowei; Zhang, Jianlu; Xia, Guanguang

2015-07-07

Redox flow battery systems having a supporting solution that contains Cl.sup.- ions can exhibit improved performance and characteristics. Furthermore, a supporting solution having mixed SO.sub.4.sup.2- and Cl.sup.- ions can provide increased energy density and improved stability and solubility of one or more of the ionic species in the catholyte and/or anolyte. According to one example, a vanadium-based redox flow battery system is characterized by an anolyte having V.sup.2+ and V.sup.3+ in a supporting solution and a catholyte having V.sup.4+ and V.sup.5+ in a supporting solution. The supporting solution can contain Cl.sup.- ions or a mixture of SO.sub.4.sup.2- and Cl.sup.- ions.

Redox flow batteries based on supporting solutions containing chloride

DOEpatents

Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Nie, Zimin; Chen, Baowei; Zhang, Jianlu; Xia, Guanguang

2015-09-01

Redox flow battery systems having a supporting solution that contains Cl.sup.- ions can exhibit improved performance and characteristics. Furthermore, a supporting solution having mixed SO.sub.4.sup.2- and Cl.sup.- ions can provide increased energy density and improved stability and solubility of one or more of the ionic species in the catholyte and/or anolyte. According to one example, a vanadium-based redox flow battery system is characterized by an anolyte having V.sup.2+ and V.sup.3+ in a supporting solution and a catholyte having V.sup.4+ and V.sup.5+ in a supporting solution. The supporting solution can contain Cl.sup.- ions or a mixture of SO.sub.4.sup.2- and Cl.sup.- ions.

Redox flow batteries based on supporting solutions containing chloride

DOEpatents

Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Nie, Zimin; Chen, Baowei; Zhang, Jianlu; Xia, Guanguang

2017-11-14

Redox flow battery systems having a supporting solution that contains Cl.sup.- ions can exhibit improved performance and characteristics. Furthermore, a supporting solution having mixed SO.sub.4.sup.2- and Cl.sup.- ions can provide increased energy density and improved stability and solubility of one or more of the ionic species in the catholyte and/or anolyte. According to one example, a vanadium-based redox flow battery system is characterized by an anolyte having V.sup.2+ and V.sup.3+ in a supporting solution and a catholyte having V.sup.4+ and V.sup.5+ in a supporting solution. The supporting solution can contain Cl.sup.- ions or a mixture of SO.sub.4.sup.2- and Cl.sup.- ions.

A simple analytical model of coupled single flow channel over porous electrode in vanadium redox flow battery with serpentine flow channel

NASA Astrophysics Data System (ADS)

Ke, Xinyou; Alexander, J. Iwan D.; Prahl, Joseph M.; Savinell, Robert F.

2015-08-01

A simple analytical model of a layered system comprised of a single passage of a serpentine flow channel and a parallel underlying porous electrode (or porous layer) is proposed. This analytical model is derived from Navier-Stokes motion in the flow channel and Darcy-Brinkman model in the porous layer. The continuities of flow velocity and normal stress are applied at the interface between the flow channel and the porous layer. The effects of the inlet volumetric flow rate, thickness of the flow channel and thickness of a typical carbon fiber paper porous layer on the volumetric flow rate within this porous layer are studied. The maximum current density based on the electrolyte volumetric flow rate is predicted, and found to be consistent with reported numerical simulation. It is found that, for a mean inlet flow velocity of 33.3 cm s-1, the analytical maximum current density is estimated to be 377 mA cm-2, which compares favorably with experimental result reported by others of ∼400 mA cm-2.

Synthesis and characterization of sodium vanadium oxide gels: the effects of water (n) and sodium (x) content on the electrochemistry of Na(x)V2O5·nH2O.

PubMed

Lee, Chia-Ying; Marschilok, Amy C; Subramanian, Aditya; Takeuchi, Kenneth J; Takeuchi, Esther S

2011-10-28

Sodium vanadium oxide gels, Na(x)V(2)O(5)·nH(2)O, of varying sodium content (0.12 < x < 0.32) were prepared by careful control of an ion exchange process. The water content (0.23 > n > 0.01) and interlayer spacing were found to be inversely proportional to the sodium level (x), thus control of sodium (x) content provided a direct, chimie douce approach for control of hydration level (n) and interlayer spacing, without the need for high temperature treatment to affect dehydration. Notably, the use of high temperatures to modify hydration levels can result in crystallization and collapse of the interlayer structure, highlighting the distinct advantage of our novel chimie douce synthesis strategy. Subsequent to synthesis and characterization, results from an electrochemical study of a series of Na(x)V(2)O(5)·nH(2)O samples highlight the significant impact of interlayer water on delivered capacity of the layered materials. Specifically, the sodium vanadium oxide gels with higher sodium content and lower water content provided higher capacities in lithium based cells, where capacity delivered to 2.0 V under C/20 discharge ranged from 170 mAh/g for Na(0.12)V(2)O(5)·0.23H(2)O to 300 mAh/g for Na(0.32)V(2)O(5)·0.01H(2)O. The capacity differences were maintained as the cells were cycled. This journal is © the Owner Societies 2011

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 27.120 12.097 Chromium 7.219 2.927 Lead...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 27.120 12.097 Chromium 7.219 2.927 Lead...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

ION EXCHANGE PROCESS FOR THE RECOVERY AND PURIFICATION OF MATERIALS

DOEpatents

Long, R.S.; Bailes, R.H.

1958-04-15

A process for the recovery of certain metallic ions from aqueous solutions by ion exchange techniques is described. It is applicable to elements such as vanadium, chromium, nnanganese, and the like, which are capable of forming lower valent cations soluble in aqueous solutions and which also form ldgher valent anions soluble in aqueous acidic solutions. For example, small amounts of vanadium occurring in phosphoric acid prepared from phosphate rock may be recovered by reducing the vanadium to a trivalent cation adsorbing; the vanadium in a cationic exchange resin, then treating the resin with a suitable oxidizing agent to convert the adsorbed vanadium to a higher valent state, and finally eluting; the vanadium as an anion from the resin by means of an aqueous acidic solution.

Architecture for improved mass transport and system performance in redox flow batteries

NASA Astrophysics Data System (ADS)

Houser, Jacob; Pezeshki, Alan; Clement, Jason T.; Aaron, Douglas; Mench, Matthew M.

2017-05-01

In this work, electrochemical performance and parasitic losses are combined in an overall system-level efficiency metric for a high performance, all-vanadium redox flow battery. It was found that pressure drop and parasitic pumping losses are relatively negligible for high performance cells, i.e., those capable of operating at a high current density while at a low flow rate. Through this finding, the Equal Path Length (EPL) flow field architecture was proposed and evaluated. This design has superior mass transport characteristics in comparison with the standard serpentine and interdigitated designs at the expense of increased pressure drop. An Aspect Ratio (AR) design is discussed and evaluated, which demonstrates decreased pressure drop compared to the EPL design, while maintaining similar electrochemical performance under most conditions. This AR design is capable of leading to improved system energy efficiency for flow batteries of all chemistries.

A well-defined terminal vanadium(III) oxo complex.

PubMed

King, Amanda E; Nippe, Michael; Atanasov, Mihail; Chantarojsiri, Teera; Wray, Curtis A; Bill, Eckhard; Neese, Frank; Long, Jeffrey R; Chang, Christopher J

2014-11-03

The ubiquity of vanadium oxo complexes in the V+ and IV+ oxidation states has contributed to a comprehensive understanding of their electronic structure and reactivity. However, despite being predicted to be stable by ligand-field theory, the isolation and characterization of a well-defined terminal mononuclear vanadium(III) oxo complex has remained elusive. We present the synthesis and characterization of a unique terminal mononuclear vanadium(III) oxo species supported by the pentadentate polypyridyl ligand 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine (PY5Me2). Exposure of [V(II)(NCCH3)(PY5Me2)](2+) (1) to either dioxygen or selected O-atom-transfer reagents yields [V(IV)(O)(PY5Me2)](2+) (2). The metal-centered one-electron reduction of this vanadium(IV) oxo complex furnishes a stable, diamagnetic [V(III)(O)(PY5Me2)](+) (3) species. The vanadium(III) oxo species is unreactive toward H- and O-atom transfer but readily reacts with protons to form a putative vanadium hydroxo complex. Computational results predict that further one-electron reduction of the vanadium(III) oxo species will result in ligand-based reduction, even though pyridine is generally considered to be a poor π-accepting ligand. These results have implications for future efforts toward low-valent vanadyl chemistry, particularly with regard to the isolation and study of formal vanadium(II) oxo species.

A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

NASA Astrophysics Data System (ADS)

Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

2018-02-01

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

Enrichment, Distribution of Vanadium-Containing Protein in Vanadium-Enriched Sea Cucumber Apostichopus japonicus and the Ameliorative Effect on Insulin Resistance.

PubMed

Liu, Yanjun; Zhou, Qingxin; Zhao, Yanlei; Wang, Yiming; Wang, Yuming; Wang, Jingfeng; Xu, Jie; Xue, Changhu

2016-05-01

Sea cucumbers are a potential source of natural organic vanadium that may improve insulin resistance. In this work, vanadium was accumulated rapidly in blood, body wall, and intestine by sea cucumber Apostichopus japonicus. Furthermore, water-soluble vanadium-containing proteins, the main form of the organic vanadium, were tentatively accumulated and isolated by a bioaccumulation experiment. It was also designed to evaluate the beneficial effect of vanadium-containing proteins (VCPs) from sea cucumber rich in vanadium on the development of hyperglycemia and insulin resistance in C57BL/6J mice fed with a high-fat high-sucrose diet (HFSD). HFSD mice treated with VCPs significantly decreased fasting blood glucose, serum insulin, and HOMA-IR values as compared to HFSD mice, respectively. Serum adiponectin, resistin, TNF-α, and leptin levels in insulin-resistant mice were dramatically reduced by a VCP supplement. These results show an ameliorative effect on insulin resistance by treatment with VCPs. Such compound seems to be a valuable therapy to achieve and/or maintain glycemic control and therapeutic agents in the treatment arsenal for insulin resistance and type 2 diabetes.

Comparison of bioavailable vanadium in alfalfa rhizosphere soil extracted by an improved BCR procedure and EDTA, HCl, and NaNO₃ single extractions in a pot experiment with V-Cd treatments.

PubMed

Yang, Jie; Teng, Yanguo; Zuo, Rui; Song, Liuting

2015-06-01

The BCR sequential extraction procedure was compared with EDTA, HCl, and NaNO3 single extractions for evaluating vanadium bioavailability in alfalfa rhizosphere soil. The amounts of vanadium extracted by these methods were in the following order: BCR (bioavailable V) > EDTA ≈ HCl > NaNO3. Both correlation analysis and stepwise regression were adopted to illustrate the extractable vanadium between different reagents. The correlation coefficients between extracted vanadium and the vanadium contents in alfalfa roots were R NaNO3 = 0.948, R HCl = 0.902, R EDTA = 0.816, and R bioavailable V = 0.819. The stepwise multiple regression equation of the NaNO3 extraction was the most significant at a 95 % confidence interval. The influence of pH, total organic carbon, and cadmium content of soil to vanadium bioavailability were not definite. In summary, both the BCR sequential extraction and the single extraction methods were valid approaches for predicting vanadium bioavailability in alfalfa rhizosphere soil, especially the single extractions.

Extraction of Vanadium from Vanadium Slag Via Non-salt Roasting and Ammonium Oxalate Leaching

NASA Astrophysics Data System (ADS)

Li, Meng; Du, Hao; Zheng, Shili; Wang, Shaona; Zhang, Yang; Liu, Biao; Dreisinger, David Bruce; Zhang, Yi

2017-10-01

A clean method featuring non-salt roasting followed by (NH4)2C2O4 leaching to recover vanadium from vanadium slag was proposed. The carcinogenic Cr6+ compounds and exhaust gases were avoided, and the water generated from vanadate precipitation may be recycled and reused in this new leaching process. The leaching residues may be easily used by a blast furnace. Moreover, (NH4)2C2O4 solution was used as a leaching medium to avoid expensive and complicated ammonium controlling operations as a result of the stability of (NH4)2C2O4 at a high temperature. The transformation mechanisms of vanadium- and chromium-bearing phases were systematically investigated by x-ray diffraction analysis and scanning electron microscopy with energy-disperse x-ray spectrometry, respectively. In addition, the effects of oxygen concentration, roasting temperature, and holding time on vanadium recovery were investigated. Finally, the effects of leaching variables on the vanadium leaching rate were also examined.

Theoretical analysis and experiments for the carburization of vanadium-bearing hot metal

NASA Astrophysics Data System (ADS)

Ma, Deng; Wu, Wei; Dai, Shifan; Liu, Zhibin

2018-01-01

In this study, the feasibility of the carburization of vanadium-bearing hot metal was first investigated by thermodynamic analysis. Next, three carburizers, namely a low-nitrogen carburizer, anthracite, and coke, were used for carburization of 500 g of vanadium-bearing hot metal at 1450 °C, 1500 °C, and 1550 °C, respectively. The carbon increments for the low-nitrogen carburizer, anthracite and coke followed decreasing order in the temperature range from 1450 °C to 1550 °C. Anthracite was the most cost-effective carburizer. Hence, anthracite is used in pilot-scale experiments of the vanadium-bearing hot metal (100 kg and 200 kg). Finally, vanadium extraction experiments of the vanadium-bearing hot metal were carried out in a top-bottom-combined blowing induction furnace. It is proved that the average superheat degree of semi-steel increases from 100 °C to 198 °C by the carburization of vanadium-containing hot metal. Foundation Item: Item Sponsored by National Science Foundation of China (51674092)

Vanadium-Binding Ability of Nucleoside Diphosphate Kinase from the Vanadium-Rich Fan Worm, Pseudopotamilla occelata.

PubMed

Yamaguchi, Nobuo; Yoshinaga, Masafumi; Kamino, Kei; Ueki, Tatsuya

2016-06-01

Polychaete fan worms and ascidians accumulate high levels of vanadium ions. Several vanadiumbinding proteins, known as vanabins, have been found in ascidians. However, no vanadium-binding factors have been isolated from the fan worm. In the present study, we sought to identify vanadiumbinding proteins in the branchial crown of the fan worm using immobilized metal ion affinity chromatography. A nucleoside diphosphate kinase (NDK) homolog was isolated and determined to be a vanadium-binding protein. Kinase activity of the NDK homologue, PoNDK, was suppressed by the addition of V(IV), but was unaffected by V(V). The effect of V(IV) on PoNDK precedes its activation by Mg(II). This is the first report to describe the relationship between NDK and V(IV). PoNDK is located in the epidermis of the branchial crown, and its distribution is very similar to that of vanadium. These results suggest that PoNDK is associated with vanadium accumulation and metabolism in P. occelata.

Critical V2O5/TeO2 Ratio Inducing Abrupt Property Changes in Vanadium Tellurite Glasses.

PubMed

Kjeldsen, Jonas; Rodrigues, Ana C M; Mossin, Susanne; Yue, Yuanzheng

2014-12-26

Transition metal containing glasses have unique electrical properties and are therefore often used for electrochemical applications, such as in batteries. Among oxide glasses, vanadium tellurite glasses exhibit the highest electronic conductivity and thus the high potential for applications. In this work, we investigate how the dynamic and physical properties vary with composition in the vanadium tellurite system. The results show that there exists a critical V(2)O(5) concentration of 45 mol %, above which the local structure is subjected to a drastic change with increasing V(2)O(5), leading to abrupt changes in both hardness and liquid fragility. Electronic conductivity does not follow the expected correlation to the valence state of the vanadium as predicted by the Mott-Austin equation but shows a linear correlation to the mean distance between vanadium ions. These findings could contribute to designing optimum vanadium tellurite compositions for electrochemical devices. The work gives insight into the mechanism of electron conduction in the vanadium tellurite systems.

Recycling of Ammonia Wastewater During Vanadium Extraction from Shale

NASA Astrophysics Data System (ADS)

Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing

2018-03-01

In the vanadium metallurgical industry, massive amounts of ammonia hydroxide or ammonia salt are added during the precipitation process to obtain V2O5; therefore, wastewater containing a high level of NH4 + is generated, which poses a serious threat to environmental and hydrologic safety. In this article, a novel process was developed to recycle ammonia wastewater based on a combination of ammonia wastewater leaching and crystallization during vanadium extraction from shale. The effects of the NH4 + concentration, temperature, time and liquid-to-solid ratio on the leaching efficiencies of vanadium, aluminum and potassium were investigated, and the results showed that 93.2% of vanadium, 86.3% of aluminum and 96.8% of potassium can be leached from sulfation-roasted shale. Subsequently, 80.6% of NH4 + was separated from the leaching solution via cooling crystallization. Vanadium was recovered via a combined method of solvent extraction, precipitation and calcination. Therefore, ammonia wastewater was successfully recycled during vanadium extraction from shale.

Recent progress on gas tungsten arc welding of vanadium alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, J.F.; Grossbeck, M.L.; Goodwin, G.M.

1997-04-01

This is a progress report on a continuing research project to acquire a fundamental understanding of the metallurgical processes in the welding of vanadium alloys. It also has the goal of developing techniques for welding structural vanadium alloys. The alloy V-4Cr-4Ti is used as a representative alloy of the group; it is also the prime candidate vanadium alloy for the U.S. Fusion Program at the present time. However, other alloys of this class were used in the research as necessary. The present work focuses on recent findings of hydrogen embrittlement found in vanadium alloy welds. It was concluded that themore » atmosphere in the inert gas glove box was insufficient for welding 6mm thick vanadium alloy plates.« less

The Influence of Vanadium on Ferrite and Bainite Formation in a Medium Carbon Steel

NASA Astrophysics Data System (ADS)

Sourmail, T.; Garcia-Mateo, C.; Caballero, F. G.; Cazottes, S.; Epicier, T.; Danoix, F.; Milbourn, D.

2017-09-01

The influence of vanadium additions on transformation kinetics has been investigated in a medium carbon forging steel. Using dilatometry to track transformation during continuous cooling or isothermal transformation, the impact of vanadium on both ferrite-pearlite and bainite has been quantified. Transmission electron microscopy and atom probe tomography have been used to establish whether vanadium was present in solid solution, or as clusters and precipitates. The results show that vanadium in solid solution has a pronounced retarding influence on ferrite-pearlite formation and that, unlike in the case of niobium, this effect can be exploited even during relatively slow cooling. The influence on bainite transformation was found to depend on temperature; an explanation in terms of the effect of vanadium on heterogeneous nucleation is tentatively proposed.

Aqua-vanadyl ion interaction with Nafion® membranes

DOE PAGES

Vijayakumar, Murugesan; Govind, Niranjan; Li, Bin; ...

2015-03-23

Lack of comprehensive understanding about the interactions between Nafion membrane and battery electrolytes prevents the straightforward tailoring of optimal materials for redox flow battery applications. In this work, we analyzed the interaction between aqua-vanadyl cation and sulfonic sites within the pores of Nafion membranes using combined theoretical and experimental X-ray spectroscopic methods. Molecular level interactions, namely, solvent share and contact pair mechanisms are discussed based on Vanadium and Sulfur K-edge spectroscopic analysis.

The structural studies of vanadium substituted lithium-bismuth-boro-tellurite glass

NASA Astrophysics Data System (ADS)

Madhu, A.; Eraiah, B.

2018-05-01

The structural studies of vanadium substituted lithium-bismuth-boro-tellurite glass is successfully prepared and certain analysis like XRD,FTIR,DTA/TGA with density, molar volume are done. The amorphous phase has been identified based on X-ray diffraction analysis. The vanadium oxide plays the role as a glass-modifier and influences on BO3 ↔ BO4 conversion. The observed nonlinear variation in Tg with vanadium oxide increase, it reflects structural changes. The nonlinear variation of density and molar volume can be attributed to vanadium oxide incorporation have increased the number of Non-bridging oxygen (NBO'S).

Quantitation and detection of vanadium in biologic and pollution materials

NASA Technical Reports Server (NTRS)

Gordon, W. A.

1974-01-01

A review is presented of special considerations and methodology for determining vanadium in biological and air pollution materials. In addition to descriptions of specific analysis procedures, general sections are included on quantitation of analysis procedures, sample preparation, blanks, and methods of detection of vanadium. Most of the information presented is applicable to the determination of other trace elements in addition to vanadium.

Porous carbon derived from disposable shaddock peel as an excellent catalyst toward VO2+/VO2+ couple for vanadium redox battery

NASA Astrophysics Data System (ADS)

Liu, J.; Wang, Z. A.; Wu, X. W.; Yuan, X. H.; Hu, J. P.; Zhou, Q. M.; Liu, Z. H.; Wu, Y. P.

2015-12-01

Functional porous carbon (PC) derived from bio-friendly shaddock peel has been firstly explored as catalyst for vanadium redox flow battery (VRB). The prepared PC is micro-mesoporous with high BET surface area of 882.7 m2 g-1, has some surface oxygen-containing functional groups, and is doped with N and P heteroatoms. These three factors greatly favor the electrochemical reactions of VO2+/VO2+ on the PC modified glass carbon (PC-GC). Compared with the naked GC and graphite modified GC, the PC-GC presents a lower peak separation (66 mV), higher anodic current density (17.1 mA cm-2) and cathodic current density (15.0 mA cm-2). The VRB using PC modified graphite felt (GF) as positive electrode demonstrates an enhanced voltage efficiency of 82.7% at the current density of 60 mA cm-2, and a better rate performance than that from the virginal GF.

Cobalt and Vanadium Trimetaphosphate Polyanions: Synthesis, Characterization, and Electrochemical Evaluation for Non-aqueous Redox-Flow Battery Applications.

PubMed

Stauber, Julia M; Zhang, Shiyu; Gvozdik, Nataliya; Jiang, Yanfeng; Avena, Laura; Stevenson, Keith J; Cummins, Christopher C

2018-01-17

An electrochemical cell consisting of cobalt ([Co II/III (P 3 O 9 ) 2 ] 4-/3- ) and vanadium ([V III/II (P 3 O 9 ) 2 ] 3-/4- ) bistrimetaphosphate complexes as catholyte and anolyte species, respectively, was constructed with a cell voltage of 2.4 V and Coulombic efficiencies >90% for up to 100 total cycles. The [Co(P 3 O 9 ) 2 ] 4- (1) and [V(P 3 O 9 ) 2 ] 3- (2) complexes have favorable properties for flow-battery applications, including reversible redox chemistry, high stability toward electrochemical cycling, and high solubility in MeCN (1.09 ± 0.02 M, [PPN] 4 [1]·2MeCN; 0.77 ± 0.06 M, [PPN] 3 [2]·DME). The [PPN] 4 [1]·2MeCN and [PPN] 3 [2]·DME salts were isolated as crystalline solids in 82 and 68% yields, respectively, and characterized by 31 P NMR, UV/vis, ESI-MS(-), and IR spectroscopy. The [PPN] 4 [1]·2MeCN salt was also structurally characterized, crystallizing in the monoclinic P2 1 /c space group. Treatment of 1 with [(p-BrC 6 H 4 ) 3 N] + allowed for isolation of the one-electron-oxidized spin-crossover (SCO) complex, [Co(P 3 O 9 ) 2 ] 3- (3), which is the active catholyte species generated during cell charging. The success of the 1-2 cell provides a promising entry point to a potential future class of transition-metal metaphosphate-based all-inorganic non-aqueous redox-flow battery electrolytes.

New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries.

PubMed

Shamie, Jack S; Liu, Caihong; Shaw, Leon L; Sprenkle, Vincent L

2017-02-08

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac) 2 , to vanadium acetylacetonate, V(acac) 3 , is introduced. V(acac) 3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac) 2 . In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H + ), the reduction can take place between 2.25 and 1.5 V versus Na/Na + via a one-electron-transfer reduction. This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na-Cs alloy as the anode. The in situ recovery of V(acac) 3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V 3+ /V 4+ and V 2+ /V 3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac) 3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of State-of-the-art Flow Cells for Energy Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ping

The worldwide energy demand is increasing every day and it necessitates rational and efficient usage of renewable energy. Undoubtedly, utilization of renewable energy can address various environmental challenges. However, all current renewable energy resources (wind, solar, and hydroelectric power) are intermittent and fluctuating in their nature that raises an important question of introducing effective energy storage solutions. Utilization of redox flow cells (RFCs) has recently been recognized as a viable technology for large-scale energy storage and, hence, is well suited for integrating renewable energy and balancing electricity grids. In brief, RFC is an electrochemical storage device (Fig. 1), where energymore » is stored in chemical bonds, similar to a battery, but with reactants external to the cell. The state-of-the-art in flow cell technology uses an aqueous acidic electrolyte and simple metal redox couples. Several of these systems have been commercialized although current technologies, such as vanadium (V) and zinc-bromine (Zn-Br 2) RFCs, for grid level energy storage, suffer from a number of drawbacks, i.e. expensive and resource-limited active materials (vanadium RFCc), and low current performance (Zn-Br 2 RFCs due to Zn dendrite formation). Thus, there is an urgent call to develop efficient (high-energy density) and low-cost RFCs to meet the efflorescent energy storage demands. Approach: To address the first challenge of achieving high-energy density, we plan to design and further modify complexes composed of bifunctional multidentate ligands and specific metal centers, capable of storing as many electrons as possible.« less

Effect of vanadium on colonic aberrant crypt foci induced in rats by 1,2 Dimethyl hydrazine

PubMed Central

Kanna, P Suresh; Mahendrakumar, CB; Chakraborty, T; Hemalatha, P; Banerjee, Pratik; Chatterjee, M

2003-01-01

AIM: To investigate the chemo preventive effects of vanadium on rat colorectal carcinogenesis induced by 1,2-dimethylhydrazine (DMH). METHODS: Male Sprague-Dawley Rats were randomly divided into four groups. Rats in Group A received saline vehicle alone for 16 weeks. Rats in Group B were given DMH injection once a week intraperitoneally for 16 weeks; rats in Group C, with the same DMH treatment as in the Group B, but received 0.5-ppm vanadium in the form ammonium monovanadate ad libitum in drinking water. Rats in the Group D received vanadium alone as in the Group C without DMH injection. RESULTS: Aberrant crypt foci (ACF) were formed in animals in DMH-treated groups at the end of week 16. Compared to DMH group, vanadium treated group had less ACF (P < 0.001). At the end of week 32, all rats in DMH group developed large intestinal tumors. Rats treated with vanadium contained significantly few colonic adenomas and carcinomas (P < 0.05) compared to rats administered DMH only. In addition, a significant reduction (P < 0.05) in colon tumor burden (sum of tumor sizes per animal) was also evident in animals of Group C when compared to those in rats of carcinogen control Group B. The results also showed that vanadium significantly lowered PCNA index in ACF (P < 0.005). Furthermore, vanadium supplementation also elevated liver GST and Cyt P-450 activities (P < 0.001 and P < 0.02, respectively). CONCLUSION: Vanadium in the form of ammonium monovanadate supplemented in drinking water ad libitum has been found to be highly effective in reducing tumor incidence and preneoplastic foci on DMH-induced colorectal carcinogenesis. These findings suggest that vanadium administration can suppress colon carcinogenesis in rats. PMID:12717849

An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite.

PubMed

Chen, Desheng; Zhao, Hongxin; Hu, Guoping; Qi, Tao; Yu, Hongdong; Zhang, Guozhi; Wang, Lina; Wang, Weijing

2015-08-30

An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite was developed. In this study, a mixed solvent system of di(2-ethylhexyl) phosphate (D2EHPA) and tri-n-butyl phosphate (TBP) diluted with kerosene was used for the selective extraction of vanadium from a hydrochloric acid leaching solution that contained low vanadium concentration with high concentrations of iron and impurities of Ca, Mg, and Al. In the extraction process, the initial solution pH and the phase ratio had considerable functions in the extraction of vanadium from the hydrochloric acid leaching solution. Under optimal extraction conditions (i.e., 30-40°C for 10min, 1:3 phase ratio (O/A), 20% D2EHPA concentration (v/v), and 0-0.8 initial solution pH), 99.4% vanadium and only 4.2% iron were extracted by the three-stage counter-current extraction process. In the stripping process with H2SO4 as the stripping agent and under optimal stripping conditions (i.e., 20% H2SO4 concentration, 5:1 phase ratio (O/A), 20min stripping time, and 40°C stripping temperature), 99.6% vanadium and only 5.4% iron were stripped by the three-stage counter-current stripping process. The stripping solution contained 40.16g/LV2O5,0.691g/L Fe, 0.007g/L TiO2, 0.006g/L SiO2 and 0.247g/L CaO. A V2O5 product with a purity of 99.12% V2O5 and only 0.026% Fe was obtained after the oxidation, precipitation, and calcination processes. The total vanadium recovered from the hydrochloric acid leaching solution was 85.5%. Copyright © 2015 Elsevier B.V. All rights reserved.

Modified lithium vanadium oxide electrode materials products and methods

DOEpatents

Thackeray, Michael M.; Kahaian, Arthur J.; Visser, Donald R.; Dees, Dennis W.; Benedek, Roy

1999-12-21

A method of improving certain vanadium oxide formulations is presented. The method concerns fluorine doping formulations having a nominal formula of LiV.sub.3 O.sub.8. Preferred average formulations are provided wherein the average oxidation state of the vanadium is at least 4.6. Herein preferred fluorine doped vanadium oxide materials, electrodes using such materials, and batteries including at least one electrode therein comprising such materials are provided.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Zhicheng; Rao, Linfeng; Abney, Carter W.

Adsorbents developed for the recovery of uranium from seawater display poor selectivity over other transition metals present in the ocean, with vanadium particularly problematic. To improve selectivity, an indispensable step is the positive identification of metal binding environments following actual seawater deployment. In this work we apply x-ray absorption fine structure (XAFS) spectroscopy to directly investigate the vanadium binding environment on seawater-deployed polyamidoxime adsorbents. Comparison of the x-ray absorption near edge spectra (XANES) reveal marked similarities to recently a reported non-oxido vanadium (V) structure formed upon binding with cyclic imidedioxime, a byproduct of generating amidoxime functionalities. Density functional theory (DFT)more » calculations provided a series of putative vanadium binding environments for both vanadium (IV) and vanadium (V) oxidation states, and with both amidoxime and cyclic imidedioxime. Fits of the extended XAFS (EXAFS) data confirmed vanadium (V) is bound exclusively by the cyclic imidedioxime moiety in a 1:2 metal:ligand fashion, though a modest structural distortion is also observed compared to crystal structure data and computationally optimized geometries which is attributed to morphology effects from the polymer graft chain and the absence of crystal packing interactions. These results demonstrate that improved selectivity for uranium over vanadium can be achieved by suppressing the formation of cyclic imidedioxime during preparation of polyamidoxime adsorbents for seawater uranium recovery.« less

Amorphous Mixed-Valence Vanadium Oxide/Exfoliated Carbon Cloth Structure Shows a Record High Cycling Stability.

PubMed

Song, Yu; Liu, Tian-Yu; Yao, Bin; Kou, Tian-Yi; Feng, Dong-Yang; Liu, Xiao-Xia; Li, Yat

2017-04-01

Previous studies show that vanadium oxides suffer from severe capacity loss during cycling in the liquid electrolyte, which has hindered their applications in electrochemical energy storage. The electrochemical instability is mainly due to chemical dissolution and structural pulverization of vanadium oxides during charge/discharge cyclings. In this study the authors demonstrate that amorphous mixed-valence vanadium oxide deposited on exfoliated carbon cloth (CC) can address these two limitations simultaneously. The results suggest that tuning the V 4+ /V 5+ ratio of vanadium oxide can efficiently suppress the dissolution of the active materials. The oxygen-functionalized carbon shell on exfoliated CC can bind strongly with VO x via the formation of COV bonding, which retains the electrode integrity and suppresses the structural degradation of the oxide during charging/discharging. The uptake of structural water during charging and discharging processes also plays an important role in activating the electrode material. The amorphous mixed-valence vanadium oxide without any protective coating exhibits record-high cycling stability in the aqueous electrolyte with no capacitive decay in 100 000 cycles. This work provides new insights on stabilizing vanadium oxide, which is critical for the development of vanadium oxide based energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Overview of environmental and occupational vanadium exposure and associated health outcomes: an article based on a presentation at the 8th International Symposium on Vanadium Chemistry, Biological Chemistry, and Toxicology, Washington DC, August 15-18, 2012.

PubMed

Fortoul, T I; Rojas-Lemus, M; Rodriguez-Lara, V; Gonzalez-Villalva, A; Ustarroz-Cano, M; Cano-Gutierrez, G; Gonzalez-Rendon, S E; Montaño, L F; Altamirano-Lozano, M

2014-01-01

Vanadium (V) has a variety of applications that make it suitable for use in ceramic production and decoration, production of pigments for a variety of products, an accelerator for drying paint, production of aniline black dye, and as a mordant in coloring textiles. Taking advantage of its hardness, resilience, ability to form alloys, and its resistance to corrosion, V is also used in the production of tools, steel, machinery, and surgical implants. V is employed in producing photographic developers, batteries, and semi-conductors, and in catalyst-based recycling processes. As technologies have evolved, the use of V has increased in jet aircraft and space technology, as well as in manufacture of ultraviolet filter glass to prevent radiation injury. Due to these myriad uses, the potential for occupational exposure to V is ever-evident. Similarly, there is an increased risk for environmental contamination by V agents themselves or as components of by-products released into the environment. For example, the use of V in sulfuric acid production results in the release of soot and/or fly ash rich in vanadium pentoxide. Petroleum refinery, smelting, welding, and cutting of V-rich steel alloy, the cleaning and repair of oil-fired boilers, and catalysis of chemical productions are other sources of increased airborne V-bearing particles in local/distant environments. Exposure of non-workers to V is an increasing health concern. Studies have demonstrated associations between exposure to airborne V-bearing particles (as part of air pollution) and increased risks of a variety of pathologies like hypertension, dysrhythmia, systemic inflammation, hyper-coagulation, cancers, and bronchial hyper-reactivity. This paper will provide a review of the history of V usage in occupational settings, documented exposure levels, environmental levels of V associated with pollution, epidemiologic data relating V exposure(s) to adverse health outcomes, and governmental responses to protect both workers and non-workers from exposure to this metal.

Hydrogen Production by Steam Reforming of Natural Gas Over Vanadium-Nickel-Alumina Catalysts.

PubMed

Yoo, Jaekyeong; Park, Seungwon; Song, Ji Hwan; Song, In Kyu

2018-09-01

A series of vanadium-nickel-alumina (xVNA) catalysts were prepared by a single-step sol-gel method with a variation of vanadium content (x, wt%) for use in the hydrogen production by steam reforming of natural gas. The effect of vanadium content on the physicochemical properties and catalytic activities of xVNA catalysts in the steam reforming of natural gas was investigated. It was found that natural gas conversion and hydrogen yield showed volcano-shaped trends with respect to vanadium content. It was also revealed that natural gas conversion and hydrogen yield increased with decreasing nickel crystallite size.

Effect of vanadium compounds on acid phosphatase activity.

PubMed

Vescina, C M; Sálice, V C; Cortizo, A M; Etcheverry, S B

1996-01-01

The direct effect of different vanadium compounds on acid phosphatase (ACP) activity was investigated. Vanadate and vanadyl but not pervanadate inhibited the wheat germ ACP activity. These vanadium derivatives did not alter the fibroblast Swiss 3T3 soluble fraction ACP activity. Using inhibitors of tyrosine phosphatases (PTPases), the wheat germ ACP was partially characterized as a PTPase. This study suggests that the inhibitory ability of different vanadium derivatives to modulate ACP activity seems to depend on the geometry around the vanadium atom more than on the oxidation state. Our results indicate a correlation between the PTPase activity and the sensitivity to vanadate and vanadyl cation.

Description and performance of a novel aqueous all-copper redox flow battery

NASA Astrophysics Data System (ADS)

Sanz, Laura; Lloyd, David; Magdalena, Eva; Palma, Jesús; Kontturi, Kyösti

2014-12-01

In this paper we present a novel aqueous redox flow battery chemistry based on copper chloro complexes. The energy density (20 Wh L-1) achieved is comparable to traditional vanadium redox flow batteries. This is due to the high solubility of copper (3 M), which offsets the relatively low cell potential (0.6 V). The electrolyte is cheap, simple to prepare and easy to recycle since no additives or catalysts are used. The stack used is based on plain graphite electrode materials and a low-cost microporous separator. The system can be operated at 60 °C eliminating the need for a heat exchanger and delivers an energy efficiency of 93, 86 and 74% at 5, 10 and 20 mA cm-2 respectively.

Electrochemical characterization of nanodimensional metal oxide materials

NASA Astrophysics Data System (ADS)

Tang, Paul Enle

Energy storage devices have become a bottleneck in performance improvements for portable electronics. This research seeks to answer basic science questions that may lead to the necessary improvements. First, this work demonstrates that insertion of multivalent ions into vanadium oxide greatly exceeds the storage capacity of materials presently used. Second, this work demonstrates that potassium ferrate exhibits a uniquely large pseudocapacitive effect. This effect can be used to great advantage when high power density and high energy density are required. Lastly, this work proposes a model of pseudocapacitance that has a greater descriptive power than that of previous models.

SUPERCONDUCTING VANADIUM BASE ALLOY

DOEpatents

Cleary, H.J.

1958-10-21

A new vanadium-base alloy which possesses remarkable superconducting properties is presented. The alloy consists of approximately one atomic percent of palladium, the balance being vanadium. The alloy is stated to be useful in a cryotron in digital computer circuits.

Mineral resource of the month: vanadium

USGS Publications Warehouse

Magyar, Michael J.

2007-01-01

Vanadium, the name of which comes from Vanadis, a goddess in Scandinavian mythology, is one of the most important ferrous metals. Vanadium has many uses, but the metal’s metallurgical applications, such as an alloying element in iron and steel, account for more than 85 percent of U.S. consumption. The dominant nonmetallurgical use of the metal is as a catalyst for the production of maleic anhydride and sulfuric acid, ceramics, vanadium chemicals and electronics.

Effect of hydrogen on fatigue crack propagation in vanadium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, D.W.; Stoloff, N.S.

The influence of hydrogen on fatigue crack propagation in unalloyed vanadium and several hydrogen-charged vanadium alloys has been investigated. The Paris--Erdogan equation, da/dN = C(..delta..K)/sup m/, was approximately obeyed for all alloys. Crack growth rates were lowest in vanadium and dilute vanadium-hydrogen alloys, and were not very sensitive to volume fraction of hydrides in more concentrated alloys. The crack growth exponent, m, is inversely proportional to the cyclic strain hardening rate, n', and the rate constant C is inversely proportional to the square of the ultimate tensile stress, sigma/sub UTS/: metallographic examination showed hydride reorientation and growth in the originallymore » hydrided alloys. No stress-induced hydrides were observed in V-H solid-solution alloys. Fractures in hydrided materials exhibited cleavage-like features, while striations were noted in unalloyed vanadium and dilute solid-solution alloys.« less

Effect of hydrogen on fatigue crack propagation in vanadium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, D.W.; Stoloff, N.S.

The influence of hydrogen on fatigue crack propagation in unalloyed vanadium and several hydrogen-charged vanadium alloys has been investigated. The Paris--Erdogan equation, da/dN = C(..delta..K)/sup m/, was approximately obeyed for all alloys. Crack growth rates were lowest in vanadium and dilute vanadium--hydrogen alloys, and were not very sensitive to volume fraction of hydrides in more concentrated alloys. The crack growth exponent, m, is inversely proportional to the cyclic strain hardening rate, n', and the rate constant C is inversely proportional to the square of the ultimate tensile stress, sigma/sub UTS/: metallographic examination showed hydride reorientation and growth in the originallymore » hydrided alloys. No stress-induced hydrides were observed in V--H solid-solution alloys. Fractures in hydrided materials exhibited cleavage-like features, while striations were noted in unalloyed vanadium and dilute solid-solution alloys.« less

Vanadium Extraction from Shale via Sulfuric Acid Baking and Leaching

NASA Astrophysics Data System (ADS)

Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing

2018-01-01

Fluorides are widely used to improve vanadium extraction from shale in China. Sulfuric acid baking-leaching (SABL) was investigated as a means of recovering vanadium which does not require the use of fluorides and avoids the productions of harmful fluoride-containing wastewater. Various effective factors were systematically studied and the experimental results showed that 90.1% vanadium could be leached from the shale. On the basis of phase transformations and structural changes after baking the shale, a mechanism of vanadium extraction from shale via SABL was proposed. The mechanism can be described as: (1) sulfuric acid diffusion into particles; (2) the formation of concentrated sulfuric acid media in the particles after water evaporation; (3) hydroxyl groups in the muscovite were removed and transient state [SO4 2-] was generated; and (4) the metals in the muscovite were sulfated by active [SO4 2-] and the vanadium was released. Thermodynamics modeling confirmed this mechanism.

Plasma enhanced chemical vapor deposition (PECVD) method of forming vanadium oxide films and vanadium oxide thin-films prepared thereby

DOEpatents

Zhang, Ji-Guang; Tracy, C. Edwin; Benson, David K.; Turner, John A.; Liu, Ping

2000-01-01

A method is disclosed of forming a vanadium oxide film on a substrate utilizing plasma enhanced chemical vapor deposition. The method includes positioning a substrate within a plasma reaction chamber and then forming a precursor gas comprised of a vanadium-containing chloride gas in an inert carrier gas. This precursor gas is then mixed with selected amounts of hydrogen and oxygen and directed into the reaction chamber. The amounts of precursor gas, oxygen and hydrogen are selected to optimize the final properties of the vanadium oxide film An rf plasma is generated within the reaction chamber to chemically react the precursor gas with the hydrogen and the oxygen to cause deposition of a vanadium oxide film on the substrate while the chamber deposition pressure is maintained at about one torr or less. Finally, the byproduct gases are removed from the plasma reaction chamber.

Graphite furnace atomic absorption spectrometric determination of vanadium after cloud point extraction in the presence of graphene oxide

NASA Astrophysics Data System (ADS)

López-García, Ignacio; Marín-Hernández, Juan José; Hernández-Córdoba, Manuel

2018-05-01

Vanadium (V) and vanadium (IV) in the presence of a small concentration of graphene oxide (0.05 mg mL-1) are quantitatively transferred to the coacervate obtained with Triton X-114 in a cloud point microextraction process. The surfactant-rich phase is directly injected into the graphite atomizer of an atomic absorption spectrometer. Using a 10-mL aliquot sample and 150 μL of a 15% Triton X-114 solution, the enrichment factor for the analyte is 103, which results in a detection limit of 0.02 μg L-1 vanadium. The separation of V(V) and V(IV) using an ion-exchanger allows speciation of the element at low concentrations. Data for seven reference water samples with certified vanadium contents confirm the reliability of the procedure. Several beer samples are also analyzed, those supplied as canned drinks showing low levels of tetravalent vanadium.

A nested case-control study of prenatal vanadium exposure and low birthweight.

PubMed

Jiang, Minmin; Li, Yuanyuan; Zhang, Bin; Zhou, Aifen; Zheng, Tongzhang; Qian, Zhengmin; Du, Xiaofu; Zhou, Yanqiu; Pan, Xinyun; Hu, Jie; Wu, Chuansha; Peng, Yang; Liu, Wenyu; Zhang, Chuncao; Xia, Wei; Xu, Shunqing

2016-09-01

Is prenatal vanadium exposure associated with adverse birth outcomes? The odds of low birthweight (LBW) are increased 2.23-fold in mothers with a urinary vanadium of ≥2.91 μg/g creatinine compared with that in mothers with a urinary vanadium of ≤1.42 μg/g creatinine. Human exposure to vanadium occurs through intake of food, water and polluted air. Vanadium has been suggested to have fetotoxicity and developmental toxicity in animal studies, and epidemiological studies have reported an association between a decrease in birthweight and vanadium exposure estimated from particulate matter. A nested case-control study involving 816 study participants (204 LBW cases and 612 matched controls) was conducted with data from the prospective Healthy Baby Cohort between 2012 and 2014 in the province of Hubei, China. Vanadium concentrations in 816 maternal urine samples collected before delivery [the median gestational age was 39 weeks (range 27-42 weeks)] were measured by inductively coupled plasma mass spectrometry. Information on the infants' birth outcomes was obtained from medical records. Conditional logistic regression was used to calculate the odds ratios (ORs) and 95% confidence intervals (CIs). The median urinary vanadium concentration of the cases was much higher than that of the controls (3.04 μg/g creatinine versus 1.93 μg/g creatinine). The results revealed a significant positive trend between the odds of LBW and level of maternal urinary vanadium [relative to the lowest tertile; adjusted OR = 1.69 (95% CI: 0.92, 3.10) for the medium tertile; adjusted OR = 2.23 (95% CI: 1.23, 4.05) for the highest tertile; P-trend = 0.02]. Additionally, the association was not modified by maternal age (P for heterogeneity = 0.70) or infant gender (P for heterogeneity = 0.21). The maternal urine sample was collected before labor, and the maternal urinary vanadium levels measured at one point in time may not accurately reflect the vanadium burden during the entire pregnancy. The results of this study can enrich the biological monitoring data on urinary vanadium in pregnant women; and may be evidence that vanadium may affect fetal development. This work was supported by the National Natural Science Foundation of China (21437002, 81372959 and 81402649), the R&D Special Fund for Public Welfare Industry (Environment) (201309048) and the Fundamental Research Funds for the Central Universities, HUST (2016YXZD043). The authors have no conflicts of interest to declare. © The Author 2016. Published by Oxford University Press on behalf of the European Society of Human Reproduction and Embryology. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Brain Metal Distribution and Neuro-Inflammatory Profiles after Chronic Vanadium Administration and Withdrawal in Mice

PubMed Central

Folarin, Oluwabusayo R.; Snyder, Amanda M.; Peters, Douglas G.; Olopade, Funmilayo; Connor, James R.; Olopade, James O.

2017-01-01

Vanadium is a potentially toxic environmental pollutant and induces oxidative damage in biological systems including the central nervous system (CNS). Its deposition in brain tissue may be involved in the pathogenesis of certain neurological disorders which after prolonged exposure can culminate into more severe pathology. Most studies on vanadium neurotoxicity have been done after acute exposure but in reality some populations are exposed for a lifetime. This work was designed to ascertain neurodegenerative consequences of chronic vanadium administration and to investigate the progressive changes in the brain after withdrawal from vanadium treatment. A total of 85 male BALB/c mice were used for the experiment and divided into three major groups of vanadium treated (intraperitoneally (i.p.) injected with 3 mg/kg body weight of sodium metavanadate and sacrificed every 3 months till 18 months); matched controls; and animals that were exposed to vanadium for 3 months and thereafter the metal was withdrawn. Brain tissues were obtained after animal sacrifice. Sagittal cut sections of paraffin embedded tissue (5 μm) were analyzed by the Laser ablation-inductively coupled plasma-mass spectrometry (LA–ICP–MS) to show the absorption and distribution of vanadium metal. Also, Haematoxylin and Eosin (H&E) staining of brain sections, and immunohistochemistry for Microglia (Iba-1), Astrocytes (GFAP), Neurons (Neu-N) and Neu-N + 4′,6-diamidine-2′-pheynylindole dihydrochloride (Dapi) Immunofluorescent labeling were observed for morphological and morphometric parameters. The LA–ICP–MS results showed progressive increase in vanadium uptake with time in different brain regions with prediction for regions like the olfactory bulb, brain stem and cerebellum. The withdrawal brains still show presence of vanadium metal in the brain slightly more than the controls. There were morphological alterations (of the layering profile, nuclear shrinkage) in the prefrontal cortex, cellular degeneration (loss of dendritic arborization) and cell death in the Hippocampal CA1 pyramidal cells and Purkinje cells of the cerebellum, including astrocytic and microglial activation in vanadium exposed brains which were all attenuated in the withdrawal group. With exposure into old age, the evident neuropathology was microgliosis, while progressive astrogliosis became more attenuated. We have shown that chronic administration of vanadium over a lifetime in mice resulted in metal accumulation which showed regional variabilities with time. The metal profile and pathological effects were not completely eliminated from the brain even after a long time withdrawal from vanadium metal. PMID:28790895

Extracting uranium from seawater: Promising AI series adsorbents

DOE PAGES

Das, Sadananda; Oyola, Y.; Mayes, Richard T.; ...

2015-11-10

A series of adsorbent (AI10 through AI17) were successfully developed at ORNL by radiation induced graft polymerization (RIGP) of acrylonitrile (AN) and vinylphosphonic acid (VPA) (at different mole/mole ratios) onto high surface area polyethylene fiber, with higher degree of grafting which ranges from 110 300%. The grafted nitrile groups were converted to amidoxime groups by reaction with 10 wt% hydroxylamine at 80 C for 72 hours. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8 ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged frommore » 171-187 g-U/kg-ads irrespective of %DOG. The performance of the adsorbents for uranium adsorption in natural seawater was also carried out using flow-through-column at Pacific Northwest National Laboratory (PNNL). The three hours KOH conditioning was better for higher uranium uptake than one hour. The adsorbent AI11 containing AN and VPA at the mole ration of 3.52, emerged as the potential candidate for higher uranium adsorption (3.35 g-U/Kg-ads.) after 56 days of exposure in the seawater in the flow-through-column. The rate vanadium adsorption over uranium was linearly increased throughout the 56 days exposure. The total vanadium uptake was ~5 times over uranium after 56 days.« less

Materials, system designs and modelling approaches in techno-economic assessment of all-vanadium redox flow batteries - A review

NASA Astrophysics Data System (ADS)

Minke, Christine; Turek, Thomas

2018-02-01

The vanadium redox flow battery (VFB) is one of the most promising stationary electrochemical storage systems. The reduction of system costs is a major challenge in the realization of its widespread application. The high complexity of this technology requires a close linking of technologic and economic aspects in system cost assessment. The present review provides an extensive literature analysis with a focus on techno-economic assessment of VFB. Considered materials, system designs and modelling approaches are assessed and compared in order to present and evaluate the current status of system cost assessment in a transparent way. Systems in a range of 2 kW-50 MW providing energy for up to 150 h are covered in literature resulting in an immense range of specific total system costs of 564-12931 € kW-1 or 89-1738 € (kWh)-1. Based on the data from the reviewed studies, guide values of 650 € (kWh)-1 and 550 € (kWh)-1 for installed VFB systems in a power range of 10-1000 kW providing energy for 4 h and 8 h respectively are derived from literature. Moreover, the relevance of precision in the definition of scope and components for meaningful results of techno-economic assessments of VFB systems is pointed out.

Extracting uranium from seawater: Promising AI series adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Sadananda; Oyola, Y.; Mayes, Richard T.

A series of adsorbent (AI10 through AI17) were successfully developed at ORNL by radiation induced graft polymerization (RIGP) of acrylonitrile (AN) and vinylphosphonic acid (VPA) (at different mole/mole ratios) onto high surface area polyethylene fiber, with higher degree of grafting which ranges from 110 300%. The grafted nitrile groups were converted to amidoxime groups by reaction with 10 wt% hydroxylamine at 80 C for 72 hours. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8 ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged frommore » 171-187 g-U/kg-ads irrespective of %DOG. The performance of the adsorbents for uranium adsorption in natural seawater was also carried out using flow-through-column at Pacific Northwest National Laboratory (PNNL). The three hours KOH conditioning was better for higher uranium uptake than one hour. The adsorbent AI11 containing AN and VPA at the mole ration of 3.52, emerged as the potential candidate for higher uranium adsorption (3.35 g-U/Kg-ads.) after 56 days of exposure in the seawater in the flow-through-column. The rate vanadium adsorption over uranium was linearly increased throughout the 56 days exposure. The total vanadium uptake was ~5 times over uranium after 56 days.« less

Extracting Uranium from Seawater: Promising AI Series Adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, S.; Oyola, Y.; Mayes, R. T.

A new series of adsorbents (AI10 through AI17) were successfully developed at ORNL by radiation induced graft polymerization (RIGP) of acrylonitrile (AN) and vinylphosphonic acid (VPA) (at different mole to mole ratios) onto high surface area polyethylene fiber, with high degrees of grafting (DOG) varying from 110 to 300%. The grafted nitrile groups were converted to amidoxime groups by reaction with 5 wt % hydroxylamine at 80 °C for 72 h. The amidoximated adsorbents were then conditioned with 0.44 M KOH at 80 °C followed by screening at ORNL with prescreening brine spiked with 8 ppm uranium. Uranium adsorption capacitiesmore » in prescreening ranged from 171 to 187 g-U/kg-ads irrespective of percent DOG. The performance of the adsorbents with respect to uranium adsorption in natural seawater was also investigated using flow-throughcolumn testing at the Pacific Northwest National Laboratory (PNNL). Three hours of KOH conditioning led to higher uranium uptake than 1 h of conditioning. The adsorbent AI11, containing AN and VPA at the mole ratio of 3.52, emerged as the potential candidate for the highest uranium adsorption (3.35 g-U/kg-ads.) after 56 days of exposure in seawater flow-through-columns. The rate of vanadium adsorption over uranium linearly increased throughout the 56 days of exposure. The total mass of vanadium uptake was ~5 times greater than uranium after 56 days.« less

Superior Electrocatalytic Activity of a Robust Carbon-Felt Electrode with Oxygen-Rich Phosphate Groups for All-Vanadium Redox Flow Batteries.

PubMed

Kim, Ki Jae; Lee, Heon Seong; Kim, Jeonghun; Park, Min-Sik; Kim, Jung Ho; Kim, Young-Jun; Skyllas-Kazacos, Maria

2016-06-08

A newly prepared type of carbon felt with oxygen-rich phosphate groups is proposed as a promising electrode with good stability for all-vanadium redox flow batteries (VRFBs). Through direct surface modification with ammonium hexafluorophosphate (NH4 PF6 ), phosphorus can be successfully incorporated onto the surface of the carbon felt by forming phosphate functional groups with -OH chemical moieties that exhibit good hydrophilicity. The electrochemical reactivity of the carbon felt toward the redox reactions of VO(2+) /VO2 (+) (in the catholyte) and V(3+) /V(2+) (in the anolyte) can be effectively improved owing to the superior catalytic effects of the oxygen-rich phosphate groups. Furthermore, undesirable hydrogen evolution can be suppressed by minimizing the overpotential for the V(3+) /V(2+) redox reaction in the anolyte of the VRFB. Cell-cycling tests with the catalyzed electrodes show improved energy efficiencies of 88.2 and 87.2 % in the 1(st) and 20(th)  cycles compared with 83.0 and 81.1 %, respectively, for the pristine electrodes at a constant current density of 32 mA cm(-2) . These improvements are mainly attributed to the faster charge transfer allowed by the integration of the oxygen-rich phosphate groups on the carbon-felt electrode. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature-gated thermal rectifier for active heat flow control.

PubMed

Zhu, Jia; Hippalgaonkar, Kedar; Shen, Sheng; Wang, Kevin; Abate, Yohannes; Lee, Sangwook; Wu, Junqiao; Yin, Xiaobo; Majumdar, Arun; Zhang, Xiang

2014-08-13

Active heat flow control is essential for broad applications of heating, cooling, and energy conversion. Like electronic devices developed for the control of electric power, it is very desirable to develop advanced all-thermal solid-state devices that actively control heat flow without consuming other forms of energy. Here we demonstrate temperature-gated thermal rectification using vanadium dioxide beams in which the environmental temperature actively modulates asymmetric heat flow. In this three terminal device, there are two switchable states, which can be regulated by global heating. In the "Rectifier" state, we observe up to 28% thermal rectification. In the "Resistor" state, the thermal rectification is significantly suppressed (<1%). To the best of our knowledge, this is the first demonstration of solid-state active-thermal devices with a large rectification in the Rectifier state. This temperature-gated rectifier can have substantial implications ranging from autonomous thermal management of heating and cooling systems to efficient thermal energy conversion and storage.

Vanadium release in whole blood, serum and urine of patients implanted with a titanium alloy hip prosthesis.

PubMed

Catalani, S; Stea, S; Beraudi, A; Gilberti, M E; Bordini, B; Toni, A; Apostoli, P

2013-08-01

Vanadium (V) is a minor constituent of the Titanium-Aluminum-Vanadium (TiAlV) alloy currently used in cementless hip prostheses. Present study aimed at verifying the correlation of vanadium levels among different matrices and assessing reference levels of the ion in a population of patients wearing a well-functioning hip prosthesis. Vanadium was measured using Inductive Coupled Plasma Mass Spectrometry (ICP-MS) in whole blood, serum and urine of 129 patients implanted with a TiAlV-alloy hip prosthesis. The values in the serum were above the upper limit of the reference values in 42% of patients (29% in urine and 13% in whole blood). A good correlation among matrices was observed (p < 0.001). The cohort of patients (N = 32) complaining of pain or in which a loosening or damage to the prosthesis was assessed showed a significantly higher excretion of vanadium in urine as compared with the remaining asymptomatic patients (p = 0.001). The 95th percentile distribution of vanadium in the cohort of patients with a well-functioning prosthesis was 0.3 μg/L in whole blood, 0.5 μg/L in serum and 2.8 μg/L in urine, higher that in the unexposed population, especially for urine. The presence of a prosthesis, even though well-functioning, may cause a possible release of vanadium into the blood and a significant urinary excretion. The reference values of vanadium of the asymptomatic patients with titanium alloy hip prostheses supplied information regarding the background exposure level of the ions and their lower and upper limits.

NH3-SCR denitration catalyst performance over vanadium-titanium with the addition of Ce and Sb.

PubMed

Xu, Chi; Liu, Jian; Zhao, Zhen; Yu, Fei; Cheng, Kai; Wei, Yuechang; Duan, Aijun; Jiang, Guiyuan

2015-05-01

Selective catalytic reduction technology using NH3 as a reducing agent (NH3-SCR) is an effective control method to remove nitrogen oxides. TiO2-supported vanadium oxide catalysts with different levels of Ce and Sb modification were prepared by an impregnation method and were characterized by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), Raman and Hydrogen temperature-programmed reduction (H2-TPR). The catalytic activities of V5CexSby/TiO2 catalysts for denitration were investigated in a fixed bed flow microreactor. The results showed that cerium, vanadium and antimony oxide as the active components were well dispersed on TiO2, and the catalysts exhibited a large number of d-d electronic transitions, which were helpful to strengthen SCR reactivity. The V5CexSby/TiO2 catalysts exhibited a good low temperature NH3-SCR catalytic activity. In the temperature range of 210 to 400°C, the V5CexSby/TiO2 catalysts gave NO conversion rates above 90%. For the best V5Ce35Sb2/TiO2 catalyst, at a reaction temperature of 210°C, the NO conversion rate had already reached 90%. The catalysts had different catalytic activity with different Ce loadings. With the increase of Ce loading, the NO conversion rate also increased. Copyright © 2015. Published by Elsevier B.V.

Reaping the redox switching capability of vanadium in Li3V2(PO4)3/HHC composite to demonstrate the rocking chair electrode performance

NASA Astrophysics Data System (ADS)

Saravanan, Karuppiah; Kalaiselvi, Nallathamby

2017-10-01

The study exploits the functional advantages of vanadium with variable oxidation states to extract maximum energy from Li3V2(PO4)3/HHC composite containing human hair derived carbon. Vanadium, present in the form of V3+ in Li3V2(PO4)3 stabilizes itself electrochemically as V4+ by forming LiV2(PO4)3 through oxidation in the potential range 3.0-4.5 V and as V1+ by forming Li7V2(PO4)3 due to the reduction of V3+ into V1+ in the 0.01-3.0 V region, thus qualifying LVP as a rocking chair electrode. In other words, Li3V2(PO4)3/HHC composite demonstrates itself as anode and as cathode for lithium-ion batteries. Li3V2(PO4)3/HHC cathode exhibits ultra high capacity, excellent rate capability at 50C and retains about 99% capacity up to 1000 cycles. As anode, Li3V2(PO4)3/HHC delivers a capacity of 428 mAh g-1 at 50 mA g-1 and tolerates 5 A g-1 condition up to 1000 cycles with a negligible capacity fade. The dual electrode behavior of Li3V2(PO4)3/HHC may be attributed to the unique architecture of HHC that provides high electronic conductivity, facilitates rapid diffusion of lithium ions and admits volume changes during intercalation/deintercalation. More importantly, HHC is a cheap and eco-friendly carbon additive derived from filthy human hair, which in turn offers ample scope for the commercial exploitation of title electrode.

UV-vis-DR study of VO x/SiO 2 catalysts prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Moussa, N.; Ghorbel, A.

2008-12-01

Vanadia-silica catalysts with different vanadium loadings were prepared by sol-gel process. UV-vis diffuse-reflectance spectroscopy was used to elucidate the effect of drying mode (i.e., xerogel vs. aerogel), vanadium loading and calcination on the molecular structure of supported vanadium species. The results indicate that for vanadium loading ranging from 2.8 to 11.2 wt.%, the band-gap energies of all catalysts varying from 2.28 to 2.68 eV which demonstrate that vanadium oxides are predominantly in octahedral structure with the presence of tetrahedral species. The discrimination of different surface VO x species has been based on their characteristic Ligand to Metal Charge Transfer (LMCT) O → V(V) and d-d transition. It was found that the LMCT band position of V dbnd O bond is not affected by calcination either in xerogels or in aerogels but the position and the shape of bands relative to bridging V sbnd O sbnd V bonds are affected by vanadium loading, calcination and drying mode. For the same V/Si ratio, band-gap energy of xerogel is lower than that of aerogel which indicate that vanadium species are more dispersed in aerogels than in xerogels. Drying and calcination led to rearrangement, dehydration, cleavage and crystallization of vanadium species which explain the presence of some amount of crystalline V 2O 5 in calcined samples.

Inverse association of plasma vanadium levels with newly diagnosed type 2 diabetes in a Chinese population.

PubMed

Wang, Xia; Sun, Taoping; Liu, Jun; Shan, Zhilei; Jin, Yilin; Chen, Sijing; Bao, Wei; Hu, Frank B; Liu, Liegang

2014-08-15

Vanadium compounds have been proposed to have beneficial effects on the pathogenesis and complications of type 2 diabetes. Our objective was to evaluate the association between plasma vanadium levels and type 2 diabetes. We performed a case-control study involving 1,598 Chinese subjects with or without newly diagnosed type 2 diabetes (December 2004-December 2007). Cases and controls were frequency-matched by age and sex. Plasma vanadium concentrations were measured and compared between groups. Analyses showed that plasma vanadium concentrations were significantly lower in cases with newly diagnosed type 2 diabetes than in controls (P = 0.001). Mean plasma vanadium levels in participants with and without diabetes were 1.0 μg/L and 1.2 μg/L, respectively. Participants in the highest quartile of plasma vanadium concentration had a notably lower risk of newly diagnosed type 2 diabetes (odds ratio = 0.26, 95% confidence interval: 0.19, 0.35; P < 0.001), compared with persons in the lowest quartile. The trend remained significant after adjustment for known risk factors and in further stratification analyses. Our results suggested that plasma vanadium concentrations were inversely associated with newly diagnosed type 2 diabetes in this Chinese population. © The Author 2014. Published by Oxford University Press on behalf of the Johns Hopkins Bloomberg School of Public Health. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

NASA Astrophysics Data System (ADS)

Mueller, Michael; Baik, Seungyun; Jeon, Hojeong; Kim, Yuchan; Kim, Jungtae; Kim, Young Jun

2015-05-01

The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V2O5 precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V2O5 precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V2O5 precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/VxOx composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V2O5 composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure, kinetics and the presence of a mineralizing aid, such as the two cysteine-constrained peptides on the phage surface, and has potential for use in nanotechnology applications.

Vanadium K-edge XAS studies on the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis.

PubMed

Renirie, Rokus; Charnock, John M; Garner, C David; Wever, Ron

2010-06-01

Vanadium K-edge X-ray Absorption Spectra have been recorded for the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis at pH 6.0. The Extended X-ray Absorption Fine Structure (EXAFS) regions provide a refinement of previously reported crystallographic data; one short V=O bond (1.54A) is present in both forms. For the native enzyme, the vanadium is coordinated to two other oxygen atoms at 1.69A, another oxygen atom at 1.93A and the nitrogen of an imidazole group at 2.02A. In the peroxo-form, the vanadium is coordinated to two other oxygen atoms at 1.67A, another oxygen atom at 1.88A and the nitrogen of an imidazole group at 1.93A. When combined with the available crystallographic and kinetic data, a likely interpretation of the EXAFS distances is a side-on bound peroxide involving V-O bonds of 1.67 and 1.88A; thus, the latter oxygen would be 'activated' for transfer. The shorter V-N bond observed in the peroxo-form is in line with the previously reported stronger binding of the cofactor in this form of the enzyme. Reduction of the enzyme with dithionite has a clear influence on the spectrum, showing a change from vanadium(V) to vanadium(IV).

Iron diminishes the in vitro biological effect of vanadium.

EPA Science Inventory

Mechanistic pathways underlying inflammatory injury following exposures to vanadium-containing compounds are not defined. We tested the postulate that the in vitro biological effect of vanadium results from its impact on iron homeostasis. Human bronchial epithelial (HBE) cells ex...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

Roasting and leaching behaviors of vanadium and chromium in calcification roasting-acid leaching of high-chromium vanadium slag

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Zhou, Mi; Gao, Hui-yang; Liu, Jia-yi; Xue, Xiang-xin

2018-05-01

Calcification roasting-acid leaching of high-chromium vanadium slag (HCVS) was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium. The effects of the purity of CaO, molar ratio between CaO and V2O5 ( n(CaO)/ n(V2O5)), roasting temperature, holding time, and the heating rate used in the oxidation-calcification processes were investigated. The roasting process and mechanism were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetry-differential scanning calorimetry (TG-DSC). The results show that most of vanadium reacted with CaO to generate calcium vanadates and transferred into the leaching liquid, whereas almost all of the chromium remained in the leaching residue in the form of (Fe0.6Cr0.4)2O3. Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with CaO. Moreover, CaO was more likely to combine with vanadium, as further confirmed by thermodynamic analysis. When the HCVS with CaO added in an n(CaO)/ n(V2O5) ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10°C/min from room temperature to 950°C and maintained at this temperature for 60 min, the leaching ratios of vanadium and chromium reached 91.14% and 0.49%, respectively; thus, efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium. Furthermore, the oxidation and calcification reactions of the spinel phases occurred at 592 and 630°C for n(CaO)/ n(V2O5) ratios of 0.5 and 5, respectively.

Facile synthesis of hierarchical porous VOx@carbon composites for supercapacitors.

PubMed

Zhao, Chunxia; Cao, Jinqiao; Yang, Yunxia; Chen, Wen; Li, Junshen

2014-08-01

Hierarchical or micro-nano structured porous VOx@carbon composites were synthesized by a one-step method using phenolic resin as the carbon precursor and ammonium metavanadate as the source of vanadium oxides. The effects of the vanadium source loading on the microstructure and electrochemical properties of the composites were investigated. X-ray diffraction results showed that as the vanadium oxides source loading increased, vanadium oxides in the composites changed oxidation states from V2O3 to mixed states of V2O3 and VO2. Electrochemical test results indicated that the micro-nano porous structure of the composites could facilitate the ion diffusion in the rich porous structure and then promote the electrochemical reaction. More importantly, we found that vanadium oxides greatly enhanced the electrochemical performance of the materials, due to the faradic capacitance generated from vanadium oxide nanoparticles. A maximum specific capacitance of 171 F/g was obtained from VOx@carbon composite with vanadium loading of ∼44 wt%. Further increasing the VOx loading over this fraction was not beneficial. Our results suggested that hierarchical porous VOx@carbon composites were promising candidates for supercapacitor applications. Copyright © 2013 Elsevier Inc. All rights reserved.

Allergic reaction to vanadium causes a diffuse eczematous eruption and titanium alloy orthopedic implant failure.

PubMed

Engelhart, Sally; Segal, Robert J

2017-04-01

Allergy as a cause of adverse outcomes in patients with implanted orthopedic hardware is controversial. Allergy to titanium-based implants has not been well researched, as titanium is traditionally thought to be inert. We highlight the case of a patient who developed systemic dermatitis and implant failure after surgical placement of a titanium alloy (Ti6Al4V) plate in the left foot. The hardware was removed and the eruption cleared in the following weeks. The plate and screws were submitted for metal analysis. The elemental composition of both the plate and screws included 3 major elements-titanium, aluminum, and vanadium-as well as trace elements. Metal analysis revealed that the plate and screws had different microstructures, and electrochemical studies demonstrated that galvanic corrosion could have occurred between the plate and screws due to their different microstructures, contributing to the release of vanadium in vivo. The patient was patch tested with several metals including components of the implant and had a positive patch test reaction only to vanadium trichloride. These findings support a diagnosis of vanadium allergy and suggests that clinicians should consider including vanadium when patch testing patients with a suspected allergic reaction to vanadium-containing implants.

Effect of Vanadyl Rosiglitazone, a New Insulin-Mimetic Vanadium Complexes, on Glucose Homeostasis of Diabetic Mice.

PubMed

Jiang, Pingzhe; Dong, Zhen; Ma, Baicheng; Ni, Zaizhong; Duan, Huikun; Li, Xiaodan; Wang, Bin; Ma, Xiaofeng; Wei, Qian; Ji, Xiangzhen; Li, Minggang

2016-11-01

Diabetes has been cited as the most challenging health problem in the twenty-first century. Accordingly, it is urgent to develop a new type of efficient and low-toxic antidiabetic medication. Since vanadium compounds have insulin-mimetic and potential hypoglycemic activities for type 1 and type 2 diabetes, a new trend has been developed using vanadium and organic ligands to form a new compound in order to increase the intestinal absorption and reduce the toxicity of vanadium compound. In the current investigation, a new organic vanadium compounds, vanadyl rosiglitazone, was synthesized and determined by infrared spectra. Vanadyl rosiglitazone and three other organic vanadium compounds were administered to the diabetic mice through oral administration for 5 weeks. The results of mouse model test indicated that vanadyl rosiglitazone could regulate the blood glucose level and relieve the symptoms of polydipsia, polyphagia, polyuria, and weight loss without side effects and was more effective than the other three organic vanadium compounds including vanadyl trehalose, vanadyl metformin, and vanadyl quercetin. The study indicated that vanadyl rosiglitazone presents insulin-mimetic activities, and it will be a good potential candidate for the development of a new type of oral drug for type 2 diabetes.

Effects of Vanadium-Containing Compounds on Membrane Lipids and on Microdomains Used in Receptor-Mediated Signaling

PubMed Central

Roess, Deborah A.; Smith, Steven M. L.; Winter, Peter; Zhou, Jun; Dou, Ping; Baruah, Bharat; Trujillo, Alejandro M.; Levinger, Nancy E.; Yang, Xioda; Barisas, B. George; Crans, Debbie C.

2011-01-01

There is increasing evidence for the involvement of plasma membrane microdomains in insulin receptor function. Moreover, disruption of these structures, which are typically enriched in sphingomyelin and cholesterol, results in insulin resistance. Treatment strategies for insulin resistance include the use of vanadium compounds which have been shown in animal models to enhance insulin responsiveness. One possible mechanism for insulin-enhancing effects might involve direct effects of vanadium compounds on membrane lipid organization. These changes in lipid organization promote the partitioning of insulin receptors and other receptors into membrane microdomains where receptors are optimally functional. To explore this possibility, we have used several strategies involving vanadium complexes such as [VO2dipic]− (pyridin-2,6-dicarboxylatodioxovanadium(V)), decavanadate (V10O286−, V10), BMOV (bis(maltolato)oxovanadium(IV)) and [VO(saltris)]2 (2-salicylideniminato-2-(hydroxymethyl)-1,3-dihydroxypropane-oxovanadium(V)). Our strategies include an evaluation of interactions between vanadium-containing compounds and model lipid systems, an evaluation of the effects of vanadium compounds on lipid fluidity in erythrocyte membranes, and studies of the effects of vanadium-containing compounds on signaling events initiated by receptors known to use membrane microdomains as signaling platforms. PMID:18729092

Ferrocene and cobaltocene derivatives for non-aqueous redox flow batteries.

PubMed

Hwang, Byunghyun; Park, Min-Sik; Kim, Ketack

2015-01-01

Ferrocene and cobaltocene and their derivatives are studied as new redox materials for redox flow cells. Their high reaction rates and moderate solubility are attractive properties for their use as active materials. The cyclability experiments are carried out in a static cell; the results showed that these materials exhibit stable capacity retention and predictable discharge potentials, which agree with the potential values from the cyclic voltammograms. The diffusion coefficients of these materials are 2 to 7 times higher than those of other non-aqueous materials such as vanadium acetylacetonate, iron tris(2,2'-bipyridine) complexes, and an organic benzene derivative. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microfluidic redox battery.

PubMed

Lee, Jin Wook; Goulet, Marc-Antoni; Kjeang, Erik

2013-07-07

A miniaturized microfluidic battery is proposed, which is the first membraneless redox battery demonstrated to date. This unique concept capitalizes on dual-pass flow-through porous electrodes combined with stratified, co-laminar flow to generate electrical power on-chip. The fluidic design is symmetric to allow for both charging and discharging operations in forward, reverse, and recirculation modes. The proof-of-concept device fabricated using low-cost materials integrated in a microfluidic chip is shown to produce competitive power levels when operated on a vanadium redox electrolyte. A complete charge/discharge cycle is performed to demonstrate its operation as a rechargeable battery, which is an important step towards providing sustainable power to lab-on-a-chip and microelectronic applications.

VANADIUM CHEMISTRY ESSENTIALS FOR TREATMENT STUDIES

EPA Science Inventory

The importance of vanadium occurrence and treatment in drinking water has been elevated by its inclusion in the Contaminant Candidate List. Though it is still too early to know the nature of new regulatory requirements for vanadium, if indeed it becomes regulated, a substantial u...

Spectrophotometric determination of vanadium and its application to gas-turbine fuel-oils.

PubMed

Banerjee, S; Sinha, B P; Dutta, R K

1975-08-01

A very sensitive spectrophotometric method for the determination of vanadium in furnace oils is described. The intense indigo-blue colour developed by the reaction of vanadium with tannin and thioglycollic acid is measured at a wavelength of 600 nm at pH 4 and obeys Beer's law between 0.5 and 5 ppm vanadium. The method is applicable to gas-turbine fuel-oil and special navy fuel-oils. The common mineral constituents usually present in such oils do not interfere.

ON THE SEPARATION OF VANADIUM, MOLYBDENUM AND TUNGSTEN BY MEANS OF PAPER CHROMATOGRAPHY. PART I

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tzou, S.; Liang, S.

1959-02-01

Molybdenum, tangsten, and vanadium are separated by chromatography as per-acids, and then detected with tannin solution. Of the seven solvents tested, n-butanolhydrogen peroxide-nitric acid mixtures offer the best separations. With the addition of dioxane, the R/sub F/ values of these elements increase, while vanadium and tungsten spots overlap. The formation of per-acids avoids the retainment of tungsten on the original spot and the tailings of vanadium and molybdenum spots. (B.O.G.)

Method for preparing high purity vanadium

DOEpatents

Schmidt, Frederick; Carlson, O. Norman

1986-09-09

A method for preparing high purity vanadium having a low silicon content has been developed. Vanadium pentoxide is reduced with a stoichiometric, or slightly deficient amount of aluminum to produce a vanadium-aluminum alloy containing an excess of oxygen. Silicon is removed by electron-beam melting the alloy under oxidizing conditions to promote the formation of SiO which is volatile at elevated temperatures. Excess oxygen is removed by heating the alloy in the presence of calcium metal to form calcium oxide.

Method for preparing high purity vanadium

DOEpatents

Schmidt, F.; Carlson, O.N.

1984-05-16

A method for preparing high purity vanadium having a low silicon content has been developed. Vanadium pentoxide is reduced with a stoichiometric, or slightly deficient amount of aluminum to produce a vanadium-aluminum alloy containing an excess of oxygen. Silicon is removed by electron-beam melting the alloy under oxidizing conditions to promote the formation of SiO which is volatile at elevated temperatures. Excess oxygen is removed by heating the alloy in the presence of calcium metal to form calcium oxide.

Vanadium inhibits DNA-protein cross-links and ameliorates surface level changes of aberrant crypt foci during 1,2-dimethylhydrazine induced rat colon carcinogenesis.

PubMed

Kanna, P Suresh; Saralaya, M G; Samanta, K; Chatterjee, M

2005-01-01

The trace mineral vanadium inhibits cancer development in a variety of experimental animal models. The present study was to gain insight into a putative anticancer effect of vanadium in a rat model of colon carcinogenesis. The in vivo study was intended to clarify the effect of vanadium on DNA-protein cross-links (DPC), surface level changes of aberrant crypt foci (ACF) and biotransformation status during 1,2-dimethylhydrazine (1,2-DMH) induced preneoplastic rat colon carcinogenesis. The comet assay showed statistically higher mean base values of DNA-protein mass (p<0.01) and mean frequencies of tailed cells (p<0.001) in the carcinogen-induced group after treatment with proteinase K. Treatment with vanadium in the form of ammonium monovanadate supplemented ad libitum in drinking water for the entire experimental period caused a significant (p<0.02) reduction (40%) in DNA-protein cross-links in colon cells. Further, the biotransformation status of vanadium was ascertained measuring the drug metabolising enzymes, glutathione S-transferase (GST) and cytochrome P-450 (Cyt P-450). Significantly, there was an increase in glutathione S-transferase and cytochrome P-450 levels (p<0.01 and p<0.02, respectively) in rats supplemented with vanadium as compared to their carcinogen controls. As an endpoint marker, we also evaluated the effect of vanadium on surface level changes of aberrant crypt foci induced by 1,2-DMH by scanning electron microscopy. Animals induced with 1,2-DMH and supplemented with vanadium showed a marked improvement in colonic architecture with less number of aberrant crypt foci in contrast to the animals induced with 1,2-DMH alone, thereby exhibiting its anti-carcinogenicity by modulating the markers studied herein.

Vanadium Induces Dopaminergic Neurotoxicity Via Protein Kinase C-Delta Dependent Oxidative Signaling Mechanisms: Relevance to Etiopathogenesis of Parkinson's Disease

PubMed Central

Afeseh Ngwa, Hilary; Kanthasamy, Arthi; Anantharam, Vellareddy; Song, Chunjuan; Witte, Travis; Houk, R. S.; Kanthasamy, Anumantha G.

2009-01-01

Environmental exposure to neurotoxic metals through various sources including exposure to welding fumes has been linked to an increased incidence of Parkinson's disease (PD). Welding fumes contain many different metals including vanadium typically present as particulates containing vanadium pentoxide (V2O5). However, possible neurotoxic effects of this metal oxide on dopaminergic neuronal cells are not well studied. In the present study, we characterized vanadium-induced oxidative stress-dependent cellular events in cell culture models of PD. V2O5 was neurotoxic to dopaminergic neuronal cells including primary nigral dopaminergic neurons and the EC50 was determined to be 37 μM in N27 dopaminergic neuronal cell model. The neurotoxic effect was accompanied by a time-dependent uptake of vanadium and upregulation of metal transporter proteins Tf and DMT1 in N27 cells. Additionally, vanadium resulted in a threefold increase in reactive oxygen species generation, followed by release of mitochondrial cytochrome c into cytoplasm and subsequent activation of caspase-9 (>fourfold) and caspase-3 (>ninefold). Interestingly, vanadium exposure induced proteolytic cleavage of native protein kinase Cdelta (PKCδ, 72-74 kDa) to yield a 41 kDa catalytically active fragment resulting in a persistent increase in PKCδ kinase activity. Co-treatment with pan-caspase inhibitor ZVAD-FMK significantly blocked vanadium-induced PKCδ proteolytic activation, indicating that caspases mediate PKCδ cleavage. Also, co-treatment with Z-VAD-FMK almost completely inhibited V2O5-induced DNA fragmentation. Furthermore, PKCδ knockdown using siRNA protected N27 cells from V2O5-induced apoptotic cell death. Collectively, these results demonstrate vanadium can exert neurotoxic effects in dopaminergic neuronal cells via caspase-3-dependent PKCδ cleavage, suggesting that metal exposure may promote nigral dopaminergic degeneration. PMID:19646462

The role of vanadium in biology.

PubMed

Rehder, Dieter

2015-05-01

Vanadium is special in at least two respects: on the one hand, the tetrahedral anion vanadate(v) is similar to the phosphate anion; vanadate can thus interact with various physiological substrates that are otherwise functionalized by phosphate. On the other hand, the transition metal vanadium can easily expand its sphere beyond tetrahedral coordination, and switch between the oxidation states +v, +iv and +iii in a physiological environment. The similarity between vanadate and phosphate may account for the antidiabetic potential of vanadium compounds with carrier ligands such as maltolate and picolinate, and also for vanadium's mediation in cardiovascular and neuronal defects. Other potential medicinal applications of more complex vanadium coordination compounds, for example in the treatment of parasitic tropical diseases, may also be rooted in the specific properties of the ligand sphere. The ease of the change in the oxidation state of vanadium is employed by prokarya (bacteria and cyanobacteria) as well as by eukarya (algae and fungi) in respiratory and enzymatic functions. Macroalgae (seaweeds), fungi, lichens and Streptomyces bacteria have available haloperoxidases, and hence enzymes that enable the 2-electron oxidation of halide X(-) with peroxide, catalyzed by a Lewis-acidic V(V) center. The X(+) species thus formed can be employed to oxidatively halogenate organic substrates, a fact with implications also for the chemical processes in the atmosphere. Vanadium-dependent nitrogenases in bacteria (Azotobacter) and cyanobacteria (Anabaena) convert N2 + H(+) to NH4(+) + H2, but are also receptive for alternative substrates such as CO and C2H2. Among the enigmas to be solved with respect to the utilization of vanadium in nature is the accumulation of V(III) by some sea squirts and fan worms, as well as the purport of the nonoxido V(IV) compound amavadin in the fly agaric.

Critical transport issues for improving the performance of aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

2017-01-01

As the fraction of electricity generated from intermittent renewable sources (such as solar and wind) grows, developing reliable energy storage technologies to store electrical energy in large scale is of increasing importance. Redox flow batteries are now enjoying a renaissance and regarded as a leading technology in providing a well-balanced solution for current daunting challenges. In this article, state-of-the-art studies of the complex multicomponent transport phenomena in aqueous redox flow batteries, with a special emphasis on all-vanadium redox flow batteries, are reviewed and summarized. Rather than elaborating on the details of previous experimental and numerical investigations, this article highlights: i) the key transport issues in each battery's component that need to be tackled so that the rate capability and cycling stability of flow batteries can be significantly improved, ii) the basic mechanisms that control the active species/ion/electron transport behaviors in each battery's component, and iii) the key experimental and numerical findings regarding the correlations between the multicomponent transport processes and battery performance.

Geochemical controls on vanadium accumulation in fossil fuels

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1989-01-01

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Geochemical controls of vanadium accumulation in fossil fuels

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1989-01-01

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Synthesis and characterization of polymeric V2O5/AlO(OH) with nanopores on alumina support.

PubMed

Ahmad, A L; Abd Shukor, S R; Leo, C P

2006-12-01

Polymeric vanadium pentoxide gel was formed via the reaction of V2O5 powder with hydrogen peroxide. The polymeric vanadium pentoxide gel was then dispersed in alumina gel. Different vanadium loading composites were coated on alumina support and calcined at 500 degrees C for 1 hr. These composite layers were characterized using TGA, FT-IR, XRD, SEM, and Autosorb. It was found that the lamellar structure of polymerized vanadium pentoxide was retained in the inorganic matrix. Crystalline alumina in gamma phase was formed after calcinations. However, the vanadium-alumina mixed oxides are lack of the well defined PXRD peaks for polycrystalline V2O5. This is possibly because the vanadia species are highly dispersed in the alumina matrix or the vanadia species are dispersed as crystalline which is smaller than 4 nm. In addition, the imbedded polymeric vanadium oxide improved the specific area and average pore diameter of the composite layer.

Microbial vanadium (V) reduction in groundwater with different soils from vanadium ore mining areas.

PubMed

Hao, Liting; Zhang, Baogang; Feng, Chuanping; Zhang, Zhenya; Lei, Zhongfang; Shimizu, Kazuya; Cao, Xuelong; Liu, Hui; Liu, Huipeng

2018-07-01

This work investigated the potential of vanadium (V) (V(V)) bioreduction by using soils sampled from four main kinds of vanadium ore mining areas, i.e. vanadium titanomagnetite, stone coal, petroleum associated minerals and uvanite as inocula. During a typical operation cycle of 60 h, the soils from vanadium titanomagnetite area and petroleum associated minerals area exhibited higher V(V) removal efficiencies, about 92.0 ± 2.0% and 91.0 ± 1.9% in comparison to 87.1 ± 1.9% and 69.0 ± 1.1% for the soils from uvanite and stone coal areas, respectively. Results from high-throughput 16 S rRNA gene pyrosequencing analysis reflect the accumulation of Bryobacter and Acidobacteriaceae with capabilities of V(V) reduction, accompanied with other functional species. This study is helpful to search new functional species for V(V) reduction and to develop in situ bioremediations of V(V) polluted groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Membranes for redox flow battery applications.

PubMed

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-06-19

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

Membranes for Redox Flow Battery Applications

PubMed Central

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-01-01

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention. PMID:24958177

Photocatalytic Activity of Vanadium-Substituted ETS-10

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash,M.; Rykov, S.; Lobo, R.

2007-01-01

Various amounts of vanadium have been isomorphously substituted for titanium in ETS-10, creating samples with V/(V+Ti) ratios of 0.13, 0.33, 0.43, and 1.00 and characterized experimentally using Raman, near-edge X-ray absorption fine structure (NEXAFS), X-ray powder diffraction, N{sub 2} adsorption, scanning electron microscopy (SEM), UV/vis spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Raman spectra reveal a disordered chain structure that contains different V-O bonds along with the presence of a V-O-Ti peak. The UV/vis spectra of the vanadium samples have three new absorption features in the visible region at 450, 594, and 850 nm, suggesting both V{sup 4+}more » and V{sup 5+} are present in the samples. NEXAFS results confirm the presence of both V{sup 5+} and V{sup 4+} in the vanadium samples, with a fraction of V{sup 4+} within the range of 0.2-0.4. The addition of vanadium lowers the band gap energy of ETS-10 from 4.32 eV to a minimum of 3.58 eV for the 0.43ETVS-10 sample. Studies of the photocatalytic polymerization of ethylene show that the 594 nm transition has no photocatalytic activity. The visible transition around 450 nm in the vanadium-incorporated samples is photocatalytically active, and the lower-concentration vanadium samples have higher photocatalytic activity than that of ETS-10 and AM-6, the all-vanadium analogue of ETS-10.« less

Catalytic destruction of PCDD/Fs over vanadium oxide-based catalysts.

PubMed

Yu, Ming-Feng; Lin, Xiao-Qing; Li, Xiao-Dong; Yan, Mi; Prabowo, Bayu; Li, Wen-Wei; Chen, Tong; Yan, Jian-Hua

2016-08-01

Vanadium oxide-based catalysts were developed for the destruction of vapour phase PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans). A vapour phase PCDD/Fs generating system was designed to supply stable PCDD/Fs steam with initial concentration of 3.2 ng I-TEQ Nm(-3). Two kinds of titania (nano-TiO2 and conventional TiO2) and alumina were used as catalyst supports. For vanadium-based catalysts supported on nano-TiO2, catalyst activity is enhanced with operating temperature increasing from 160 to 300 °C and then reduces with temperature rising further to 350 °C. It is mainly due to the fact that high volatility of organic compounds at 350 °C suppresses adsorption of PCDD/Fs on catalysts surface and then further inhibits the reaction between catalyst and PCDD/Fs. The optimum loading of vanadium on nano-TiO2 support is 5 wt.% where vanadium oxide presents highly dispersed amorphous state according to the Raman spectra and XRD patterns. Excessive vanadium will block the pore space and form microcrystalline V2O5 on the support surface. At the vanadium loading of 5 wt.%, nano-TiO2-supported catalyst performs best on PCDD/Fs destruction compared to Al2O3 and conventional TiO2. Chemical states of vanadium in the fresh, used and reoxidized VOx(5 %)/TiO2 catalysts at different operating temperature are also analysed by XPS.

Protective effect of alpha glucosyl hesperidin (G-hesperidin) on chronic vanadium induced testicular toxicity and sperm nuclear DNA damage in male Sprague Dawley rats.

PubMed

Vijaya Bharathi, B; Jaya Prakash, G; Krishna, K M; Ravi Krishna, C H; Sivanarayana, T; Madan, K; Rama Raju, G A; Annapurna, A

2015-06-01

The study was conducted to evaluate the vanadium-induced testicular toxicity and its effect on sperm parameters, sperm nuclear DNA damage and histological alterations in Sprague Dawley rats and to assess the protective effect of G-hesperidin against this damage. Treatment of rats with vanadium at a dose of 1 mg kg bw(-1) for 90 days resulted in significant reduction in serum testosterone levels, sperm count and motility. Further, a parallel increase in abnormal sperm morphology and adverse histopathological changes in testis was also associated with vanadium administration when compared to normal control. Moreover, sperm chromatin dispersion assay revealed that vanadium induces sperm nuclear DNA fragmentation. A marked increase in testicular malondialdehyde levels and decreased activity of antioxidant enzymes such as superoxide dismutase and catalase indicates vanadium-induced oxidative stress. Co-administration of G-hesperidin at a dose of 25 and 50 mg kg bw(-1) significantly attenuated the sperm parameters and histological changes by restoring the antioxidant levels in rat testis. These results suggested that vanadium exposure caused reduced bioavailability of androgens to the tissue and increased free radical formation, thereby causing structural and functional changes in spermatozoa. G-hesperidin exhibited antioxidant effect by protecting the rat testis against vanadium-induced oxidative damage, further ensures antioxidant potential of bioflavonoids. © 2014 Blackwell Verlag GmbH.

Oxidative Stress as a Mechanism Involved in Kidney Damage After Subchronic Exposure to Vanadium Inhalation and Oral Sweetened Beverages in a Mouse Model.

PubMed

Espinosa-Zurutuza, Maribel; González-Villalva, Adriana; Albarrán-Alonso, Juan Carlos; Colín-Barenque, Laura; Bizarro-Nevares, Patricia; Rojas-Lemus, Marcela; López-Valdéz, Nelly; Fortoul, Teresa I

Kidney diseases have notably increased in the last few years. This is partially explained by the increase in metabolic syndrome, diabetes, and systemic blood hypertension. However, there is a segment of the population that has neither of the previous risk factors, yet suffers kidney damage. Exposure to atmospheric pollutants has been suggested as a possible risk factor. Air-suspended particles carry on their surface a variety of fuel combustion-related residues such as metals, and vanadium is one of these. Vanadium might produce oxidative stress resulting in the damage of some organs such as the kidney. Additionally, in countries like Mexico, the ingestion of sweetened beverages is a major issue; whether these beverages alone are responsible for direct kidney damage or whether their ingestion promotes the progression of an existing renal damage generates controversy. In this study, we report the combined effect of vanadium inhalation and sweetened beverages ingestion in a mouse model. Forty CD-1 male mice were distributed in 4 groups: control, vanadium inhalation, 30% sucrose in drinking water, and vanadium inhalation plus sucrose 30% in drinking water. Our results support that vanadium inhalation and the ingestion of 30% sucrose induce functional and histological kidney damage and an increase in oxidative stress biomarkers, which were higher in the combined effect of vanadium plus 30% sucrose. The results also support that the ingestion of 30% sucrose alone without hyperglycemia also produces kidney damage.

Quantitative LIBS analysis of vanadium in samples of hexagonal mesoporous silica catalysts.

PubMed

Pouzar, Miloslav; Kratochvíl, Tomás; Capek, Libor; Smoláková, Lucie; Cernohorský, Tomás; Krejcová, Anna; Hromádko, Ludek

2011-02-15

The method for the analysis of vanadium in hexagonal mesoporous silica (V-HMS) catalysts using Laser Induced Breakdown Spectrometry (LIBS) was suggested. Commercially available LIBS spectrometer was calibrated with the aid of authentic V-HMS samples previously analyzed by ICP OES after microwave digestion. Deposition of the sample on the surface of adhesive tape was adopted as a sample preparation method. Strong matrix effect connected with the catalyst preparation technique (1st vanadium added in the process of HMS synthesis, 2nd already synthesised silica matrix was impregnated by vanadium) was observed. The concentration range of V in the set of nine calibration standards was 1.3-4.5% (w/w). Limit of detection was 0.13% (w/w) and it was calculated as a triple standard deviation from five replicated determinations of vanadium in the real sample with a very low vanadium concentration. Comparable results of LIBS and ED XRF were obtained if the same set of standards was used for calibration of both methods and vanadium was measured in the same type of real samples. LIBS calibration constructed using V-HMS-impregnated samples failed for measuring of V-HMS-synthesized samples. LIBS measurements seem to be strongly influenced with different chemical forms of vanadium in impregnated and synthesised samples. The combination of LIBS and ED XRF is able to provide new information about measured samples (in our case for example about procedure of catalyst preparation). Copyright © 2010 Elsevier B.V. All rights reserved.

Rapid Repairs: Surface Preparation of Ti-3 Al-2.5V Alloy Tubes by Fiber Laser and Welding

DTIC Science & Technology

2008-11-01

processing of titanium 6Al - 4V alloy for potential aerospace component cleaning application, Appl Surf Sci 2005;247:623-630. [11] Turner MW, Crouse...Debroy T, Heat transfer and fluid flow during keyhole mode laser welding of tantalum, Ti- 6Al - 4V , 304 Stainless Steel and Vanadium, J Phy D : Appl Phy...14Titanium alloys are used extensively in aerospace applications mainly due to their superior strength to weight ratio. Different grades of titanium

Field Testing Pulsed Power Inverters in Welding Operations to Control Heavy Metal Emissions

DTIC Science & Technology

2009-12-01

diameter glass fiber media material. After gases passed through the CI, they entered four glass impingers, in series, that were chilled in an ice...Vanadium 0.05 0.05 0.01 (as V2O5 ) 0.00038 - Zinc 2 (as ZnO) 5 (as ZnO) 5 (as ZnO) 0.058 0.166 1...the impactor’s requirement for a specific optimum volumetric flow range. Filter media for each stage of the cascade impactor ( glass fiber filter

Vanadium-pumped titanium x-ray laser

DOEpatents

Nilsen, J.

1992-05-26

A resonantly photo-pumped x-ray laser is formed of a vanadium and titanium foil combination that is driven by two beams of intense line focused optical laser radiation. Ground state neon-like titanium ions are resonantly photo-pumped by line emission from fluorine-like vanadium ions. 4 figs.

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the...

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the...

40 CFR 440.80 - Applicability; description of the vanadium ore subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... vanadium ore subcategory. 440.80 Section 440.80 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Vanadium Ore Subcategory (Mined Alone and Not as a Byproduct) § 440.80 Applicability; description of the...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... uranium, radium and vanadium ores subcategory. 440.30 Section 440.30 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.30 Applicability; description of the...

The Electronic Structure and Field Effects of an Organic-Based Room Temperature Magnetic Semiconductor

DTIC Science & Technology

2007-01-01

used. Other materials used in this study include: microscope slide glass for transistor substrates (Gold Seal), silicon nitride, Si3N4, sputtering...with the top in place. At LBNL the glass tubes were placed in a nitrogen filled glove bag attached to the XAS sample chamber where they were...valences such as vanadium(II) oxide (VO), vanadium(III) oxide (V2O3), vanadium(IV) oxide (VO2), and vanadium(IV) oxide ( V2O5 ). V2O3 in particular is an

One-step hydrothermal synthesis of hexangular starfruit-like vanadium oxide for high power aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Shao, Jie; Li, Xinyong; Qu, Qunting; Zheng, Honghe

2012-12-01

Homogenous hexangular starfruit-like vanadium oxide was prepared for the first time by a one-step hydrothermal method. The assembly process of hexangular starfruit-like structure was observed from TEM images. The electrochemical performance of starfruit-like vanadium oxide was examined by cyclic voltammetry and galvanostatic charge/discharge. The obtained starfruit-like vanadium oxide exhibits a high power capability (19 Wh kg-1 at the specific power of 3.4 kW kg-1) and good cycling stability for supercapacitors application.

Nuclear reactor fuel element with vanadium getter on cladding

DOEpatents

Johnson, Carl E.; Carroll, Kenneth G.

1977-01-01

A nuclear reactor fuel element is described which has an outer cladding, a central core of fissionable or mixed fissionable and fertile fuel material and a layer of vanadium as an oxygen getter on the inner surface of the cladding. The vanadium reacts with oxygen released by the fissionable material during irradiation of the core to prevent the oxygen from reacting with and corroding the cladding. Also described is a method for coating the inner surface of small diameter tubes of cladding with a layer of vanadium.

Vanadium As a Potential Membrane Material for Carbon Capture: Effects of Minor Flue Gas Species.

PubMed

Yuan, Mengyao; Liguori, Simona; Lee, Kyoungjin; Van Campen, Douglas G; Toney, Michael F; Wilcox, Jennifer

2017-10-03

Vanadium and its surface oxides were studied as a potential nitrogen-selective membrane material for indirect carbon capture from coal or natural gas power plants. The effects of minor flue gas components (SO 2 , NO, NO 2 , H 2 O, and O 2 ) on vanadium at 500-600 °C were investigated by thermochemical exposure in combination with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and in situ X-ray diffraction (XRD). The results showed that SO 2 , NO, and NO 2 are unlikely to have adsorbed on the surface vanadium oxides at 600 °C after exposure for up to 10 h, although NO and NO 2 may have exhibited oxidizing effects (e.g., exposure to 250 ppmv NO/N 2 resulted in an 2.4 times increase in surface V 2 O 5 compared to exposure to just N 2 ). We hypothesize that decomposition of surface vanadium oxides and diffusion of surface oxygen into the metal bulk are both important mechanisms affecting the composition and morphology of the vanadium membrane. The results and hypothesis suggest that the carbon capture performance of the vanadium membrane can potentially be strengthened by material and process improvements such as alloying, operating temperature reduction, and flue gas treatment.

Current status and associated human health risk of vanadium in soil in China.

PubMed

Yang, Jie; Teng, Yanguo; Wu, Jin; Chen, Haiyang; Wang, Guoqiang; Song, Liuting; Yue, Weifeng; Zuo, Rui; Zhai, Yuanzheng

2017-03-01

A detailed assessment of vanadium contamination characteristics in China was conducted based on the first national soil pollution survey. The map overlay analysis was used to evaluate the contamination level of vanadium and the non-carcinogenic risk assessment model was calculated to quantify the vanadium exposure risks to human health. The results showed that, due to the drastically increased mining and smelting activities, 26.49% of soils were contaminated by vanadium scattered in southwest of China. According to Canadian soil quality guidelines, about 8.6% of the national soil pollution survey samples were polluted, and pose high non-carcinogenic risks to the public, especially to children living in the vicinity of heavily polluted mining areas. We propose the area near the boundary of Yunnan, Guizhou, Guangxi, and Sichuan provinces as priority control areas due to their higher geochemical background or higher health risks posed to the public. Finally, recommendations for management are proposed, including minimization of contaminant inputs, establishing stringent monitoring program, using phytoremediation, and strengthening the enforcement of relevant laws. Therefore, this study provides a comprehensive assessment of soil vanadium contamination in China, and the results will provide valuable information for China's soil vanadium management and risk avoidance. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

PubMed

Bock, David C; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2013-06-01

Silver vanadium oxide (Ag 2 V 4 O 11 , SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag 2 VO 2 PO 4 , SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO 4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.

Transformation and precipitation in vanadium treated steels

NASA Astrophysics Data System (ADS)

Vassiliou, Andreas D.

A series of carbon manganese steels containing varying amounts of carbon, vanadium and nitrogen was investigated in relation to the solubility of VC and VN in austenite, the grain coarsening characteristics of austenite, the tempering of martensite and other structures, the transformation during continuous cooling, the effect of vanadium addition and increasing nitrogen content on the thermo-mechanical processing of austenite, and the transformation of various morphologies of austenite to ferrite.The sites for preferential nucleation and growth of ferrite were identified and the effect of ferrite grain size inhomogeneity was investigated with a view to minimising it.The C/N ratio in the V(CN) precipitates was largely controlled by C/N ratio in the steel and it was also influenced by the austenitising treatment. As expected, the solubility of VN was less than that of VC.A systematic investigation of austenitising time and temperature on the grain coarsening characteristics was carried out showing the effects of vanadium, carbon and nitrogen. It was tentatively suggested that C-C and N-N clustering in the vanadium free steels controlled the grain growth whereas in the presence of vanadium, it was shown that VN and VC pinned the austenite grain boundaries and restricted grain growth. However coarsening or solution of VC and VN allowed the grain bondaries to migrate and grain coarsening occurred. The grain coarsening temperature was controlled predominantly by VN, whilst the VC dissolved frequently below the grain coarsening temperature.In the as quenched martensite, increasing nitrogen progressively increased the as quenched hardness, and the hardness also greatly increased with increasing carbon and vanadium added together. Examining the precipitation strengthening in tempered martensite showed that in the absence of vanadium, martensite softened progressively with increasing temperature and time. Vanadium additions increased the hardness level during low temperature tempering and at higher tempering temperature introduced secondary hardening. The intensity of secondary hardening increased with increasing vanadium, whereas austenitising temperature had little or no effect. The softening after the secondary hardening was faster after austenitising at the higher temperature and when recrystallisation occurred at the highest tempering temperatures, the hardness was lower due to coarse recrystallised ferrite.Isothermal transformation studies showed that vanadium additions raised the Ar3 temperature and accelerated ferrite nucleation, whilst the growth of ferrite was delayed due to the formation of V(CN) interphase and general precipitation pinning, of the transformation front. Increasing nitrogen content in the V-steel increased the incubation period for ferrite nucleation and increasingly reduced the ferrite growth by increasing V(CN) precipitation pinning of the transformation front.Transformation during continuous cooling was examined in relation to the effect of vanadium, carbon and nitrogen together with the effect of austenitising temperature. Increasing austenitising temperature increased the austenite grain size, and it then became apparent that increasing vanadium, carbon and nitrogen increased the hardenability and raised the hardness level of the jominy curve for the non-martensitic products. (Abstract shortened by ProQuest.).

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

40 CFR 437.44 - Effluent limitations attainable by the application of the best available technology economically...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2... Lead Mercury Nickel Silver Tin Titanium Vanadium Zinc (2) The in-plant limitations that apply to metal... parameters Antimony Arsenic Cadmium Chromium Cobalt Copper Lead Mercury Nickel Silver Tin Titanium Vanadium...

Vanadium-pumped titanium x-ray laser

DOEpatents

Nilsen, Joseph

1992-01-01

A resonantly photo-pumped x-ray laser (10) is formed of a vanadium (12) and titanium (14) foil combination (16) that is driven by two beams (18, 20) of intense line focused (22, 24) optical laser radiation. Ground state neon-like titanium ions (34) are resonantly photo-pumped by line emission from fluorine-like vanadium ions (32).

Effective Recovery of Vanadium from Oil Refinery Waste into Vanadium-Based Metal-Organic Frameworks.

PubMed

Zhan, Guowu; Ng, Wei Cheng; Lin, Wenlin Yvonne; Koh, Shin Nuo; Wang, Chi-Hwa

2018-03-06

Carbon black waste, an oil refinery waste, contains a high concentration of vanadium(V) leftover from the processing of crude oil. For the sake of environmental sustainability, it is therefore of interest to recover the vanadium as useful products instead of disposing of it. In this work, V was recovered in the form of vanadium-based metal-organic frameworks (V-MOFs) via a novel pathway by using the leaching solution of carbon black waste instead of commercially available vanadium chemicals. Two different types of V-MOFs with high levels of crystallinity and phase purity were fabricated in very high yields (>98%) based on a coordination modulation method. The V-MOFs exhibited well-defined and controlled shapes such as nanofibers (length: > 10 μm) and nanorods (length: ∼270 nm). Furthermore, the V-MOFs showed high catalytic activities for the oxidation of benzyl alcohol to benzaldehyde, indicating the strong potential of the waste-derived V-MOFs in catalysis applications. Overall, our work offers a green synthesis pathway for the preparation of V-MOFs by using heavy metals of industrial waste as the metal source.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage.

PubMed

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; Neuefeind, Joerg; Xu, Wenqian; Teng, Xiaowei

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate of 5 mV s -1 , corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full cells after 5,000 cycles at 10 C). The promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.

In situ self-sacrificed template synthesis of vanadium nitride/nitrogen-doped graphene nanocomposites for electrochemical capacitors.

PubMed

Liu, Hong-Hui; Zhang, Hong-Ling; Xu, Hong-Bin; Lou, Tai-Ping; Sui, Zhi-Tong; Zhang, Yi

2018-03-15

Vanadium nitride and graphene have been widely used as pseudo-capacitive and electric double-layer capacitor electrode materials for electrochemical capacitors, respectively. However, the poor cycling stability of vanadium nitride and the low capacitance of graphene impeded their practical applications. Herein, we demonstrated an in situ self-sacrificed template method for the synthesis of vanadium nitride/nitrogen-doped graphene (VN/NGr) nanocomposites by the pyrolysis of a mixture of dicyandiamide, glucose, and NH 4 VO 3 . Vanadium nitride nanoparticles of the size in the range of 2 to 7 nm were uniformly embedded into the nitrogen-doped graphene skeleton. Furthermore, the VN/NGr nanocomposites with a high specific surface area and pore volume showed a high specific capacitance of 255 F g -1 at 10 mV s -1 , and an excellent cycling stability (94% capacitance retention after 2000 cycles). The excellent capacitive properties were ascribed to the excellent conductivity of nitrogen-doped graphene, high surface area, high pore volume, and the synergistic effect between vanadium nitride and nitrogen-doped graphene.

Reduction of Vanadium Oxide (VOx) under High Vacuum Conditions as Investigated by X-Ray Photoelectron Spectroscopy

NASA Astrophysics Data System (ADS)

Chourasia, A.

2015-03-01

Vanadium oxide thin films were formed by depositing thin films of vanadium on quartz substrates and oxidizing them in an atmosphere of oxygen. The deposition was done by the e-beam technique. The oxide films were annealed at different temperatures for different times under high vacuum conditions. The technique of x-ray photoelectron spectroscopy has been employed to study the changes in the oxidation states of vanadium and oxygen in such films. The spectral features in the vanadium 2p, oxygen 1s, and the x-ray excited Auger regions were investigated. The Auger parameter has been utilized to study the changes. The complete oxidation of elemental vanadium to V2O5 was observed to occur at 700°C. At any other temperature, a mixture of oxides consisting of V2O5 and VO2 was observed in the films. Annealing of the films resulted in the gradual loss of oxygen followed by reduction in the oxidation state from +5 to 0. The reduction was observed to depend upon the annealing temperature and the annealing time. Organized Research, TAMU-Commerce.

Effect of substrate temperature on thermochromic vanadium dioxide thin films sputtered from vanadium target

NASA Astrophysics Data System (ADS)

Madiba, I. G.; Kotsedi, L.; Ngom, B. D.; Khanyile, B. S.; Maaza, M.

2018-05-01

Vanadium dioxide films have been known as the most promising thermochromic thin films for smart windows which self-control the solar radiation and heat transfer for energy saving, comfort in houses and automotives. Such an attractive technological application is due to the fact that vanadium dioxide crystals exhibit a fast semiconductor-to-metal phase transition at a transition temperature Tc of about 68 °C, together with sharp optical changes from high transmitive to high reflective coatings in the IR spectral region. The phase transition has been associated with the nature of the microstructure, stoichiometry and stresses related to the oxide. This study reports on the effect of the crystallographic quality controlled by the substrate temperature on the thermochromic properties of vanadium dioxide thin films synthesized by reactive radio frequency inverted cylindrical magnetron sputtering from vanadium target. The reports results are based on X-ray diffraction, Atomic force microscopy, and UV-Visible spectrophotometer. The average crystalline grain size of VO2 increases with the substrate temperature, inducing stress related phenomena within the films.

Nuclear microscope analysis of blood cells from the tropical ascidian Phallusia philippinensis

NASA Astrophysics Data System (ADS)

Hogarth, A. N.; Thong, P. S. P.; Lane, D. J. W.; Watt, F.

1997-07-01

The present study examines the concentrations of vanadium, bromine and sulphur contained within cryofixed/freeze dried blood cells of the ascidian Phallusia philippinensis (Millar, 1975). Elemental profiles of seven cell types were obtained using the National University of Singapore nuclear microscope. Morula cells were found to contain the following mean values; 0.8% vanadium, 3.5% bromine and 6.1% sulphur. Signet ring cells contained 0.5% vanadium, 2.4% bromine and 1.5% sulphur. Compartment cells had 0.1% vanadium, 2.1% bromine and 2.4% sulphur. Other less abundant cell types such as lymphocytes, macrogranular amoebocytes, carotenoid pigment cells and granular amoebocytes were also analysed and found to contain 0.4%, 0.7%, 0.2% and 1.0% vanadium, 2.0%, 1.6%, 0.6% and 1.2% bromine and 1.3%, 1.5%, 0.3% and 4.3% sulphur respectively. Sulphur occurred in high levels in all cell types, which could indicate its involvement in the vanadium concentration process, while bromine, incorporated into complexes, may be utilised for anti-fouling rather than as a deterrent to predators.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE PAGES

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; ...

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

A Disposable Alkaline Phosphatase-Based Biosensor for Vanadium Chronoamperometric Determination

PubMed Central

Alvarado-Gámez, Ana Lorena; Alonso-Lomillo, María Asunción; Domínguez-Renedo, Olga; Arcos-Martínez, María Julia

2014-01-01

A chronoamperometric method for vanadium ion determination, based on the inhibition of the enzyme alkaline phosphatase, is reported. Screen-printed carbon electrodes modified with gold nanoparticles were used as transducers for the immobilization of the enzyme. The enzymatic activity over 4-nitrophenyl phosphate sodium salt is affected by vanadium ions, which results in a decrease in the chronoamperometric current registered. The developed method has a detection limit of 0.39 ± 0.06 μM, a repeatability of 7.7% (n = 4) and a reproducibility of 8% (n = 3). A study of the possible interferences shows that the presence of Mo(VI), Cr(III), Ca(II) and W(VI), may affect vanadium determination at concentration higher than 1.0 mM. The method was successfully applied to the determination of vanadium in spiked tap water. PMID:24569772

A-15 Superconducting composite wires and a method for making

DOEpatents

Suenaga, Masaki; Klamut, Carl J.; Luhman, Thomas S.

1984-01-01

A method for fabricating superconducting wires wherein a billet of copper containing filaments of niobium or vanadium is rolled to form a strip which is wrapped about a tin-alloy core to form a composite. The alloy is a tin-copper alloy for niobium filaments and a gallium-copper alloy for vanadium filaments. The composite is then drawn down to a desired wire size and heat treated. During the heat treatment process, the tin in the bronze reacts with the niobium to form the superconductor niobium tin. In the case where vanadium is used, the gallium in the gallium bronze reacts with the vanadium to form the superconductor vanadium gallium. This new process eliminates the costly annealing steps, external tin plating and drilling of bronze ingots required in a number of prior art processes.

Wrapping process for fabrication of A-15 superconducting composite wires

DOEpatents

Suenaga, M.; Klamut, C.J.; Luhman, T.S.

1980-08-15

A method for fabricating superconducting wires wherein a billet of copper containing filaments of niobium or vanadium is rolled to form a strip which is wrapped about a tin-alloy core to form a composite. The alloy is a tin-copper alloy for niobium filaments and a gallium-copper alloy for vanadium filaments. The composite is then drawn down to a desired wire size and heat treated. During the heat treatment process, the tin in the bronze reacts with the niobium to form the superconductor niobium tin. In the case where vanadium is used, the gallium in the gallium bronze reacts with the vanadium to form the superconductor vanadium gallium. This new process eliminates the costly annealing steps, external tin plating and drilling of bronze ingots required in a number of prior art processes.

Fusion materials: Technical evaluation of the technology of vandium alloys for use as blanket structural materials in fusion power systems

NASA Astrophysics Data System (ADS)

1993-08-01

The Committee's evaluation of vanadium alloys as a structural material for fusion reactors was constrained by limited data and time. The design of the International Thermonuclear Experimental Reactor is still in the concept stage, so meaningful design requirements were not available. The data on the effect of environment and irradiation on vanadium alloys were sparse, and interpolation of these data were made to select the V-5Cr-5Ti alloy. With an aggressive, fully funded program it is possible to qualify a vanadium alloy as the principal structural material for the ITER blanket in the available 5 to 8-year window. However, the data base for V-5Cr-5Ti is limited and will require an extensive development and test program. Because of the chemical reactivity of vanadium the alloy will be less tolerant of system failures, accidents, and off-normal events than most other candidate blanket structural materials and will require more careful handling during fabrication of hardware. Because of the cost of the material more stringent requirements on processes, and minimal historical working experience, it will cost an order of magnitude to qualify a vanadium alloy for ITER blanket structures than other candidate materials. The use of vanadium is difficult and uncertain; therefore, other options should be explored more thoroughly before a final selection of vanadium is confirmed. The Committee views the risk as being too high to rely solely on vanadium alloys. In viewing the state and nature of the design of the ITER blanket as presented to the Committee, it is obvious that there is a need to move toward integrating fabrication, welding, and materials engineers into the ITER design team. If the vanadium alloy option is to be pursued, a large program needs to be started immediately. The commitment of funding and other resources needs to be firm and consistent with a realistic program plan.

[Interaction Between Occupational Vanadium Exposure and hsp70-hom on Neurobehavioral Function].

PubMed

Zhang, Qin; Liu, Yun-xing; Cui, Li; Li, Shun-pin; Gao, Wei; Hu, Gao-lin; Zhang, Zu-hui; Lan, Ya-jia

2016-01-01

In determine the effect of heat shock protein 70-hom gene (hsp70-hom) polymorphism on the neurobehavioral function of workers exposed to vanadium. Workers from the vanadium products and chemical industry were recruited by cluster sampling. Demographic data and exposure information were collected using a questionnaire. Neurobehavioral function was assessed by Neurobehavioral Core Test Battery. The hsp70-hom genotype was detected by restricted fragment length polymorphism-polymerase chain reaction (RFLP-PCR). A neurobehavioral index (NBI) was formulated through principal component analysis. Workers with a T/C genotype had worse performance in average reaction time, visual retention, digital span (backward), Santa Ana aiming (non-habitual hand), pursuit aiming (right points, total points), digit symbol and NBI score than others (P < 0.05). The relative risk of abnormal NBI score of the workers with a T/C genotype was 1.748 fold of those with a T/T genotype. The relative risk of abnormal.NBI score of the workers exposed to vanadium was 3.048 fold of controls (P < 0.05). But after adjustment with age and education, only vanadium exposure appeared with a significant effect on NBI score. When gene polymorphism and vanadium exposure coexisted, the effect of vanadium on neurobehavioral function was attenuated, but the influence of T/C genotype increased Codds ratio (OR = 4.577, P < 0.05). After adjustment with age and education, the OR of T/C genotype further increased to 7.777 (P < 0.05). Vanadium exposure and T/C genotype had.a bio-interaction effect on NBI score Crelative excess risk due to interaction (RERI) = 4.12, attributable proportion (AP) = 0.7, synergy index (S) = 6.45]. After adjustment with age and education, the RERI became 2.49 and the AP became 0.75, but no coefficient of interaction was produced. Priorities of occupational protection should be given to vanadium-exposed workers with a hsp70-hom T/C genotype and low education level.

Structural and silver/vanadium ratio effects on silver vanadium phosphorous oxide solution formation kinetics: impact on battery electrochemistry.

PubMed

Bock, David C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

2015-01-21

The detailed understanding of non-faradaic parasitic reactions which diminish battery calendar life is essential to the development of effective batteries for use in long life applications. The dissolution of cathode materials including manganese, cobalt and vanadium oxides in battery systems has been identified as a battery failure mechanism, yet detailed dissolution studies including kinetic analysis are absent from the literature. The results presented here provide a framework for the quantitative and kinetic analyses of the dissolution of cathode materials which will aid the broader community in more fully understanding this battery failure mechanism. In this study, the dissolution of silver vanadium oxide, representing the primary battery powering implantable cardioverter defibrillators (ICD), is compared with the dissolution of silver vanadium phosphorous oxide (Ag(w)VxPyOz) materials which were targeted as alternatives to minimize solubility. This study contains the first kinetic analyses of silver and vanadium solution formation from Ag0.48VOPO4·1.9H2O and Ag2VP2O8, in a non-aqueous battery electrolyte. The kinetic results are compared with those of Ag2VO2PO4 and Ag2V4O11 to probe the relationships among crystal structure, stoichiometry, and solubility. For vanadium, significant dissolution was observed for Ag2V4O11 as well as for the phosphate oxide Ag0.49VOPO4·1.9H2O, which may involve structural water or the existence of multiple vanadium oxidation states. Notably, the materials from the SVPO family with the lowest vanadium solubility are Ag2VO2PO4 and Ag2VP2O8. The low concentrations and solution rates coupled with their electrochemical performance make these materials interesting alternatives to Ag2V4O11 for the ICD application.

Electrochemical modification of a pyrolytic graphite sheet for improved negative electrode performance in the vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Kabir, Humayun; Gyan, Isaiah O.; Francis Cheng, I.

2017-02-01

The vanadium redox flow battery is a promising technology for buffering renewable energies. It is recognized that negative electrode is the limitation in this device where there are problems of slow heterogeneous electron transfer (HET) of V3+/2+ and parasitic H2 evolution. Any methods aimed at addressing one of these barriers must assess the effects on the other. We examine electrochemical enhancement of a common commercially available material. Treatment of Panasonic pyrolytic graphite sheets is through oxidation at 2.1 V vs. Ag/AgCl for 1 min in 1 M H2SO4. This increases the standard HET rate for V3+/2+ from 3.2 × 10-7 to 1 × 10-3 cm/s, one of the highest in literature and shifts voltammetric reductive peak potential from -1.0 V to -0.65 V in 50 mM V3+ in 1 M H2SO4. Infrared analysis of the surfaces indicates formation of Csbnd OH, Cdbnd O, and Csbnd O functionalities. These groups catalyze HET with V3+/2+ as hypothesized by Skyllas-Kasacos. Also of significance is that electrode modification decreases the fraction of the current directed towards H2 evolution. This proportion decreases by two orders of a magnitude from 12% to 0.1% as measured at the respective voltammetric peak potentials of -1.0 V (pristine) and -0.65 V (modified).

Homology of vanadium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasyutinskii, N.A.

1987-05-01

The authors examine the homology of vanadium oxide and note that data on the existence of phases and homogeneity limits in the V-O system are very contradictory. A graphical illustration shows the homologous series of vanadium oxides. The predominant part of the discrete formations in the system V-O is characterized by integral stoichiometry and forms six homologous series. It is found that homologous series of vanadium oxides are not only a basis for systematization of such oxides, but also may serve as a means for predicting the composition of new phases, limits of homogeneity, their structure, and properties.

Cytotoxic effect of vanadium and oil-fired fly ash on hamster tracheal epithelium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schiff, L.J.; Graham, J.A.

1984-08-01

Hamster tracheal organ cultures were used to study the in vitro effects of vanadium and oil-fired fly ash on mucociliary respiratory epithelium. Two vanadium compounds, VOSO/sub 4/ and V/sub 2/O/sub 5/, and fly ash from an oil-fueled power plant were dissolved or suspended in culture medium over a range of concentrations and epithelia were exposed for 1 hr/day, for 9 consecutive days. At intervals during this period, alterations in cilia-beating frequency, cytology, and histology were documented by light microscopy. Explants treated with VOSO/sub 4/ either decreased ciliary activity or produced ciliostasis depending upon the concentration and length of exposure. Earlymore » morphological alterations consisted of vacuolization of both nuclei and cytoplasm. After multiple exposures, cytology of VOSO/sub 4/-treated respiratory mucosa was markedly affected. Similar changes were observed in cultures exposed to V/sub 2/O/sub 5/; however, the cytotoxicity appeared earlier and was more pronounced. Fly ash-treated explants produced similar biological effects when compared to both vanadium compounds. Thus, the data indicate that the extent of vanadium toxicity depends, at least in part, on the vanadium content of the compound tested, and that exposure to this metal and vanadium-rich fly ash can inhibit normal mucociliary function, a vital clearance mechanism in the respiratory tract.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, G.N.; Coyle, C.L.; Hales, B.J.

Evidence for the existence of a vanadium-containing nitrogenase has existed for more than half a century, but progress in understanding this enzyme has only come recently. In 1980, Bishop and co-workers proposed that an alternative nitrogen-fixing enzyme exists in Azotobacter vinelandii and subsequently proposed that vanadium was involved. In 1986, Robson et al. demonstrated clearly that the alternate nitrogenase from Azotobacter chroococcum, Acl*, contained vanadium instead of molybdenum. Hales et al. have shown the vanadium is also found in the Azotobacter vinelandii alternative component I, Avl'. The molybdenum and vanadium nitrogenase proteins are similar in many respects. Like the molybdenummore » enzyme, both Acl* and Avl' exhibit an EPR spectrum characteristic of a species with an S = 3/2 ground state; Avl' also contains the so-called P-clusters. Additionally Acl* has recently been shown to possess an N-methylformamide soluble cofactor, FeVco, analogous to the well-known iron-molybdenum cofactor FeMoco. Arber et al. have reported X-ray absorption spectra for the Acl* enzyme and interpreted the EXAFS as evidence for a V-Fe-S cluster. The local vanadium structure is proposed to resemble a recently synthesized cubane-like VFe/sub 3/S/sub 4/ cluster, and analogies are drawn with the EXAFS-derived structure reported for the molybdenum nitrogenases. The authors report herein an X-ray absorption spectroscopic study of A. vinelandii vanadium nitrogenase, Avl', which supports and extends the work of Arber et al.« less

Preliminary investigation of the elemental variation and diagenesis of a tabular uranium deposit, La Sal Mine, San Juan County, Utah

USGS Publications Warehouse

Brooks, Robert A.; Campbell, John A.

1976-01-01

Ore in the La Sal mine, San Juan County, Utah, occurs as a typical tabular-type uranium deposit of the-Colorado Plateau. Uranium-vanadium occurs in the Salt Wash Member of the Jurassic Morrison Formation. Chemical and petrographic analyses were used to determine elemental variation and diagenetic aspects across the orebody. Vanadium is concentrated in the dark clay matrix, which constitutes visible ore. Uranium content is greater above the vanadium zone. Calcium, carbonate carbon, and lead show greater than fifty-fold increase across the ore zone, whereas copper and organic carbon show only a several-fold increase. Large molybdenum concentrations are present in and above the tabular layer, and large selenium concentrations occur below the uranium zone within the richest vanadium zone. Iron is enriched in the vanadium horizon. Chromium is depleted from above the ore and strongly enriched below. Elements that vary directly with the vanadium content include magnesium, iron, selenium, zirconium, strontium, titanium, lead, boron, yttrium, and scandium. The diagenetic sequence is as follows: (1) formation of secondary quartz overgrowths as cement; (2) infilling and lining of remaining pores with amber opaline material; (3) formation of vanadium-rich clay matrix, which has replaced overgrowths as well as quartz grains; (4) replacement of overgrowths and detrital grains by calcite; (5) infilling of pores with barite and the introduction of pyrite and marcasite.

40 CFR 421.222 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... technical grade molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 40.778 18.145 Chromium... vanadium plus pure grade molybdenum produced Arsenic 121.720 54.162 Chromium 25.625 10.483 Lead 24.460 11... times. (c) Vanadium decomposition wet air pollution control. BPT Limitations for the Secondary...

Vanadium hydride deuterium-tritium generator

DOEpatents

Christensen, Leslie D.

1982-01-01

A pressure controlled vanadium hydride gas generator to provide deuterium-tritium gas in a series of pressure increments. A high pressure chamber filled with vanadium-deuterium-tritium hydride is surrounded by a heater which controls the hydride temperature. The heater is actuated by a power controller which responds to the difference signal between the actual pressure signal and a programmed pressure signal.

77 FR 46712 - Ferrovanadium and Nitrided Vanadium From the Russian Federation: Negative Final Determination of...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-06

... Determination We determine that the importation of vanadium pentoxide from the Russian Federation (Russia) by...) from Russia, within the meaning of section 781(a) of the Tariff Act of 1930, as amended (the Act). \\1... its negative preliminary determination that Evraz's imports of vanadium pentoxide from Russia that are...

Comparison of W-VC-C composites against Co-60, Se-75 and Sb-125 for gamma radioisotope sources

NASA Astrophysics Data System (ADS)

Demir, Ertugrul; Tugrul, A. Beril; Buyuk, Bulent; Yilmaz, Ozan; Ovecoglu, Lutfi

2018-02-01

Tungsten based materials are considered to be the promising materials for nuclear applications due to the good properties. The tungsten composite materials have so many advantages in nuclear technological applications especially fusion reactor systems. In this paper, Tungsten-Vanadium carbide-Graphite (W-VC-C) which include 93% tungsten (W), 6% vanadium carbide (VC) and 1% graphite (C) also which has three different alloying time (6-12-24 hours) were produced by mechanical alloying method. Co-60, Se-75 and Sb-125 gamma radioisotopeswere used as a gamma sources in order to determine behavior of gamma attenuation properties of the composite materials. The experimental results were compared with each other to clarify effects of varying gamma energies on the tungsten based composite materials. The mass attenuation coefficients of the samples were obtained by using XCOM computer code and compared with experimental data. The gamma linear attenuation, the mass attenuation coefficients and half value thickness (HVL) of the samples were evaluated and compared with Co-60, Se-75 and Sb-125 for gamma radioisotopes. Results showed that gamma attenuation coefficients of the samples depend on gamma energies and mechanical alloying time has negatively effect on the gamma shielding properties for the all studied W-VC-C.

Adsorption of Vanadium (V) from SCR Catalyst Leaching Solution and Application in Methyl Orange.

PubMed

Sha, Xuelong; Ma, Wei; Meng, Fanqing; Wang, Ren; Fuping, Tian; Wei, Linsen

2016-12-01

  In this study, we explored an effective and low-cost catalyst and its adsorption capacity and catalytic capacity for Methyl Orange Fenton oxidation degradation were investigated. The catalyst was directly prepared by reuse of magnetic iron oxide (Fe3O4) after saturated adsorption of vanadium (V) from waste SCR (Selective Catalytic Reduction) catalyst. The obtained catalyst was characterized by FTIR, XPS and the results showed that vanadium (V) adsorption process of Fe3O4 nanoparticles was non-redox reaction. The effects of pH, adsorption kinetics and equilibrium isotherms of adsorption were assessed. Adsorption of vanadium (V) ions by Fe3O4 nanoparticles could be well described by the Sips isotherm model which controlled by the mixed surface reaction and diffusion (MSRDC) adsorption kinetic model. The results show that vanadium (V) was mainly adsorbed on external surface of the Fe3O4 nanoparticles. The separation-recovering tungsten (VI) and vanadium (V) from waste SCR catalyst alkaline solution through pH adjustment was also investigated in this study. The results obtained from the experiments indicated that tungsten (VI) was selectively adsorbed from vanadium (V)/tungsten (VI) mixed solution in certain acidic condition by Fe3O4 nanoparticle to realize their recovery. Tungsten (V) with some impurity can be obtained by releasing from adsorbent, which can be confirmed by ICP-AES. The Methyl Orange degradation catalytic performance illustrated that the catalyst could improve Fenton reaction effectively at pH = 3.0 compare to Fe3O4 nanoparticles alone. Therefore, Fe3O4 nanoparticle adsorbed vanadium (V) has a potential to be employed as a heterogeneous Fenton-like catalyst in the present contribution, and its catalytic activity was mainly evaluated in terms of the decoloration efficiency of Methyl Orange.

Structural study of VO {sub x} doped aluminium fluoride and aluminium oxide catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheurell, Kerstin; Scholz, Gudrun; Kemnitz, Erhard

The structural properties of vanadium doped aluminium oxyfluorides and aluminium oxides, prepared by a modified sol-gel synthesis route, were thoroughly investigated. The influence of the preparation technique and the calcination temperature on the coordination of vanadium, aluminium and fluorine was analysed by different spectroscopic methods such as Raman, MAS NMR and ESR spectroscopy. In all samples calcined at low temperatures (350 deg. C), vanadium coexists in two oxidation states V{sup IV} and V{sup V}, with V{sup IV} as dominating species in the vanadium doped aluminium oxyfluorides. In the fluoride containing solids aluminium as well as vanadium are coordinated by fluorinemore » and oxygen. Thermal annealing of 800 deg. C leads to an extensive reorganisation of the original matrices and to the oxidation of V{sup IV} to V{sup V} in both systems. - Graphical abstract: Structure model for VO {sub x} doped aluminium oxide.« less

TEM investigation of ductile iron alloyed with vanadium.

PubMed

Dymek, S; Blicharski, M; Morgiel, J; Fraś, E

2010-03-01

This article presents results of the processing and microstructure evolution of ductile cast iron, modified by an addition of vanadium. The ductile iron was austenitized closed to the solidus (1095 degrees C) for 100 h, cooled down to 640 degrees C and held on at this temperature for 16 h. The heat treatment led to the dissolution of primary vanadium-rich carbides and their subsequent re-precipitation in a more dispersed form. The result of mechanical tests indicated that addition of vanadium and an appropriate heat treatment makes age hardening of ductile iron feasible. The precipitation processes as well as the effect of Si content on the alloy microstructure were examined by scanning and transmission electron microscopy. It was shown that adjacent to uniformly spread out vanadium-rich carbides with an average size of 50 nm, a dispersoid composed of extremely small approximately 1 nm precipitates was also revealed.

Insight into the adsorption mechanisms of vanadium(V) on a high-efficiency biosorbent (Ti-doped chitosan bead).

PubMed

Liu, Xin; Zhang, Lingfan

2015-08-01

In this present study, a new chitosan bead modified with titanium ions (TiCB) was prepared and employed for the adsorption of vanadium ions from aqueous solutions. Batch adsorption experiments were performed to research the effect of various factors, including pH, temperature, contact time and initial concentration of vanadium(V) ions. The adsorption of vanadium was followed by the pseudo second-order kinetic and the Langmuir isotherm model, with a remarkable maximum adsorption capacity of 210 mg/g. The analysis of thermodynamic parameters (ΔG°, ΔH° and ΔS°) revealed that the nature of adsorption was feasible, spontaneous (ΔG°<0) and endothermic (ΔH°>0) process. FTIR, EDS, EMI and XPS studies suggested that the mechanisms of adsorption were possibly attributed to electrostatic attraction, ligand-exchange and redox reaction between TiCB and vanadium ions. Copyright © 2015 Elsevier B.V. All rights reserved.

Vanadium removal from LD converter slag using bacteria and fungi.

PubMed

Mirazimi, S M J; Abbasalipour, Z; Rashchi, F

2015-04-15

Removal of vanadium from Linz-Donawits (LD) converter slag was investigated by means of three different species of microbial systems: Acidithiobacillus thiooxidans (autotrophic bacteria), Pseudomonas putida (heterotrophic bacteria) and Aspergillus niger (fungi). The bioleaching process was carried out in both one-step and two-step process and the leaching efficiencies in both cases were compared. Formation of inorganic and organic acids during the leaching process caused mobilization of vanadium. In order to reduce toxic effects of the metal species on the above mentioned microorganisms, a prolonged adaptation process was performed. Both bacteria, A. thiooxidans and P. putida were able to remove more than 90% of vanadium at slag concentrations of 1-5 g L(-1) after 15 days. Also, the maximum achievable vanadium removal in the fungal system was approximately 92% at a slag concentration of 1 g L(-1) after 22 days. Copyright © 2015 Elsevier Ltd. All rights reserved.

Vanadium K-edge X-ray absorption spectroscopy of bromoperoxidase from Ascophyllum nodosum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arber, J.M.; de Boer, E.; Garner, C.D.

Bromoperoxidase from Ascophyllum nodusum was the first vanadium-containing enzyme to be isolated. X-ray absorption spectra have now been collected in order to investigate the coordination of vanadium in the native, native plus bromide, native plus hydrogen peroxide, and dithionite-reduced forms of the enzyme. The edge and X-ray absorption near-edge structures show that, in the four samples studied, it is only on reduction of the native enzyme that the metal site is substantially altered. In addition, these data are consistent with the presence of vanadium(IV) in the reduced enzyme and vanadium(V) in the other samples. Extended X-ray absorption fine structure datamore » confirm that there are structural changes at the metal site on reduction of the native enzyme, notably a lengthening of the average inner-shell distance, and the presence of terminal oxygen together with histidine and oxygen-donating residues.« less

Minor elements in Keweenawan lavas, Michigan

USGS Publications Warehouse

Cornwall, H.R.; Rose, H.J.

1957-01-01

The distribution of minor elements in three basaltic flows of the Keweenawan series, of Michigan, is related to differentiation in the flows. Thus, nickel is most abundant in the early differentiates; nickel, chromium, and barium are generally deficient in the pegmatites, which formed late; whereas copper, vanadium, yttrium, and other minor elements are concentrated in the pegmatites. The minor-element content of individual minerals in the Greenstone flow varies markedly from one mineral to another and seems to depend primarily on the presence or absence in the minerals of major elements for which the minor elements can substitute. Minor elements have substituted most readily for those major elements with similar ionic radii. Valence and electronegativity also seem to influence the ease of substitution. The distribution of other minor elements in copper-bearing lodes of the Michigan copper district shows no apparent relation to copper mineralization. ?? 1957.

Vanadium Microalloyed High Strength Martensitic Steel Sheet for Hot-Dip Coating

NASA Astrophysics Data System (ADS)

Hutchinson, Bevis; Komenda, Jacek; Martin, David

Cold rolled steels with various vanadium and nitrogen levels have been treated to simulate the application of galvanizing and galvannealing to hardened martensitic microstructures. Strength levels were raised 100-150MPa by alloying with vanadium, which mitigates the effect of tempering. This opens the way for new ultra-high strength steels with corrosion resistant coatings produced by hot dip galvanising.

Vanadium hydride deuterium-tritium generator

DOEpatents

Christensen, L.D.

1980-03-13

A pressure controlled vanadium hydride gas generator was designed to provide deuterium-tritium gas in a series of pressure increments. A high pressure chamber filled with vanadium-deuterium-tritium hydride is surrounded by a heater which controls the hydride temperature. The heater is actuated by a power controller which responds to the difference signal between the actual pressure signal and a programmed pressure signal.

Synthesis of nanostructured vanadium powder by high-energy ball milling: X-ray diffraction and high-resolution electron microscopy characterization

NASA Astrophysics Data System (ADS)

Krishnan, Vinoadh Kumar; Sinnaeruvadi, Kumaran

2016-10-01

Vanadium metal powders, ball milled with different surfactants viz., stearic acid, KCl and NaCl, have been studied by X-ray diffraction and transmission electron microscopy. The surfactants alter the microstructural and morphological characteristics of the powders. Ball milling with stearic acid results in solid-state amorphization, while powders milled with KCl yield vanadium-tungsten carbide nanocomposite mixtures. NaCl proved to be an excellent surfactant for obtaining nanostructured fusion-grade vanadium powders. In order to understand the reaction mechanism behind any interstitial addition in the ball-milled powders, CHNOS analysis was performed.

Vanadium doped tin dioxide as a novel sulfur dioxide sensor.

PubMed

Das, S; Chakraborty, S; Parkash, O; Kumar, D; Bandyopadhyay, S; Samudrala, S K; Sen, A; Maiti, H S

2008-04-15

Considering the short-term exposure limit of SO2 to be 5 ppm, we first time report that semiconductor sensors based on vanadium doped SnO2 can be used for SO2 leak detection because of their good sensitivity towards SO2 at concentrations down to 5 ppm. Such sensors are quite selective in presence of other gases like carbon monoxide, methane and butane. The high sensitivity of vanadium doped tin dioxide towards SO2 may be understood by considering the oxidation of sulfur dioxide to sulfur trioxide on SnO2 surface through redox cycles of vanadium-sulfur-oxygen adsorbed species.

Amorphous and Crystalline Vanadium Oxides as High-Energy and High-Power Cathodes for Three-Dimensional Thin-Film Lithium Ion Batteries.

PubMed

Mattelaer, Felix; Geryl, Kobe; Rampelberg, Geert; Dendooven, Jolien; Detavernier, Christophe

2017-04-19

Flexible wearable electronics and on-chip energy storage for wireless sensors drive rechargeable batteries toward thin-film lithium ion batteries. To enable more charge storage on a given surface, higher energy density materials are required, while faster energy storage and release can be obtained by going to thinner films. Vanadium oxides have been examined as cathodes in classical and thin-film lithium ion batteries for decades, but amorphous vanadium oxide thin films have been mostly discarded. Here, we investigate the use of atomic layer deposition, which enables electrode deposition on complex three-dimensional (3D) battery architectures, to obtain both amorphous and crystalline VO 2 and V 2 O 5 , and we evaluate their thin-film cathode performance. Very high volumetric capacities are found, alongside excellent kinetics and good cycling stability. Better kinetics and higher volumetric capacities were observed for the amorphous vanadium oxides compared to their crystalline counterparts. The conformal deposition of these vanadium oxides on silicon micropillar structures is demonstrated. This study shows the promising potential of these atomic layer deposited vanadium oxides as cathodes for 3D all-solid-state thin-film lithium ion batteries.

Vanadium oxide thin films produced by magnetron sputtering from a V2O5 target at room temperature

NASA Astrophysics Data System (ADS)

de Castro, Marcelo S. B.; Ferreira, Carlos L.; de Avillez, Roberto R.

2013-09-01

Vanadium oxide thin films were grown by RF magnetron sputtering from a V2O5 target at room temperature, an alternative route of production of vanadium oxide thin films for infrared detector applications. The films were deposited on glass substrates, in an argon-oxygen atmosphere with an oxygen partial pressure from nominal 0% to 20% of the total pressure. X-ray diffraction (XRD) and X-ray photon spectroscopy (XPS) analyses showed that the films were a mixture of several vanadium oxides (V2O5, VO2, V5O9 and V2O3), which resulted in different colors, from yellow to black, depending on composition. The electrical resistivity varied from 1 mΩ cm to more than 500 Ω cm and the thermal coefficient of resistance (TCR), varied from -0.02 to -2.51% K-1. Computational thermodynamics was used to simulate the phase diagram of the vanadium-oxygen system. Even if plasma processes are far from equilibrium, this diagram provides the range of oxygen pressures that lead to the growth of different vanadium oxide phases. These conditions were used in the present work.

Effect of vanadium doping on structural and magnetic properties of defective nano-nickel ferrite

NASA Astrophysics Data System (ADS)

Heiba, Zein K.; Mohamed, Mohamed Bakr; Wahba, Adel Maher; Almalowi, M. I.

2018-04-01

Nano-nickel ferrites defected by vanadium doping (NiV x Fe2-1.67 x O4, 0 ≤ x ≤ 0.25) were prepared using a simple sol gel method. Rietveld analysis revealed a nonmonotonic change in lattice parameter, oxygen parameter and magnetization upon doping with vanadium. Cation distributions suggested from either Rietveld analysis or from experimental magnetic moments were in a good agreement. For low doping values ( x = 0.05), vanadium was residing mainly in octahedral sites, while for samples with vanadium content ( x ≥ 0.1) a significant part of vanadium ions resided at tetrahedral sites; a result which has been confirmed by the analysis of Fourier-transform infrared (FTIR) spectrums obtained for the samples. The transmission electron microscope (TEM) image showed fine spherical particles with size of ˜ 11 nm. All samples showed a superparamagnetic nature with a nonmonotonic change of either magnetization ( M S) or coercivity (H C) with the content of nonmagnetic V5+. The cation occupancies indicated presence of an enormous number of vacancies through doping with high valence cation V5+, making present samples potential electrodes for Li- or Na-ion batteries.

Visible light driven photocatalyst of vanadium (V3+) doped TiO2 synthesized using sonochemical method

NASA Astrophysics Data System (ADS)

Aini, N.; Ningsih, R.; Maulina, D.; Lami’, F. F.; Chasanah, S. N.

2018-03-01

TiO2 has been widely investigated due to its superior photocatalytic activity under ultraviolet irradiation among the photocatalyst materials. In this research, vanadium (V3+) was doped into TiO2 to enhance its light response under visible irradiation for wider application. Vanadium was introduced into TiO2 lattice at various concentration respectively 0.3, 0.5, 0.7 and 0.9% using simple and fast sonochemical method. X-Ray Diffraction data show that vanadium doped TiO2 crystallized in anatase phase with I41amd space group. X-Ray Diffraction pattern shifted to lower value of 2θ due to vanadium dopant. It indicated that V3+ was incorporated into anatase lattice. UV-Vis Diffuse Reflectance Spectra was revealed that the doped TiO2 has lowered reflectance and enhanced absorption coefficient in visible region than undoped TiO2 and commercial anatase TiO2. Band gap energy for undoped and doped TiO2 were respectively 3.22, 3.05, 2.93, 3.03 and 2.40 eV. Therefore vanadium doped TiO2 had potential to be applied under visible light.

Comparative erythropoietic effects of three vanadium compounds.

PubMed

Hogan, G R

2000-07-10

The biotoxic effects of vanadium are variable depending upon a number of factors including the oxidation state of the test compound. This study reports the effects of three vanadium compounds on peripheral erythrocytes. On day 0 female ICR mice received a single injection of vanadium chloride (V-III), vanadyl sulfate (V-IV), or sodium orthovandate (V-V). At scheduled intervals post-injection, the number of circulating erythrocytes [red blood cells per millimeter cubed (RBC/mm3)], reticulocyte percentages, and radioiron uptake percentages were determined and compared to mice receiving saline only. Data show that all three test substances promoted a significant lowering of RBC/mm3 beginning on day 1 for V-IV and V-V and on day 2 for V-III through day 4. The reticulocyte percentages increase followed the same time course as that of the peripheral RBC decrease. Peak reticulocytosis was noted on days 2 and 4 for all three vanadium-treated groups; for V-IV and V-V the increase continued to day 6. Radioiron data showed an erythropoietic stimulation by a significant increase in uptake percentages on days 4-6 after vanadium injections compared to saline-treated controls.

Vanadium(IV/V) complexes of Triapine and related thiosemicarbazones: Synthesis, solution equilibrium and bioactivity.

PubMed

Kowol, Christian R; Nagy, Nóra V; Jakusch, Tamás; Roller, Alexander; Heffeter, Petra; Keppler, Bernhard K; Enyedy, Éva A

2015-11-01

The stoichiometry and thermodynamic stability of vanadium(IV/V) complexes of Triapine and two related α(N)-heterocyclic thiosemicarbazones (TSCs) with potential antitumor activity have been determined by pH-potentiometry, EPR and (51)V NMR spectroscopy in 30% (w/w) dimethyl sulfoxide/water solvent mixtures. In all cases, mono-ligand complexes in different protonation states were identified. Dimethylation of the terminal amino group resulted in the formation of vanadium(IV/V) complexes with considerably higher stability. Three of the most stable complexes were also synthesized in solid state and comprehensively characterized. The biological evaluation of the synthesized vanadium complexes in comparison to the metal-free ligands in different human cancer cell lines revealed only minimal influence of the metal ion. Thus, in addition the coordination ability of salicylaldehyde thiosemicarbazone (STSC) to vanadium(IV/V) ions was investigated. The exchange of the pyridine nitrogen of the α(N)-heterocyclic TSCs to a phenolate oxygen in STSC significantly increased the stability of the complexes in solution. Finally, this also resulted in increased cytotoxicity activity of a vanadium(V) complex of STSC compared to the metal-free ligand. Copyright © 2015 Elsevier Inc. All rights reserved.

Determination of mercury and vanadium concentration in Johnius belangerii (C) fish in Musa estuary in Persian Gulf.

PubMed

Fard, Neamat Jaafarzadeh Haghighi; Ravanbakhsh, Maryam; Ramezani, Zahra; Ahmadi, Mehdi; Angali, Kambiz Ahmadi; Javid, Ahmad Zare

2015-08-15

The main aim of this study was to determine the concentrations of mercury and vanadium in Johnius belangerii (C) fish in the Musa estuary. A total of 67 fishes were caught from the Musa estuary during five intervals of 15days in the summer of 2013. After biometric measurements were conducted, the concentrations of mercury and vanadium were measured in the muscle tissue of fish using a direct method analyzer (DMA) and a graphite furnace atomic absorption spectrophotometer, respectively. The mean concentration of mercury and vanadium in the muscle tissue of fish was 3.154±1.981 and 2.921±0.873mg/kg w.w, respectively. The generalized linear model (GLM) analysis showed a significantly positive relationship among mercury concentration, length, and weight (P=0.000). In addition, there was a significantly negative relationship between vanadium concentration and fish length (P=0.000). A reverse association was found between concentrations of mercury and vanadium. Mercury concentration exceeded the allowable standards of the Environmental Protection Agency (EPA), the World Health Organization (WHO), and the Food and Drug Administration (FDA) in J. belangerii (C). Copyright © 2015 Elsevier Ltd. All rights reserved.

Nickel and vanadium in air particulates at Dhahran (Saudi Arabia) during and after the Kuwait oil fires

NASA Astrophysics Data System (ADS)

Sadiq, M.; Mian, A. A.

Air particulates, both the total suspended (TSP) and inhalable (PM 10, smaller than 10 microns in size), were collected during and after the Kuwait oil fires (from March 1991 to July 1992) using Hi-Vol samplers. These samples were wet-digested at 120°C in an aqua regia and perchloric acids mixture for 3 h. Air particulate samples collected in 1982 at the same location were prepared similarly. Concentrations of nickel and vanadium were determined in the aliquot samples using an inductively coupled argon plasma analyser (ICAP). The monthly mean concentrations of nickel and vanadium, on volume basis, increased rapidly from March to June and decreased sharply during July-August in 1991. The minimum mean concentrations of these elements were found in the particulate samples collected in December 1991 which gradually increased through May 1992. Like 1991, nickel and vanadium concentrations in the air particulates spiked in June and decreased again in July 1992. This distribution pattern of nickel and vanadium concentrations was similar to that of the predominant wind from the north (Kuwait). In general, concentrations of these elements were higher in the air particulates collected during April-July 1991 as compared with those collected in 1992 during the same period. The TSPs contained higher concentrations of nickel and vanadium than those found in the PM 10 samples. However, this trend was reversed when concentrations of nickel and vanadium, on were expressed on particulate weight basis. The monthly mean concentrations of nickel and vanadium, on weight basis, decreased gradually through 1991 and increased slightly from March to July 1992. Concentrations of these elements were significantly higher in the air particulate samples collected in 1991 than those samples collected during 1982 at the same location. The data of this study suggest a contribution of the Kuwait oil fires in elevating nickel and vanadium concentrations in the air particulates at Dhahran during April-July 1991. Concentrations of these elements were largely below their proposed limits in the ambient air (for nickel-50 μg m -3, air; for vanadium—1 μg m -3 air). It is, therefore, anticipated that concentrations of nickel and vanadium in the air particulate samples were not a health concern during Kuwait oil fires at Dhahran, Saudi Arabia.

A microfluidic fuel cell with flow-through porous electrodes.

PubMed

Kjeang, Erik; Michel, Raphaelle; Harrington, David A; Djilali, Ned; Sinton, David

2008-03-26

A microfluidic fuel cell architecture incorporating flow-through porous electrodes is demonstrated. The design is based on cross-flow of aqueous vanadium redox species through the electrodes into an orthogonally arranged co-laminar exit channel, where the waste solutions provide ionic charge transfer in a membraneless configuration. This flow-through architecture enables improved utilization of the three-dimensional active area inside the porous electrodes and provides enhanced rates of convective/diffusive transport without increasing the parasitic loss required to drive the flow. Prototype fuel cells are fabricated by rapid prototyping with total material cost estimated at 2 USD/unit. Improved performance as compared to previous microfluidic fuel cells is demonstrated, including power densities at room temperature up to 131 mW cm-2. In addition, high overall energy conversion efficiency is obtained through a combination of relatively high levels of fuel utilization and cell voltage. When operated at 1 microL min-1 flow rate, the fuel cell produced 20 mW cm-2 at 0.8 V combined with an active fuel utilization of 94%. Finally, we demonstrate in situ fuel and oxidant regeneration by running the flow-through architecture fuel cell in reverse.

Stack developments in a kW class all vanadium mixed acid redox flow battery at the Pacific Northwest National Laboratory

DOE PAGES

Reed, David M.; Thomsen, Edwin C.; Li, Bin; ...

2015-11-21

Over the past several years, efforts have been focused on improving the performance of kW class stacks with increasing current density. The influence of the Nafion membrane resistance, an interdigitated design to reduce the pressure drop in the electrolyte circuit, the temperature of the electrolyte, and the electrode structure will be discussed and correlated to the electrical performance. Furthermore, improvements to the stack energy efficiency and how those translate to the overall system efficiency will also be discussed.

Atomic site preferences and structural evolution in vanadium-doped ZrSiO4 from multinuclear solid-state NMR

NASA Astrophysics Data System (ADS)

Dajda, N.; Dixon, J. M.; Smith, M. E.; Carthey, N.; Bishop, P. T.

2003-01-01

Solid state NMR spectra of 29Si are reported from pure and vanadium-doped zircon (V-ZrSiO4) samples. The vanadium concentration is varied up to ˜1-mol % V4+ by using both conventional-firing and sol-gel routes, and 51V NMR data are also recorded. 17O NMR of 17O isotopically enriched samples shows that the initial gel is completely amorphous with the whole range of possible M-O-M' linkages detected, and that this structure evolves into a fully ordered ZrSiO4 structure with calcination. Static 91Zr NMR data is reported from a pure zircon sample. The NMR data are used to quantify the amount of vanadium entering the zircon structure, and to elucidate its site preference within the lattice. Two contact shifted peaks with very different T1 relaxation from the main zircon peak but attributable to the zircon lattice are observed in the 29Si NMR spectra for all samples. These spectra are consistent with vanadium substitution on both the tetrahedral and dodecahedral sites, with a slight preference for the silicon site. The data show that the relative occupation of these two sites is almost independent of the preparation method and vanadium concentration. At a higher vanadium concentration a third additional peak is observed which may indicate another substitution site. Variable temperature NMR and susceptibility measurements indicate the hyperfine nature of the interactions influencing silicon from V4+ ions in the different sites.

Molybdenum and vanadium do not replace tungsten in the catalytically active forms of the three tungstoenzymes in the hyperthermophilic archaeon Pyrococcus furiosus.

PubMed Central

Mukund, S; Adams, M W

1996-01-01

Three different types of tungsten-containing enzyme have been previously purified from Pyrococcus furiosus (optimum growth temperature, 100 degrees C): aldehyde ferredoxin oxidoreductase (AOR), formaldehyde ferredoxin oxidoreductase (FOR), and glyceraldehyde-3-phosphate oxidoreductase (GAPOR). In this study, the organism was grown in media containing added molybdenum (but not tungsten or vanadium) or added vanadium (but not molybdenum or tungsten). In both cell types, there were no dramatic changes compared with cells grown with tungsten, in the specific activities of hydrogenase, ferredoxin:NADP oxidoreductase, or the 2-keto acid ferredoxin oxidoreductases specific for pyruvate, indolepyruvate, 2-ketoglutarate, and 2-ketoisovalerate. Compared with tungsten-grown cells, the specific activities of AOR, FOR, and GAPOR were 40, 74, and 1%, respectively, in molybdenum-grown cells, and 7, 0, and 0%, respectively, in vanadium-grown cells. AOR purified from vanadium-grown cells lacked detectable vanadium, and its tungsten content and specific activity were both ca. 10% of the values for AOR purified from tungsten-grown cells. AOR and FOR purified from molybdenum-grown cells contained no detectable molybdenum, and their tungsten contents and specific activities were > 70% of the values for the enzymes purified from tungsten-grown cells. These results indicate that P. furiosus uses exclusively tungsten to synthesize the catalytically active forms of AOR, FOR, and GAPOR, and active molybdenum- or vanadium-containing isoenzymes are not expressed when the cells are grown in the presence of these other metals. PMID:8550411

In vitro and ex vivo vanadium antitumor activity in (TGF-β)-induced EMT. Synergistic activity with carboplatin and correlation with tumor metastasis in cancer patients.

PubMed

Petanidis, Savvas; Kioseoglou, Efrosini; Domvri, Kalliopi; Zarogoulidis, Paul; Carthy, Jon M; Anestakis, Doxakis; Moustakas, Aristidis; Salifoglou, Athanasios

2016-05-01

Epithelial to mesenchymal transition (EMT) plays a key role in tumor progression and metastasis as a crucial event for cancer cells to trigger the metastatic niche. Transforming growth factor-β (TGF-β) has been shown to play an important role as an EMT inducer in various stages of carcinogenesis. Previous reports had shown that antitumor vanadium inhibits the metastatic potential of tumor cells by reducing MMP-2 expression and inducing ROS-dependent apoptosis. However, the role of vanadium in (TGF-β)-induced EMT remains unclear. In the present study, we report for the first time on the inhibitory effects of vanadium on (TGF-β)-mediated EMT followed by down-regulation of ex vivo cancer stem cell markers. The results demonstrate blockage of (TGF-β)-mediated EMT by vanadium and reduction in the mitochondrial potential of tumor cells linked to EMT and cancer metabolism. Furthermore, combination of vanadium and carboplatin (a) resulted in synergistic antitumor activity in ex vivo cell cultures, and (b) prompted G0/G1 cell cycle arrest and sensitization of tumor cells to carboplatin-induced apoptosis. Overall, the findings highlight the multifaceted antitumor action of vanadium and its synergistic antitumor efficacy with current chemotherapy drugs, knowledge that could be valuable for targeting cancer cell metabolism and cancer stem cell-mediated metastasis in aggressive chemoresistant tumors. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Deterioration Seen in Myelin Related Morphophysiology in Vanadium Exposed Rats is Partially Protected by Concurrent Iron Deficiency.

PubMed

Usende, Ifukibot Levi; Leitner, Dominque F; Neely, Elizabeth; Connor, James R; Olopade, James O

2016-08-30

Oligodendrocyte development and myelination occurs vigorously during the early post natal period which coincides with the period of peak mobilization of iron. Oligodendrocyte progenitor cells (OPCs) are easily disturbed by any agent that affects iron homeostasis and its assimilation into these cells. Environmental exposure to vanadium, a transition metal can disrupt this iron homeostasis. We investigated the interaction of iron deficiency and vanadium exposure on the myelination infrastructure and its related neurobehavioural phenotypes, and neurocellular profiles in developing rat brains. Control group (C) dams were fed normal diet while Group 2 (V) dams were fed normal diet and pups were injected with 3mg/kg body weight of sodium metavanadate daily from postnatal day (PND) 1-21. Group 3 (I+V) dams were fed iron deficient diet after delivery and pups injected with 3mg/kg body weight sodium metavanadate from PND1-21. Body and brain weights deteriorated in I+V relative to C and V while neurobehavioral deficit occurred more in V. Whereas immunohistochemical staining shows more astrogliosis and microgliosis indicative of neuroinflammation in I+V, more intense OPCs depletion and hypomyelination were seen in the V, and this was partially protected in I+V. In in vitro studies, vanadium induced glial cells toxicity was partially protected only at the LD 50 dose with the iron chelator, desferroxamine. The data indicate that vanadium promotes myelin damage and iron deficiency in combination with vanadium partially protects this neurotoxicological effects of vanadium.

[Effect of vanadium exposure on neurobehavioral function in workers].

PubMed

Zhu, C W; Liu, Y X; Huang, C J; Gao, W; Hu, G L; Li, J; Zhang, Q; Lan, Y J

2016-02-20

To establish the comprehensive indicators for neurobehavioral function test, and to investigate the possible adverse effect of long-time vanadium exposure on neurobehavioral function and its features in workers. From July to November, 2012, The Neurobehavioral Core Test Battery(NCTB) recommended by WHO was used to conduct tests for 128 workers in vanadium exposure group and 128 workers in control group. The t-test and analysis of covariance were used to compare the differences in each indicator in NCTB between different populations, and the principal component analysis was used to establish the comprehensive neurobehavioral index(NBI) and investigate the effect of vanadium on workers' neurobehavioral function. The vanadium exposure group had significantly lower visual retention score(6.9±1.9), digit span(order) score(8.9±2.9), lifting and turning dexterity(the non-handed hand) score (14.1±3.6), pursuit aiming test(the number of correct dots) score(65.7±24.8), and digit symbol score (31.1±15.0) than the control group (8.2±1.3, 9.4±2.7, 15.5±3.0, 76.5±23.8, and 33.7±9.5)(all P<0.05). The vanadium exposure group also had a significantly lower NBI than the control group(-0.167±0.602 vs 0.168±0.564, P<0.05). Long-term vanadium exposure can influence the workers' neurobehavioral function, with the manifestations of decreased hearing and visual memory, movement velocity, accuracy, and coordination.

Lactational Vitamin E Protects Against the Histotoxic Effects of Systemically Administered Vanadium in Neonatal Rats.

PubMed

Olaolorun, F A; Obasa, A A; Balogun, H A; Aina, O O; Olopade, J O

2014-12-29

The work investigated the protective role of lactational vitamin E administration on vanadium-induced histotoxicity. Three groups of Wistar rats, with each group comprising of two dams and their pups, were used in this study. Group I pups were administered intraperitoneal injection of sterile water at volumes corresponding to the dose rate of the vanadium (sodium metavanadate) treated group from postnatal day (PND) 1-14 while those in Group II were administered intraperitoneal injection of 3mg/kg vanadium from PND 1-14. Group III pups were administered intraperitoneal injection of 3mg/kg vanadium while the dam received oral vitamin E (500 mg) concurrently every 72 hours. The results showed that group II pups exhibited histopathological changes which included seminiferous tubule disruption of the testes characterised by vacuolar degeneration and coagulative necrosis of spermatogonia and Sertoli cells with reduction in mitosis, and areas of interstitial thickening with fibroblast proliferation. In addition, the lungs showed disruption of the bronchiolar wall and denudation of the bronchiolar respiratory epithelium while the liver showed hydropic degeneration and coagulative necrosis of the centrilobular hepatocytes. These histotoxic changes were ameliorated in the vanadium + vitamin E group. We conclude that lactational vitamin E protects against the histotoxic effects of vanadium and could be a consideration for supplementation in the occupationally and environmentally exposed neonates. However, caution should be taken in vitamin E supplementation because there is still equivocal evidence surrounding its benefits as a supplement at the moment.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clausen, Jonathan R.; Brunini, Victor E.; Moffat, Harry K.

We develop a capability to simulate reduction-oxidation (redox) flow batteries in the Sierra Multi-Mechanics code base. Specifically, we focus on all-vanadium redox flow batteries; however, the capability is general in implementation and could be adopted to other chemistries. The electrochemical and porous flow models follow those developed in the recent publication by [28]. We review the model implemented in this work and its assumptions, and we show several verification cases including a binary electrolyte, and a battery half-cell. Then, we compare our model implementation with the experimental results shown in [28], with good agreement seen. Next, a sensitivity study ismore » conducted for the major model parameters, which is beneficial in targeting specific features of the redox flow cell for improvement. Lastly, we simulate a three-dimensional version of the flow cell to determine the impact of plenum channels on the performance of the cell. Such channels are frequently seen in experimental designs where the current collector plates are borrowed from fuel cell designs. These designs use a serpentine channel etched into a solid collector plate.« less

VANADIUM ALLOYS

DOEpatents

Smith, K.F.; Van Thyne, R.J.

1959-05-12

This patent deals with vanadium based ternary alloys useful as fuel element jackets. According to the invention the ternary vanadium alloys, prepared in an arc furnace, contain from 2.5 to 15% by weight titanium and from 0.5 to 10% by weight niobium. Characteristics of these alloys are good thermal conductivity, low neutron capture cross section, good corrosion resistance, good welding and fabricating properties, low expansion coefficient, and high strength.

Insulin and vanadium protect against osteoarthritis development secondary to diabetes mellitus in rats.

PubMed

El Karib, Abbas O; Al-Ani, Bahjat; Al-Hashem, Fahaid; Dallak, Mohammad; Bin-Jaliah, Ismaeel; El-Gamal, Basiouny; Bashir, Salah O; Eid, Refaat A; Haidara, Mohamed A

2016-07-01

Diabetic complications such as cardiovascular disease and osteoarthritis (OA) are among the common public health problems. The effect of insulin on OA secondary to diabetes has not been investigated before in animal models. Therefore, we sought to determine whether insulin and the insulin-mimicking agent, vanadium can protect from developing OA in diabetic rats. Type 1 diabetes mellitus (T1DM) was induced in Sprague-Dawley rats and treated with insulin and/or vanadium. Tissues harvested from the articular cartilage of the knee joint were examined by scanning electron microscopy, and blood samples were assayed for oxidative stress and inflammatory biomarkers. Eight weeks following the induction of diabetes, a profound damage to the knee joint compared to the control non-diabetic group was observed. Treatment of diabetic rats with insulin and/or vanadium differentially protected from diabetes-induced cartilage damage and deteriorated fibrils of collagen fibers. The relative biological potencies were insulin + vanadium > insulin > vanadium. Furthermore, there was about 2- to 5-fold increase in TNF-α (from 31.02 ± 1.92 to 60.5 ± 1.18 pg/ml, p < 0.0001) and IL-6 (from 64.67 ± 8.16 to 338.0 ± 38.9 pg/ml, p < 0.0001) cytokines and free radicals measured as TBARS (from 3.21 ± 0.37 to 11.48 ± 1.5 µM, p < 0.0001) in the diabetic group, which was significantly reduced with insulin and or vanadium. Meanwhile, SOD decreased (from 17.79 ± 8.9 to 8.250.29, p < 0.0001) and was increased with insulin and vanadium. The relative potencies of the treating agents on inflammatory and oxidative stress biomarkers were insulin + vanadium > insulin > vanadium. The present study demonstrates that co-administration of insulin and vanadium to T1DM rats protect against diabetes-induced OA possibly by lowering biomarkers of inflammation and oxidative stress.

Numerical investigation and thermodynamic analysis of the effect of electrolyte flow rate on performance of all vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Khazaeli, Ali; Vatani, Ali; Tahouni, Nassim; Panjeshahi, Mohammad Hassan

2015-10-01

In flow batteries, electrolyte flow rate plays a crucial role on the minimizing mass transfer polarization which is at the compensation of higher pressure drop. In this work, a two-dimensional numerical method is applied to investigate the effect of electrolyte flow rate on cell voltage, maximum depth of discharge and pressure drop a six-cell stack of VRFB. The results show that during the discharge process, increasing electrolyte flow rate can raise the voltage of each cell up to 50 mV on average. Moreover, the maximum depth of discharge dramatically increases with electrolyte flow rate. On the other hand, the pressure drop also positively correlates with electrolyte flow rate. In order to investigate all these effects simultaneously, average energy and exergy efficiencies are introduced in this study for the transient process of VRFB. These efficiencies give insight into choosing an appropriate strategy for the electrolyte flow rate. Finally, the energy efficiency of electricity storage using VRFB is investigated and compared with other energy storage systems. The results illustrate that this kind of battery has at least 61% storage efficiency based on the second law of thermodynamics, which is considerably higher than that of their counterparts.

Effects of H sub 2 S addition on the performance of fresh vs. used CoMo catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rankel, L.A.

1991-01-01

When a Co/Mo catalyst is used for processing vanadium-containing heavy oils, vanadium deposits on the catalyst. As the amount of vanadium on the CoMo catalyst increases, the catalytic effects of CoMo decline and the presence of vanadium starts to influence the hydroprocessing products. Model feeds have been used to explore the changes in the catalytic activity of CoMo, aged CoMo, and VS{sub x} on alumina. Desulfurization, denitrogenation, deoxygenation, aromatics hydrogenation, and metals removal were monitored. This paper reports that, upon the addition of hydrogen sulfide to hydrogen, improvements in the catalysts for aromatics hydrogenation, denitrogenation and metals removal were observed.

Graphene-modified nanostructured vanadium pentoxide hybrids with extraordinary electrochemical performance for Li-ion batteries

DOE PAGES

Liu, Qi; Li, Zhe-Fei; Liu, Yadong; ...

2015-01-20

The long-standing issues of low intrinsic electronic conductivity, slow lithium-ion diffusion and irreversible phase transitions on deep discharge prevent the high specific capacity/energy (443 mAh g -1 and 1,550 Wh kg -1) vanadium pentoxide from being used as the cathode material in practical battery applications. Here we develop a method to incorporate graphene sheets into vanadium pentoxide nanoribbons via the sol–gel process. The resulting graphene-modified nanostructured vanadium pentoxide hybrids contain only 2 wt. % graphene, yet exhibits extraordinary electrochemical performance: a specific capacity of 438 mAh g -1, approaching the theoretical value (443 mAh g -1), a long cyclability andmore » significantly enhanced rate capability. Such performance is the result of the combined effects of the graphene on structural stability, electronic conduction, vanadium redox reaction and lithium-ion diffusion supported by various experimental studies. Finally, this method provides a new avenue to create nanostructured metal oxide/graphene materials for advanced battery applications.« less

Recovery of Vanadium from Magnetite Ore Using Direct Acid Leaching: Optimization of Parameters by Plackett-Burman and Response Surface Methodologies

NASA Astrophysics Data System (ADS)

Nejad, Davood Ghoddocy; Khanchi, Ali Reza; Taghizadeh, Majid

2018-06-01

Recovery of vanadium from magnetite ore by direct acid leaching is discussed. The proposed process, which employs a mixture of nitric and sulfuric acids, avoids pyrometallurgical treatments since such treatment consumes a high amount of energy. To determine the optimum conditions of vanadium recovery, the leaching process is optimized through Plackett-Burman (P-B) design and response surface methodology (RSM). In this respect, temperature (80-95°C), liquid to solid ratio (L/S) (3-10 mL g-1), sulfuric acid concentration (3-6 M), nitric acid concentration (5-10 vol.%) and time (4-8 h) are considered as the independent variables. According to the P-B approach, temperature and acid concentrations are, respectively, the most effective parameters in the leaching process. These parameters are optimized using RSM to maximize recovery of vanadium by direct acid leaching. In this way, 86.7% of vanadium can be extracted from magnetic ore.

A Contemporary Treatment Approach to Both Diabetes and Depression by Cordyceps sinensis, Rich in Vanadium

PubMed Central

Guo, Jian-You; Han, Chun-Chao

2010-01-01

Diabetes mellitus is accompanied by hormonal and neurochemical changes that can be associated with anxiety and depression. Both diabetes and depression negatively interact, in that depression leads to poor metabolic control and hyperglycemia exacerbates depression. We hypothesize one novel vanadium complex of vanadium-enriched Cordyceps sinensis (VECS), which is beneficial in preventing depression in diabetes, and influences the long-term course of glycemic control. Vanadium compounds have the ability to imitate the action of insulin, and this mimicry may have further favorable effects on the level of treatment satisfaction and mood. C. sinensis has an antidepressant-like activity, and attenuates the diabetes-induced increase in blood glucose concentrations. We suggest that the VECS may be a potential strategy for contemporary treatment of depression and diabetes through the co-effect of C. sinensis and vanadium. The validity of the hypothesis can most simply be tested by examining blood glucose levels, and swimming and climbing behavior in streptozotocin-induced hyperglycemic rats. PMID:19948751

Effect of diet composition on vanadium toxicity for the chick

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, L.R.

1966-01-01

Studies to determine the effect of diet composition on the toxicity of 20 ppm added vanadium for the young chick have shown: growth depression of 25-30% with a corn-soybean meal ration but only 3-7% with a corn-herring fish meal diet. Growth depression of 35-40% with a semi-purified sucrose-soybean meal diet and approximately 50% with a diet of sucrose and herring fish meal. Adding graded levels of corn to the sucrose-fish meal ration and fish meal to the corn-soybean meal ration reduced vanadium toxicity. The corn fractions, ash, oil, starch, zein and gluten did not reduce vanadium toxicity. Removing the addedmore » magnesium (300 ppm) and potassium (2000 ppm) from the sucrose-fish meal ration did not affect growth rate or mortality. However removal of these materials from the basal ration increased growth depression due to added vanadium from 43-56% and increased mortality from 10-80%. 4 references, 9 tables.« less

Bipolar resistive switching in room temperature grown disordered vanadium oxide thin-film devices

NASA Astrophysics Data System (ADS)

Wong, Franklin J.; Sriram, Tirunelveli S.; Smith, Brian R.; Ramanathan, Shriram

2013-09-01

We demonstrate bipolar switching with high OFF/ON resistance ratios (>104) in Pt/vanadium oxide/Cu structures deposited entirely at room temperature. The SET (RESET) process occurs when negative (positive) bias is applied to the top Cu electrode. The vanadium oxide (VOx) films are amorphous and close to the vanadium pentoxide stoichiometry. We also investigated Cu/VOx/W structures, reversing the position of the Cu electrode, and found the same polarity dependence with respect to the top and bottom electrodes, which suggests that the bipolar nature is linked to the VOx layer itself. Bipolar switching can be observed at 100 °C, indicating that it not due to a temperature-induced metal-insulator transition of a vanadium dioxide second phase. We discuss how ionic drift can lead to the bipolar electrical behavior of our junctions, similar to those observed in devices based on several other defective oxides. Such low-temperature processed oxide switches could be of relevance to back-end or package integration processing schemes.

Fabrication of vanadium dioxide polycrystalline films with higher temperature coefficient of resistance

NASA Astrophysics Data System (ADS)

Li, Jinhua; Yuan, Ningyi; Jiang, Meiping; Kun, Li

2011-08-01

Vanadium Dioxide Polycrystalline Films with High Temperature Coefficient of Resistance(TCR) were fabricated by modified Ion Beam Enhanced Deposition(IBED) method. The TCR of the Un-doping VO2 was about -4%/K at room temperature after appropriate thermal annealing. The XRD results clearly showed that IBED polycrystalline VO2 films had a single [002] orientation of VO2(M). The TCR of 5at.%W and 7at.% Ta doped Vanadium Dioxide Polycrystalline Films were high up to -18%/K and -12%/K at room temperature, respectively. Using 7at.% Ta and 2at.% Ti co-doping, the TCR of the co-doped vanadium oxide film was -7%/K and without hysteresis during temperature increasing and decresing from 0-80°C. It should indicate that the W-doped vanadium dioxide films colud be used for high sensing IR detect and the Ta/Ti co-doped film without hysteresis is suitable for infrarid imaging application.

Imaging metal-like monoclinic phase stabilized by surface coordination effect in vanadium dioxide nanobeam

PubMed Central

Li, Zejun; Wu, Jiajing; Hu, Zhenpeng; Lin, Yue; Chen, Qi; Guo, Yuqiao; Liu, Yuhua; Zhao, Yingcheng; Peng, Jing; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2017-01-01

In correlated systems, intermediate states usually appear transiently across phase transitions even at the femtosecond scale. It therefore remains an open question how to determine these intermediate states—a critical issue for understanding the origin of their correlated behaviour. Here we report a surface coordination route to successfully stabilize and directly image an intermediate state in the metal-insulator transition of vanadium dioxide. As a prototype metal-insulator transition material, we capture an unusual metal-like monoclinic phase at room temperature that has long been predicted. Coordinate bonding of L-ascorbic acid molecules with vanadium dioxide nanobeams induces charge-carrier density reorganization and stabilizes metallic monoclinic vanadium dioxide, unravelling orbital-selective Mott correlation for gap opening of the vanadium dioxide metal–insulator transition. Our study contributes to completing phase-evolution pathways in the metal-insulator transition process, and we anticipate that coordination chemistry may be a powerful tool for engineering properties of low-dimensional correlated solids. PMID:28613281

Thymic cytoarchitecture changes in mice exposed to vanadium.

PubMed

Ustarroz-Cano, Martha; Garcia-Pelaez, Isabel; Cervantes-Yepez, Silvana; Lopez-Valdez, Nelly; Fortoul, Teresa I

2017-12-01

The thymus is a vital immune system organ wherein selection of T-lymphocytes occurs in a process regulated by dendritic and epithelial thymic cells. Previously, we have reported that in a mouse model of vanadium inhalation, a decrease in CD11c dendritic cells was observed. In the present study, we report on a thymic cortex-medulla distribution distortion in these hosts due to apparent effects of the inhaled vanadium on cytokeratin-5 (K5 + ) epithelial cells in the same mouse model - after 1, 2, and 4 weeks of exposure - by immunohistochemistry. These cells - together with dendritic cells - eliminate autoreactive T-cell clones and regulate the production of regulatory T-cells in situ. Because both cell types are involved in the negative selection of autoreactive clones, a potential for an increase in development of autoimmune conditions could be a possible consequence among individuals who might be exposed often to vanadium in air pollution, including dwellers of highly polluted cities with elevated levels of particulate matter onto which vanadium is often adsorbed.

Properties of vanadium-loaded iron sorbent after alkali regeneration.

PubMed

Khalid, Muhammad Kamran; Leiviskä, Tiina; Tanskanen, Juha

2017-11-01

The aim of this research was to investigate the regeneration and reuse of a commercial granular iron sorbent (mainly goethite) when used in vanadium removal. A regeneration rate of 3 M NaOH was the highest (85%) achieved, followed by 2 M NaOH (79%) and 1 M NaOH (68%). The breakthrough curves show that the regenerated material can be reused. The BET (Brunauer-Emmett-Teller) surface area increased by 35-38% and the total pore volume increased by 123-130% as a consequence of NaOH treatment. The results indicated that sodium hydroxide could be used for the regeneration of iron sorbent although the regeneration was incomplete. This may be explained by the fact that vanadium diffusion into pores is a significant sorption mechanism in addition to complex formation with surface functional groups. As a consequence, vanadium desorbability from pores is not as effective as the regeneration of surface sites. X-ray photoelectron spectroscopy analyses confirmed a very low vanadium content on the surface of the NaOH-treated iron sorbent.

Recovery of Vanadium from Magnetite Ore Using Direct Acid Leaching: Optimization of Parameters by Plackett-Burman and Response Surface Methodologies

NASA Astrophysics Data System (ADS)

Nejad, Davood Ghoddocy; Khanchi, Ali Reza; Taghizadeh, Majid

2018-03-01

Recovery of vanadium from magnetite ore by direct acid leaching is discussed. The proposed process, which employs a mixture of nitric and sulfuric acids, avoids pyrometallurgical treatments since such treatment consumes a high amount of energy. To determine the optimum conditions of vanadium recovery, the leaching process is optimized through Plackett-Burman (P-B) design and response surface methodology (RSM). In this respect, temperature (80-95°C), liquid to solid ratio (L/S) (3-10 mL g-1), sulfuric acid concentration (3-6 M), nitric acid concentration (5-10 vol.%) and time (4-8 h) are considered as the independent variables. According to the P-B approach, temperature and acid concentrations are, respectively, the most effective parameters in the leaching process. These parameters are optimized using RSM to maximize recovery of vanadium by direct acid leaching. In this way, 86.7% of vanadium can be extracted from magnetic ore.

Effect of Mechanical Activation Treatment on the Recovery of Vanadium from Converter Slag

NASA Astrophysics Data System (ADS)

Xiang, Junyi; Huang, Qingyun; Lv, Xuewei; Bai, Chenguang

2017-10-01

The high roasting temperature and low leaching efficiency of vanadium from vanadium-bearing converter slag are regarded as the main factors significantly influencing the application of calcification roasting-acid leaching processes in the cleaner production of vanadium. In this study, a mechanical activation treatment was performed to enhance the extraction of vanadium from converter slag. The enhancement effects obtained from mechanical activation were comprehensively evaluated through indices such as the roasting temperature and leaching efficiency. The effects of mechanical activation time, roasting temperature, leaching temperature, solid to liquid ratio, particle size, and acid concentration on the leaching efficiency were investigated. Microstructure morphology and elemental analyses of the raw materials and leaching residue were also investigated using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results demonstrated that the mechanical activation significantly decreased the optimum roasting temperature from 1173 K to 1073 K (900 °C to 800 °C) and increased the leaching efficiency from 86.0 to 90.9 pct.

Nanocrystalline ordered vanadium carbide: Superlattice and nanostructure

NASA Astrophysics Data System (ADS)

Kurlov, A. S.; Gusev, A. I.; Gerasimov, E. Yu.; Bobrikov, I. A.; Balagurov, A. M.; Rempel, A. A.

2016-02-01

The crystal structure, micro- and nanostructure of coarse- and nanocrystalline powders of ordered vanadium carbide V8C7 have been examined by X-ray and neutron diffraction and electron microscopy methods. The synthesized coarse-crystalline powder of ordered vanadium carbide has flower-like morphology. It was established that the real ordered phase has the composition V8C7-δ (δ ≅ 0.03) deviating from perfect stoichiometric composition V8C7. The vanadium atoms forming the octahedral environment □V6 of vacant sites in V8C7-δ are displaced towards the vacancy □. The presence of carbon onion-like structures was found in the vanadium carbide powders with a small content of free (uncombined) carbon. The nanopowders of V8C7-δ carbide with average particle size of 20-30 nm produced by high-energy milling of coarse-crystalline powder retain the crystal structure of the initial powder, but differ in the lattice deformation distortion anisotropy.

Vanadium pentoxide nanoparticles mimic vanadium haloperoxidases and thwart biofilm formation

NASA Astrophysics Data System (ADS)

Natalio, Filipe; André, Rute; Hartog, Aloysius F.; Stoll, Brigitte; Jochum, Klaus Peter; Wever, Ron; Tremel, Wolfgang

2012-08-01

Marine biofouling--the colonization of small marine microorganisms on surfaces that are directly exposed to seawater, such as ships' hulls--is an expensive problem that is currently without an environmentally compatible solution. Biofouling leads to increased hydrodynamic drag, which, in turn, causes increased fuel consumption and greenhouse gas emissions. Tributyltin-free antifouling coatings and paints based on metal complexes or biocides have been shown to efficiently prevent marine biofouling. However, these materials can damage the environment through metal leaching (for example, of copper and zinc) and bacteria resistance. Here, we show that vanadium pentoxide nanowires act like naturally occurring vanadium haloperoxidases to prevent marine biofouling. In the presence of bromide ions and hydrogen peroxide, the nanowires catalyse the oxidation of bromide ions to hypobromous acid (HOBr). Singlet molecular oxygen (1O2) is formed and this exerts strong antibacterial activity, which prevents marine biofouling without being toxic to marine biota. Vanadium pentoxide nanowires have the potential to be an alternative approach to conventional anti-biofouling agents.

Correlation between molten vanadium salts and the structural degradation of HK-type steel superheater tubes

NASA Astrophysics Data System (ADS)

de Carvalho Nunes, Frederico; de Almeida, Luiz Henrique; Ribeiro, André Freitas

2006-12-01

HK steels are among the most used heat-resistant cast stainless steels, being corrosion-resistant and showing good mechanical properties at high service temperatures. These steels are widely used in reformer furnaces and as superheater tubes. During service, combustion gases leaving the burners come in contact with these tubes, resulting in corrosive attack and a large weight loss occurs due to the presence of vanadium, which forms low melting point salts, removing the protective oxide layer. In this work the external surface of a tube with dramatic wall thickness reduction was analyzed using light microscopy, scanning electron microscopy, and transmission electron microscopy. The identification of the phases was achieved by energy dispersive spectroscopy (EDS) analyses. The results showed oxides arising from the external surface. In this oxidized region vanadium compounds inside chromium carbide particles were also observed, due to inward vanadium diffusion during corrosion attack. A chemical reaction was proposed to explain the presence of vanadium in the metal microstructure.

Plasmonic Structures for CMOS Photonics and Control of Spontaneous Emission

DTIC Science & Technology

2013-04-01

structures; v) developed CMOS Si photonic switching device based on the vanadium dioxide ( VO2 ) phase transition. vi) also engaged in a partnership with...CMOS Si photonic switching device based on the vanadium dioxide ( VO2 ) phase transition. vii. exploring approaches to enhance spontaneous emission in...size and bandwidth, we are exploring phase-change materials and, in particular, vanadium dioxide. VO2 undergoes an insulator-to-metal phase transition

Imaging of Vanadium in Microfossils: A New Potential Biosignature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, Craig P.; Marshall, Alison Olcott; Aitken, Jade B.

Being able to distinguish unambiguously the biogenicity of microfossil-like structures in the ancient rock record is a fundamental predicament facing Archean paleobiologists and astrobiologists. Therefore, novel methods for discriminating biological from non-biological chemistries of microfossil-like structures are of the utmost importance in the search for evidence of early life on Earth. This too, is important for the search for life on Mars; either by in situ analyses via rovers, or sample return missions for future analysis here on Earth. Here, we report the application of synchrotron X-ray fluorescence imaging of vanadium, within thermally altered organic-walled microfossils of bona fide biologicalmore » origin. From our data, we demonstrate that vanadium is present within microfossils of undisputable biological origin. It is well known in the organic geochemistry literature, that elements such as vanadium are enriched and contained within crude oils, asphalts, and black shales that have been formed by diagensis of biological organic material. It has been demonstrated that the origin of vanadium is due to the diagenetic alteration of precursor chlorophyll and heme porphyrin pigment compounds from living organisms. Here, we propose that taken together, microfossil-like morphology, carbonaceous composition, and the presence of vanadium could be used in tandem as a biosignature to ascertain the biogenecity of putative microfossil-like structures.« less

Improved capacitance characteristics of electrospun ACFs by pore size control and vanadium catalyst.

PubMed

Im, Ji Sun; Woo, Sang-Wook; Jung, Min-Jung; Lee, Young-Seak

2008-11-01

Nano-sized carbon fibers were prepared by using electrospinning, and their electrochemical properties were investigated as a possible electrode material for use as an electric double-layer capacitor (EDLC). To improve the electrode capacitance of EDLC, we implemented a three-step optimization. First, metal catalyst was introduced into the carbon fibers due to the excellent conductivity of metal. Vanadium pentoxide was used because it could be converted to vanadium for improved conductivity as the pore structure develops during the carbonization step. Vanadium catalyst was well dispersed in the carbon fibers, improving the capacitance of the electrode. Second, pore-size development was manipulated to obtain small mesopore sizes ranging from 2 to 5 nm. Through chemical activation, carbon fibers with controlled pore sizes were prepared with a high specific surface and pore volume, and their pore structure was investigated by using a BET apparatus. Finally, polyacrylonitrile was used as a carbon precursor to enrich for nitrogen content in the final product because nitrogen is known to improve electrode capacitance. Ultimately, the electrospun activated carbon fibers containing vanadium show improved functionality in charge/discharge, cyclic voltammetry, and specific capacitance compared with other samples because of an optimal combination of vanadium, nitrogen, and fixed pore structures.

Imaging of Vanadium in Microfossils: A New Potential Biosignature

DOE PAGES

Marshall, Craig P.; Marshall, Alison Olcott; Aitken, Jade B.; ...

2017-11-01

Being able to distinguish unambiguously the biogenicity of microfossil-like structures in the ancient rock record is a fundamental predicament facing Archean paleobiologists and astrobiologists. Therefore, novel methods for discriminating biological from non-biological chemistries of microfossil-like structures are of the utmost importance in the search for evidence of early life on Earth. This too, is important for the search for life on Mars; either by in situ analyses via rovers, or sample return missions for future analysis here on Earth. Here, we report the application of synchrotron X-ray fluorescence imaging of vanadium, within thermally altered organic-walled microfossils of bona fide biologicalmore » origin. From our data, we demonstrate that vanadium is present within microfossils of undisputable biological origin. It is well known in the organic geochemistry literature, that elements such as vanadium are enriched and contained within crude oils, asphalts, and black shales that have been formed by diagensis of biological organic material. It has been demonstrated that the origin of vanadium is due to the diagenetic alteration of precursor chlorophyll and heme porphyrin pigment compounds from living organisms. Here, we propose that taken together, microfossil-like morphology, carbonaceous composition, and the presence of vanadium could be used in tandem as a biosignature to ascertain the biogenecity of putative microfossil-like structures.« less

Molecular geometry of vanadium dichloride and vanadium trichloride: a gas-phase electron diffraction and computational study.

PubMed

Varga, Zoltán; Vest, Brian; Schwerdtfeger, Peter; Hargittai, Magdolna

2010-03-15

The molecular geometries of VCl2 and VCl3 have been determined by computations and gas-phase electron diffraction (ED). The ED study is a reinvestigation of the previously published analysis for VCl2. The structure of the vanadium dichloride dimer has also been calculated. According to our joint ED and computational study, the evaporation of a solid sample of VCl2 resulted in about 66% vanadium trichloride and 34% vanadium dichloride in the vapor. Vanadium dichloride is unambiguously linear in its 4Sigma(g)+ ground electronic state. For VCl3, all computations yielded a Jahn-Teller-distorted ground-state structure of C(2v) symmetry. However, it lies merely less than 3 kJ/mol lower than the 3E'' state (D(3h) symmetry). Due to the dynamic nature of the Jahn-Teller effect in this case, rigorous distinction cannot be made between the planar models of either D(3h) symmetry or C(2v) symmetry for the equilibrium structure of VCl3. Furthermore, the presence of several low-lying excited electronic states of VCl3 is expected in the high-temperature vapor. To our knowledge, this is the first experimental and computational study of the VCl3 molecule.

Imaging of Vanadium in Microfossils: A New Potential Biosignature

NASA Astrophysics Data System (ADS)

Marshall, Craig P.; Marshall, Alison Olcott; Aitken, Jade B.; Lai, Barry; Vogt, Stefan; Breuer, Pierre; Steemans, Philippe; Lay, Peter A.

2017-11-01

The inability to unambiguously distinguish the biogenicity of microfossil-like structures in the ancient rock record is a fundamental predicament facing Archean paleobiologists and astrobiologists. Therefore, novel methods for discriminating biological from nonbiological chemistries of microfossil-like structures are of the utmost importance in the search for evidence of early life on Earth. This, too, is important for the search for life on Mars by in situ analyses via rovers or sample return missions for future analysis here on Earth. Here, we report the application of synchrotron X-ray fluorescence imaging of vanadium, within thermally altered organic-walled microfossils of bona fide biological origin. From our data, we demonstrate that vanadium is present within microfossils of undisputable biological origin. It is well known in the organic geochemistry literature that elements such as vanadium are enriched and contained within crude oils, asphalts, and black shales that have been formed by diagenesis of biological organic material. It has been demonstrated that the origin of vanadium is due to the diagenetic alteration of precursor chlorophyll and heme porphyrin pigment compounds from living organisms. We propose that, taken together, microfossil-like morphology, carbonaceous composition, and the presence of vanadium could be used in tandem as a biosignature to ascertain the biogenicity of putative microfossil-like structures.

Understanding the Reduction Kinetics of Aqueous Vanadium(V) and Transformation Products Using Rotating Ring-Disk Electrodes.

PubMed

Chen, Gongde; Liu, Haizhou

2017-10-17

Vanadium(V) is an emerging contaminant in the most recent Environmental Protection Agency's candidate contaminant list (CCL4). The redox chemistry of vanadium controls its occurrence in the aquatic environment, but the impact of vanadium(V) speciation on the redox properties remains largely unknown. This study utilized the rotating ring-disk electrode technique to examine the reduction kinetics of four pH- and concentration-dependent vanadium(V) species in the presence and the absence of phosphate. Results showed that the reduction of VO 2 + , H x V 4 O 12+x (4+x)- (V 4 ), and HVO 4 2- proceeded via a one-electron transfer, while that of Na x H y V 10 O 28 (6-x-y)- (V 10 ) underwent a two-electron transfer. Koutecky-Levich and Tafel analyses showed that the intrinsic reduction rate constants followed the order of V 10 > VO 2 + > V 4 > HVO 4 2- . Ring-electrode collection efficiency indicated that the reduction product of V 10 was stable, while those of VO 2 + , HVO 4 2- , and V 4 had short half-lives that ranged from milliseconds to seconds. With molar ratios of phosphate to vanadium(V) varying from 0 to 1, phosphate accelerated the reduction kinetics of V 10 and V 4 and enhanced the stability of the reduction products of VO 2 + , V 4 , and HVO 4 2- . This study suggests that phosphate complexation could enhance the reductive removal of vanadium(V) and inhibit the reoxidation of its reduction product in water treatment.

Removal and recovery of vanadium from alkaline steel slag leachates with anion exchange resins.

PubMed

Gomes, Helena I; Jones, Ashley; Rogerson, Mike; Greenway, Gillian M; Lisbona, Diego Fernandez; Burke, Ian T; Mayes, William M

2017-02-01

Leachable vanadium (V) from steel production residues poses a potential environmental hazard due to its mobility and toxicity under the highly alkaline pH conditions that characterise these leachates. This work aims to test the efficiency of anion exchange resins for vanadium removal and recovery from steel slag leachates at a representative average pH of 11.5. Kinetic studies were performed to understand the vanadium sorption process. The sorption kinetics were consistent with a pseudo-first order kinetic model. The isotherm data cannot differentiate between the Langmuir and Freundlich models. The maximum adsorption capacity (Langmuir value q max ) was 27 mg V g -1 resin. In column anion exchange, breakthrough was only 14% of the influent concentration after passing 90 L of steel slag leachate with 2 mg L -1 V through the column. When eluting the column 57-72% of vanadium was recovered from the resin with 2 M NaOH. Trials on the reuse of the anion exchange resin showed it could be reused 20 times without loss of efficacy, and on average 69% of V was recovered during regeneration. The results document for the first time the use of anion exchange resins to remove vanadium from steel slag leachate. As an environmental contaminant, removal of V from leachates may be an obligation for long-term management requirements of steel slag repositories. Vanadium removal coupled with the recovery can potentially be used to offset long-term legacy treatment costs. Copyright © 2016 The Author(s). Published by Elsevier Ltd.. All rights reserved.

A comparative assessment of the acute inhalation toxicity of vanadium compounds.

PubMed

Rajendran, N; Seagrave, J C; Plunkett, L M; MacGregor, J A

2016-11-01

Vanadium compounds have become important in industrial processes, resulting in workplace exposure potential and are present in ambient air as a result of fossil fuel combustion. A series of acute nose-only inhalation toxicity studies was conducted in both rats and mice in order to obtain comparative data on the acute toxicity potential of compounds used commercially. V 2 O 3 , V 2 O 4 , and V 2 O 5 , which have different oxidation states (+3, +4, +5, respectively), were delivered as micronized powders; the highly water-soluble and hygroscopic VOSO 4 (+4) could not be micronized and was instead delivered as a liquid aerosol from an aqueous solution. V 2 O 5 was the most acutely toxic micronized powder in both species. Despite its lower overall percentage vanadium content, a liquid aerosol of VOSO 4 was more toxic than the V 2 O 5 particles in mice, but not in rats. These data suggest that an interaction of characteristics, i.e., bioavailability, solubility and oxidation state, as well as species sensitivity, likely affect the toxicity potential of vanadium compounds. Based on clinical observations and gross necropsy findings, the lung appeared to be the target organ for all compounds. The level of hazard posed will depend on the specific chemical form of the vanadium. Future work to define the inhalation toxicity potential of vanadium compounds of various oxidation states after repeated exposures will be important in understanding how the physico-chemical and biological characteristics of specific vanadium compounds interact to affect toxicity potential and the potential risks posed to human health.

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.

Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm andmore » two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.« less

Quantitative Assessment of Proliferative Effects of Oral Vanadium on Pancreatic Islet Volumes and Beta Cell Numbers of Diabetic Rats

PubMed Central

Pirmoradi, Leila; Noorafshan, Ali; Safaee, Akbar; Dehghani, Gholam Abbas

2016-01-01

Background: Oral vanadyl sulfate (vanadium) induces normoglycemia, proliferates beta cells and prevents pancreatic islet atrophy in streptozotocin-induced diabetic rats. Soteriological method is used to quantitate the proliferative effects of vanadium on beta-cell numbers and islet volumes of normal and diabetic rats. Methods: Adult male Sprague-Dawley rats were made diabetic with intravenous streptozotocin injection (40 mg/kg). Normal and diabetic rats were divided into four groups. While control normal and diabetic (CD) groups used water, vanadium-treated normal (VTN) and diabetic (VTD) groups used solutions containing vanadyl sulfate (0.5-1 mg/mL, VOSO4+5H2O). Tail blood samples were used to measure blood glucose (BG) and plasma insulin. Two months after treatment, rats were sacrificed, pancreata prepared, and stereology method was used to quantitatively evaluate total beta cell numbers (TBCN) and total islet volumes (TISVOL). Results: Normoglycemia persisted in VTN with significantly decreased plasma insulin (0.190.08 vs. 0.970.27 ng/dL, P<0.002). The respective high BG (53249 vs. 14446 mg/dL, P<0.0001) and reduced plasma insulin (0.260.15 vs. 0.540.19 ng/dL, P<0.002) seen in CD were reversed in VTD during vanadium treatment or withdrawal. While the induction of diabetes, compared to their control, significantly decreased TISVOL (1.90.2 vs. 3.030.6 mm3, P<0.003) and TBCN (0.990.1 vs. 3.20.2 x 106, P<0.003), vanadium treatment significantly increased TISVOL (2.90.8 and 4.071.0 mm3, P<0.003) and TBCN (1.50.3 and 3.80.6 x 106, P<0.03). Conclusion: Two-month oral vanadium therapy in STZ-diabetic rats ameliorated hyperglycemia by partially restoring plasma insulin. This action was through proliferative actions of vanadium in preventing islet atrophy by increasing beta-cell numbers. PMID:26459400

A dynamic plug flow reactor model for a vanadium redox flow battery cell

NASA Astrophysics Data System (ADS)

Li, Yifeng; Skyllas-Kazacos, Maria; Bao, Jie

2016-04-01

A dynamic plug flow reactor model for a single cell VRB system is developed based on material balance, and the Nernst equation is employed to calculate cell voltage with consideration of activation and concentration overpotentials. Simulation studies were conducted under various conditions to investigate the effects of several key operation variables including electrolyte flow rate, upper SOC limit and input current magnitude on the cell charging performance. The results show that all three variables have a great impact on performance, particularly on the possibility of gassing during charging at high SOCs or inadequate flow rates. Simulations were also carried out to study the effects of electrolyte imbalance during long term charging and discharging cycling. The results show the minimum electrolyte flow rate needed for operation within a particular SOC range in order to avoid gassing side reactions during charging. The model also allows scheduling of partial electrolyte remixing operations to restore capacity and also avoid possible gassing side reactions during charging. Simulation results also suggest the proper placement for cell voltage monitoring and highlight potential problems associated with setting the upper charging cut-off limit based on the inlet SOC calculated from the open-circuit cell voltage measurement.

Improving the electrocatalytic performance of carbon nanotubes for VO2+/VO2+ redox reaction by KOH activation

NASA Astrophysics Data System (ADS)

Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

2017-04-01

In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO2+/VO2+ redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO2+/VO2+ redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO2+/VO2+ redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO2+/VO2+ redox reaction for VRFB system.

An adaptive model for vanadium redox flow battery and its application for online peak power estimation

NASA Astrophysics Data System (ADS)

Wei, Zhongbao; Meng, Shujuan; Tseng, King Jet; Lim, Tuti Mariana; Soong, Boon Hee; Skyllas-Kazacos, Maria

2017-03-01

An accurate battery model is the prerequisite for reliable state estimate of vanadium redox battery (VRB). As the battery model parameters are time varying with operating condition variation and battery aging, the common methods where model parameters are empirical or prescribed offline lacks accuracy and robustness. To address this issue, this paper proposes to use an online adaptive battery model to reproduce the VRB dynamics accurately. The model parameters are online identified with both the recursive least squares (RLS) and the extended Kalman filter (EKF). Performance comparison shows that the RLS is superior with respect to the modeling accuracy, convergence property, and computational complexity. Based on the online identified battery model, an adaptive peak power estimator which incorporates the constraints of voltage limit, SOC limit and design limit of current is proposed to fully exploit the potential of the VRB. Experiments are conducted on a lab-scale VRB system and the proposed peak power estimator is verified with a specifically designed "two-step verification" method. It is shown that different constraints dominate the allowable peak power at different stages of cycling. The influence of prediction time horizon selection on the peak power is also analyzed.

Elution of uranium and transition metals from amidoxime-based polymer adsorbents for sequestering uranium from seawater

DOE PAGES

Pan, Horng-Bin; Kuo, Li-Jung; Miyamoto, Naomi; ...

2015-11-30

High-surface-area amidoxime and carboxylic acid grafted polymer adsorbents developed at Oak Ridge National Laboratory were tested for sequestering uranium in a flowing seawater flume system at the PNNL-Marine Sciences Laboratory. FTIR spectra indicate that a KOH conditioning process is necessary to remove the proton from the carboxylic acid and make the sorbent effective for sequestering uranium from seawater. The alkaline conditioning process also converts the amidoxime groups to carboxylate groups in the adsorbent. Both Na 2CO 3 H 2O 2 and hydrochloric acid elution methods can remove ~95% of the uranium sequestered by the adsorbent after 42 days of exposuremore » in real seawater. The Na 2CO 3 H 2O 2 elution method is more selective for uranium than conventional acid elution. Iron and vanadium are the two major transition metals competing with uranium for adsorption to the amidoxime-based adsorbents in real seawater. Tiron (4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium salt, 1 M) can remove iron from the adsorbent very effectively at pH around 7. The coordination between vanadium (V) and amidoxime is also discussed based on our 51V NMR data.« less

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V.; West, William C.; Kindler, Andrew; Smart, Marshall C.

2013-01-01

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Exploratory Phase Transition-Based Switches Using Functional Oxides

DTIC Science & Technology

2011-02-02

TECHNICAL REPORT Abstract Vanadium dioxide ( VO2 ) undergoes a sharp metal-insulator transition (MIT) in the vicinity of room temperature and there is...18 The mechanisms governing metal-insulator transition (MIT) in vanadium dioxide ( VO2 ) is an intensively explored subject in condensed matter...textured vanadium dioxide films were grown on single crystal Al2O3 (0001) substrates by RF-sputtering from a VO2 target (99.5%, AJA International Inc

Temperature Dependence of Uranium and Vanadium Adsorption on Amidoxime-Based Adsorbents in Natural Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuo, Li-Jung; Gill, Gary A.; Tsouris, Costas

The apparent enthalpy and entropy of the complexation of uranium (VI) and vanadium (V) with amidoxime ligands grafted onto polyethylene fiber was determined using time series measurements of adsorption capacities in natural seawater at three different temperatures. The complexation of uranium was highly endothermic, while the complexation of vanadium showed minimal temperature sensitivity. Amidoxime-based polymeric adsorbents exhibit significantly increased uranium adsorption capacities and selectivity in warmer waters.

Amorphous vanadium oxide coating on graphene by atomic layer deposition for stable high energy lithium ion anodes.

PubMed

Sun, Xiang; Zhou, Changgong; Xie, Ming; Hu, Tao; Sun, Hongtao; Xin, Guoqing; Wang, Gongkai; George, Steven M; Lian, Jie

2014-09-21

Uniform amorphous vanadium oxide films were coated on graphene via atomic layer deposition and the nano-composite displays an exceptional capacity of ~900 mA h g(-1) at 200 mAg(-1) with an excellent capacity retention at 1 A g(-1) after 200 cycles. The capacity contribution (1161 mA h g(-1)) from vanadium oxide only almost reaches its theoretical value.

VOC Emission Reduction Study at the Hill Air Force Base Building 515 Painting Facility

DTIC Science & Technology

1990-09-01

occurs during painting. A system for decreasing the flow to a downstream VOC emission control device can be designed that takes advantage of this...paint application process. A flow-reducing ventilation system that takes advantage of this operating characteristic can be designed in which the...flow from the second duct is vented to a VOC emission control device. The advantage of this system is that the flow rate to a VOC emission contro

Growth control of the oxidation state in vanadium oxide thin films

DOE PAGES

Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; ...

2014-12-05

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metalinsulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V₂⁺²O₃, V⁺⁴O₂, and V₂⁺⁵O₅. A well pronounced MIT was only observed in VO₂ films grown in a very narrow range of oxygen partial pressure P(O₂). The films grown either in lower (< 10 mTorr) or higher P(O₂) (> 25 mTorr) result in V₂O₃ and V₂O₅ phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO₂ thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an 3 improved MIT behavior.« less

Evaluating electrically insulating films deposited on V-4% Cr-4% Ti by reactive CVD

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, J.H.; Cho, W.D.

1997-04-01

Previous CaO coatings on V-4%Cr-4%Ti exhibited high-ohmic insulator behavior even though a small amount of vanadium from the alloy was incorporated in the coating. However, when the vanadium concentration in the coatings is > 15 wt%, the coating becomes conductive. When the vanadium concentration is high in localized areas, a calcium vanadate phase that exhibits semiconductor behavior can form. To explore this situation, CaO and Ca-V-O coatings were produced on vanadium alloys by chemical vapor deposition (CVD) and by a metallic-vapor process to investigate the electrical resistance of the coatings. Initially, the vanadium alloy specimens were either charged with oxygenmore » in argon that contained trace levels of oxygen, or oxidized for 1.5-3 h in a 1% CO-CO{sub 2} gas mixture or in air to form vanadium oxide at 625-650{degrees}C. Most of the specimens were exposed to calcium vapor at 800-850{degrees}C. Initial and final weights were obtained to monitor each step, and surveillance samples were removed for examination by optical and scanning electron microscopy and electron-energy-dispersive and X-ray diffraction analysis; the electrical resistivity was also measured. The authors found that Ca-V-O films exhibited insulator behavior when the ratio of calcium concentration to vanadium concentration R in the film was > 0.9, and semiconductor or conductor behavior for R < 0.8. However, in some cases, semiconductor behavior was observed when CaO-coated samples with R > 0.98 were exposed in liquid lithium. Based on these studies, the authors conclude that semiconductor behavior occurs if a conductive calcium vanadate phase is present in localized regions in the CaO coating.« less

Growth control of the oxidation state in vanadium oxide thin films

NASA Astrophysics Data System (ADS)

Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; Egami, Takeshi; Lee, Ho Nyung

2014-12-01

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase pure epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V2 + 3 O 3 , V + 4 O 2 , and V2 + 5 O 5 . A well pronounced MIT was only observed in VO2 films grown in a very narrow range of oxygen partial pressure P(O2). The films grown either in lower (<10 mTorr) or higher P(O2) (>25 mTorr) result in V2O3 and V2O5 phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO2 thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.

High-Fat Diet Increased Renal and Hepatic Oxidative Stress Induced by Vanadium of Wistar Rat.

PubMed

Wang, J P; Cui, R Y; Zhang, K Y; Ding, X M; Luo, Y H; Bai, S P; Zeng, Q F; Xuan, Y; Su, Z W

2016-04-01

The study was conducted to assess the effect of vanadium (V) in high-fat diet on the liver and kidney of rats in a 5-week trial. Seventy-two female Wistar rats (BW = 95 ± 5 g) were randomly allotted into eight groups. Groups I, II, III, and IV obtained low-fat diet containing 0, 3, 15, and 30 mg/kg V, and V, VI, VII, and VIII groups received the respective vanadium doses with high-fat diet, respectively. There were lesions in the liver and kidney of V, VI, VII, and VIII groups, granular degeneration and vacuolar degeneration were observed in the renal tubular and glomerulus epithelial cells, and hepatocytes showed granular degeneration and vacuolar degeneration. Supplemented high-fat diet with vanadium was shown to decrease (P < 0.05) activities of superoxide dismutase, total antioxidant capacity, glutathione-S transferase, and NAD(P)H/quinone oxidoreductase 1 (NQO1) and increase malondialdehyde content in the liver and kidney. The relative expression of hepatic nuclear factor erythroid 2-related factor 2 (Nrf-2) and NQO1 mRNA was downregulated by V addition and high-fat diet, and the effect of V was more pronounced in high-fat diet (interaction, P < 0.05), with VIII group having the lowest mRNA expression of Nrf-2 and NQO1 in the liver and kidney. In conclusion, it suggested that dietary vanadium ranging from 15 to 30 mg/kg could lead to oxidative damage and vanadium accumulation in the liver and kidney, which caused renal and hepatic toxicity. The high-fat diet enhanced vanadium-induced hepatic and renal damage, and the mechanism was related to the modulation of the hepatic and renal mRNA expression of Nrf-2 and NQO1.

Does the relief of glucose toxicity act as a mediator in proliferative actions of vanadium on pancreatic islet beta cells in streptozocin diabetic rats?

PubMed

Pirmoradi, Leila; Mohammadi, Mohammad Taghi; Safaei, Akbar; Mesbah, Fakhardin; Dehghani, Gholam Abbas

2014-07-01

Data shows vanadium protects pancreatic beta cells (BC) from diabetic animals. Whether this effect is direct or through the relief of glucose toxicity is not clear. This study evaluated the potential effect of oral vanadyl sulfate (vanadium) on glycemic status and pancreatic BC of normal and diabetic rats. Rats were divided into five groups of normal and diabetic. Diabetes was induced with streptozocin (40 mg/kg, i.v.). Normal rats used water (CN) or vanadium (1 mg/ml VOSO4, VTN). Diabetic rats used water (CD), water plus daily neutral protamine Hagedorn insulin injection (80 U/kg, ITD) or vanadium (VTD). Blood samples were taken for blood glucose (BG, mg/dL) and insulin (ng/dL) measurements. After two months, the pancreata of sacrificed rats were prepared for islet staining. Pre-treated normal BG was 88 ± 2, and diabetic BG was 395 ± 9. The final BG in CD, VTD, and ITD was 509 ± 22, 138 ± 14, and 141 ± 14, respectively. Insulin in VTN (0.75 ± 0.01) and VTD (0.78 ± 0.01) was similar, higher than CD (0.51 ± 0.07) but lower than CN (2.51 ± 0.02). VTN islets compared to CN had larger size and denser central core insulin immunoreactivity with plentiful BC. CD and ITD islets were atrophied and had scattered insulin immunoreactivity spots and low BC mass. VTD islets were almost similar to CN. Besides insulin-like activity, vanadium protected pancreatic islet BC, and the relief of glucose toxicity happening with vanadium had a little role in this action.

Effect of Vanadium and Tea Polyphenols on Intestinal Morphology, Microflora and Short-Chain Fatty Acid Profile of Laying Hens.

PubMed

Yuan, Z H; Wang, J P; Zhang, K Y; Ding, X M; Bai, S P; Zeng, Q F; Xuan, Y; Su, Z W

2016-12-01

Vanadium (V) is a trace element which can induce dysfunction of gastro-intestine and egg quality deterioration of laying hens. This study was conducted to determine the effect of tea polyphenols (TP) on intestinal morphology, microflora, and short-chain fatty acid (SCFA) profile of laying hens fed vanadium containing diets. A total of 120 Lohman laying hens (67-week-old) were randomly divided into 4 groups with 6 replicates and 5 birds each for a 35-day feeding trial. The dietary treatments were as follows: (1) control (CON), fed a basal diet; (2) vanadium treatment (V10), CON +10 mg V/kg; (3) TP treatment 1 (TP1): V10 + 600 mg TP/kg; (4) TP treatment 2 (TP2): V10 + 1000 mg TP/kg. Fed 10 mg V/kg diets to laying hens did not affect the cecum flora diversity index (H), degree of homogeneity (EH), and richness (S), but hens fed TP2 diet decreased the H, EH, and S (P < 0.05). The cecum butyrate acid concentration was lower in V10 treatment and higher in TP2 treatment (P < 0.05). Addition of 10 mg/kg V resulted in an increased (P < 0.01) duodenal cell apoptosis rate, and 1000 mg/kg TP supplementation overcame (P < 0.01) this reduction effect induced by vanadium. The results indicated that supplementation of 10 mg/kg vanadium increased duodenal cell apoptosis and reduced cecum butyrate acid content. Addition of 1000 mg/kg TP increased the SCFA production to affect cecum flora ecology and protected the duodenal cell from excess apoptosis caused by vanadium.

Does the Relief of Glucose Toxicity Act As a Mediator in Proliferative Actions of Vanadium on Pancreatic Islet Beta Cells in Streptozocin Diabetic Rats?

PubMed Central

Pirmoradi, Leila; Mohammadi, Mohammad Taghi; Safaei, Akbar; Mesbah, Fakhardin; Dehghani, Gholam Abbas

2014-01-01

Background: Data shows vanadium protects pancreatic beta cells (BC) from diabetic animals. Whether this effect is direct or through the relief of glucose toxicity is not clear. This study evaluated the potential effect of oral vanadyl sulfate (vanadium) on glycemic status and pancreatic BC of normal and diabetic rats. Methods: Rats were divided into five groups of normal and diabetic. Diabetes was induced with streptozocin (40 mg/kg, i.v.). Normal rats used water (CN) or vanadium (1 mg/ml VOSO4, VTN). Diabetic rats used water (CD), water plus daily neutral protamine Hagedorn insulin injection (80 U/kg, ITD) or vanadium (VTD). Blood samples were taken for blood glucose (BG, mg/dL) and insulin (ng/dL) measurements. After two months, the pancreata of sacrificed rats were prepared for islet staining. Results: Pre-treated normal BG was 88 ± 2, and diabetic BG was 395 ± 9. The final BG in CD, VTD, and ITD was 509 ± 22, 138 ± 14, and 141 ± 14, respectively. Insulin in VTN (0.75 ± 0.01) and VTD (0.78 ± 0.01) was similar, higher than CD (0.51 ± 0.07) but lower than CN (2.51 ± 0.02). VTN islets compared to CN had larger size and denser central core insulin immunoreactivity with plentiful BC. CD and ITD islets were atrophied and had scattered insulin immunoreactivity spots and low BC mass. VTD islets were almost similar to CN. Conclusion: Besides insulin-like activity, vanadium protected pancreatic islet BC, and the relief of glucose toxicity happening with vanadium had a little role in this action. PMID:24842144

Growth control of the oxidation state in vanadium oxide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Shinbuhm; Meyer, Tricia L.; Lee, Ho Nyung, E-mail: hnlee@ornl.gov

2014-12-01

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V{sub 2}{sup +3}O{sub 3}, V{sup +4}O{sub 2}, and V{sub 2}{sup +5}O{sub 5}. A well pronounced MIT was only observed in VO{sub 2} films grown in a very narrow range of oxygen partial pressure P(O{sub 2}). The films grown either in lower (<10 mTorr) or higher P(O{sub 2}) (>25 mTorr) result in V{sub 2}O{sub 3} and V{sub 2}O{sub 5} phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO{sub 2} thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.« less

An Ultrastable Heterobimetallic Uranium(IV)/Vanadium(III) Solid Compound Protected by a Redox-Active Phosphite Ligand: Crystal Structure, Oxidative Dissolution, and First-Principles Simulation.

PubMed

Gui, Daxiang; Dai, Xing; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Chen, Lanhua; Zhang, Chao; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2018-02-05

The first heterobimetallic uranium(IV)/vanadium(III) phosphite compound, Na 2 UV 2 (HPO 3 ) 6 (denoted as UVP), was synthesized via an in situ redox-active hydrothermal reaction. It exhibits superior hydrolytic and antioxidant stability compared to the majority of structures containing low-valent uranium or vanadium, further elucidated by first-principles simulations, and therefore shows potential applications in nuclear waste management.

Positron lifetime in vanadium oxide bronzes

NASA Astrophysics Data System (ADS)

Dryzek, J.; Dryzek, E.

2003-09-01

The positron lifetime (PL) and Doppler broadening (DB) of annihilation line measurements have been performed in vanadium oxide bronzes MxV2O5. The dependence of these annihilation characteristics on the kind and concentration of the metal M donor has been observed. In the PL spectrum only one lifetime component has been detected in all studied bronzes. The results indicate the positron localization in the structural tunnels present in the crystalline lattice of the vanadium oxide bronzes. (

Molecular based magnets comprising vanadium tetracyanoethylene complexes for shielding electromagnetic fields

DOEpatents

Epstein, A.J.; Morin, B.G.

1998-10-13

The invention presents a vanadium tetracyanoethylene solvent complex for electromagnetic field shielding, and a method for blocking low frequency and magnetic fields using these vanadium tetracyanoethylene compositions. The compositions of the invention can be produced at ambient temperature and are light weight, low density and flexible. The materials of the present invention are useful as magnetic shields to block low frequency fields and static fields, and for use in cores in transformers and motors. 21 figs.

Molecular based magnets comprising vanadium tetracyanoethylene complexes for shielding electromagnetic fields

DOEpatents

Epstein, Arthur J.; Morin, Brian G.

1998-01-01

The invention presents a vanadium tetracyanoethylene solvent complex for electromagnetic field shielding, and a method for blocking low frequency and magnetic fields using these vanadium tetracyanoethylene compositions. The compositions of the invention can be produced at ambient temperature and are light weight, low density and flexible. The materials of the present invention are useful as magnetic shields to block low frequency fields and static fields, and for use in cores in transformers and motors.

Butanol Dehydration over V₂O₅-TiO₂/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition.

PubMed

Choi, Hyeonhee; Bae, Jung-Hyun; Kim, Do Heui; Park, Young-Kwon; Jeon, Jong-Ki

2013-04-29

MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO₂-V₂O₅/MCM-41 catalysts were analyzed using XRF, BET, NH₃-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO₂/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH₃-TPD and Py-IR results indicated that weak acid sites were produced over the TiO₂/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V₂O₅(12.1)-TiO₂/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.

Effect of Variable Oxidation States of Vanadium on the Structural, Optical, and Dielectric Properties of B2O3-Li2O-ZnO-V2O5 Glasses.

PubMed

Arya, S K; Danewalia, S S; Arora, Manju; Singh, K

2016-12-01

In the present study, the effect of variable vanadium oxidation states on the structural, optical, and dielectric properties of vanadium oxide containing lithium borate glasses has been investigated. Electron paramagnetic resonance studies indicate that vanadium in these glasses is mostly in the V 4+ state, having a tetragonal symmetry. As the glass composition of V 2 O 5 increases, tetragonality also increases at the cost of octahedral symmetry. The photoluminescence (PL) spectra of these glasses are dominated by zinc oxide transition, whereas the peaks pertaining to the vanadyl group are not visible in the PL spectra. The optical absorption spectra show a single wide absorption band, which is attributed to V 4+ ions in these glasses. The ac conductivity of the glasses increases with an increase in vanadium content. The highest electrical conductivity observed is ∼10 -5 S cm -1 at 250 °C for the glass with 2.5 mol % V 2 O 5 . Electrical conductivity is dominated by electron conduction, as indicated by the activation energy calculation.

Thermally Stable Solution Processed Vanadium Oxide as a Hole Extraction Layer in Organic Solar Cells

PubMed Central

Alsulami, Abdullah; Griffin, Jonathan; Alqurashi, Rania; Yi, Hunan; Iraqi, Ahmed; Lidzey, David; Buckley, Alastair

2016-01-01

Low-temperature solution-processable vanadium oxide (V2Ox) thin films have been employed as hole extraction layers (HELs) in polymer bulk heterojunction solar cells. V2Ox films were fabricated in air by spin-coating vanadium(V) oxytriisopropoxide (s-V2Ox) at room temperature without the need for further thermal annealing. The deposited vanadium(V) oxytriisopropoxide film undergoes hydrolysis in air, converting to V2Ox with optical and electronic properties comparable to vacuum-deposited V2O5. When s-V2Ox thin films were annealed in air at temperatures of 100 °C and 200 °C, OPV devices showed similar results with good thermal stability and better light transparency. Annealing at 300 °C and 400 °C resulted in a power conversion efficiency (PCE) of 5% with a decrement approximately 15% lower than that of unannealed films; this is due to the relative decrease in the shunt resistance (Rsh) and an increase in the series resistance (Rs) related to changes in the oxidation state of vanadium. PMID:28773356

Switching adhesion forces by crossing the metal–insulator transition in Magnéli-type vanadium oxide crystals

PubMed Central

Klemm, Matthias; Horn, Siegfried; Woydt, Mathias

2011-01-01

Summary Magnéli-type vanadium oxides form the homologous series VnO2 n -1 and exhibit a temperature-induced, reversible metal–insulator first order phase transition (MIT). We studied the change of the adhesion force across the transition temperature between the cleavage planes of various vanadium oxide Magnéli phases (n = 3 … 7) and spherical titanium atomic force microscope (AFM) tips by systematic force–distance measurements with a variable-temperature AFM under ultrahigh vacuum conditions (UHV). The results show, for all investigated samples, that crossing the transition temperatures leads to a distinct change of the adhesion force. Low adhesion corresponds consistently to the metallic state. Accordingly, the ability to modify the electronic structure of the vanadium Magnéli phases while maintaining composition, stoichiometry and crystallographic integrity, allows for relating frictional and electronic material properties at the nano scale. This behavior makes the vanadium Magnéli phases interesting candidates for technology, e.g., as intelligent devices or coatings where switching of adhesion or friction is desired. PMID:21977416

Doping of vanadium to nanocrystalline diamond films by hot filament chemical vapor deposition

PubMed Central

2012-01-01

Doping an impure element with a larger atomic volume into crystalline structure of buck crystals is normally blocked because the rigid crystalline structure could not tolerate a larger distortion. However, this difficulty may be weakened for nanocrystalline structures. Diamonds, as well as many semiconductors, have a difficulty in effective doping. Theoretical calculations carried out by DFT indicate that vanadium (V) is a dopant element for the n-type diamond semiconductor, and their several donor state levels are distributed between the conduction band and middle bandgap position in the V-doped band structure of diamond. Experimental investigation of doping vanadium into nanocrystalline diamond films (NDFs) was first attempted by hot filament chemical vapor deposition technique. Acetone/H2 gas mixtures and vanadium oxytripropoxide (VO(OCH2CH2CH3)3) solutions of acetone with V and C elemental ratios of 1:5,000, 1:2,000, and 1:1,000 were used as carbon and vanadium sources, respectively. The resistivity of the V-doped NDFs decreased two orders with the increasing V/C ratios. PMID:22873631