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 comparative study of all-vanadium and iron-chromium redox flow batteries for large-scale energy storage

NASA Astrophysics Data System (ADS)

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

2015-12-01

The promise of redox flow batteries (RFBs) utilizing soluble redox couples, such as all vanadium ions as well as iron and chromium ions, is becoming increasingly recognized for large-scale energy storage of renewables such as wind and solar, owing to their unique advantages including scalability, intrinsic safety, and long cycle life. An ongoing question associated with these two RFBs is determining whether the vanadium redox flow battery (VRFB) or iron-chromium redox flow battery (ICRFB) is more suitable and competitive for large-scale energy storage. To address this concern, a comparative study has been conducted for the two types of battery based on their charge-discharge performance, cycle performance, and capital cost. It is found that: i) the two batteries have similar energy efficiencies at high current densities; ii) the ICRFB exhibits a higher capacity decay rate than does the VRFB; and iii) the ICRFB is much less expensive in capital costs when operated at high power densities or at large capacities.

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.

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.

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.

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.

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.

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.

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.

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

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.

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…

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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).

Patents on Membranes Based on Non-Fluorinated Polymers for Vanadium Redox Flow Batteries.

PubMed

Choi, So-Won; Kim, Tae-Ho; Cha, Sang-Ho

2017-07-10

Vanadium redox flow batteries (VRFBs) have received considerable attention as large-scale electrochemical energy storage systems. In particular, VRFBs offer a higher power and energy density than other RFBs and mitigate undesirable performance fading, such as inevitable ion crossover, because of the unique advantage that only the vanadium ion is employed as the active species in the two electrolytes. The key constituent of VRFBs is a separator to conduct protons and prevent cross-mixing of the positive and negative electrolytes. For this purpose, ion exchange membranes like sulfonated polymer membranes can be used. Although this type of membrane does not have ion exchange groups, it can achieve an ion exchange capacity by the formation of pores. This review highlights the patents on the preparation of non-fluorinated membranes (sulfonated aromatic polymer membranes and porous membranes) as alternatives to high-cost perfluorinated polymers and their VRFB performance. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

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.

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.

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.

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.

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.

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.

Efficiency improvement of an all-vanadium redox flow battery by harvesting low-grade heat

NASA Astrophysics Data System (ADS)

Reynard, Danick; Dennison, C. R.; Battistel, Alberto; Girault, Hubert H.

2018-06-01

Redox flow batteries (RFBs) are rugged systems, which can withstand several thousand cycles and last many years. However, they suffer from low energy density, low power density, and low efficiency. Integrating a Thermally Regenerative Electrochemical Cycle (TREC) into the RFB, it is possible to mitigate some of these drawbacks. The TREC takes advantage of the temperature dependence of the cell voltage to convert heat directly into electrical energy. Here, the performance increase of a TREC-RFB is investigated using two kinds of all-vanadium electrolyte chemistries: one containing a typical concentration of sulfuric acid and one containing a large excess of hydrochloric acid. The results show that the energy density of the system was increased by 1.3Wh L-1 and 0.8Wh L-1, respectively and the overall energy efficiency also increased by 9 and 5 percentage points, respectively. The integration of the heat exchangers necessary to change the battery temperature is readily facilitated by the design of the redox flow battery, which already utilizes fluid circulation loops.

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.

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.

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.

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 .

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.

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.

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.

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.

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.

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.

"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%.

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.

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

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.

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

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.

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.

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.

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.

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.

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

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.

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.

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.

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

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.

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

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

A Membrane‐Free Redox Flow Battery with Two Immiscible Redox Electrolytes

PubMed Central

Navalpotro, Paula; Palma, Jesus; Anderson, Marc

2017-01-01

Abstract Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short‐lifetimes, and expensive ion‐selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane‐free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof‐of‐concept of a membrane‐free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L−1, and is able to deliver 90 % of its theoretical capacity while showing excellent long‐term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). PMID:28658538

A Membrane-Free Redox Flow Battery with Two Immiscible Redox Electrolytes.

PubMed

Navalpotro, Paula; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

2017-10-02

Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short-lifetimes, and expensive ion-selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane-free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof-of-concept of a membrane-free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L -1 , and is able to deliver 90 % of its theoretical capacity while showing excellent long-term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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.

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.

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.

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.

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.

Interactions of vanadium( iv ) with amidoxime ligands: redox reactivity

DOE PAGES

Parker, B. F.; Hohloch, S.; Pankhurst, J. R.; ...

2018-01-01

Vanadium is the main competitor for uranium extraction from seawater, and V( iv ) comprises a minor but important portion of this. V( iv ) undergoes redox reactions with oximes and amidoxime ligands under seawater-relevant conditions, leading to V( v ) complexes and loss of oxime functional groups.

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.

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

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.

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

Estimating the system price of redox flow batteries for grid storage

NASA Astrophysics Data System (ADS)

Ha, Seungbum; Gallagher, Kevin G.

2015-11-01

Low-cost energy storage systems are required to support extensive deployment of intermittent renewable energy on the electricity grid. Redox flow batteries have potential advantages to meet the stringent cost target for grid applications as compared to more traditional batteries based on an enclosed architecture. However, the manufacturing process and therefore potential high-volume production price of redox flow batteries is largely unquantified. We present a comprehensive assessment of a prospective production process for aqueous all vanadium flow battery and nonaqueous lithium polysulfide flow battery. The estimated investment and variable costs are translated to fixed expenses, profit, and warranty as a function of production volume. When compared to lithium-ion batteries, redox flow batteries are estimated to exhibit lower costs of manufacture, here calculated as the unit price less materials costs, owing to their simpler reactor (cell) design, lower required area, and thus simpler manufacturing process. Redox flow batteries are also projected to achieve the majority of manufacturing scale benefits at lower production volumes as compared to lithium-ion. However, this advantage is offset due to the dramatically lower present production volume of flow batteries compared to competitive technologies such as lithium-ion.

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.

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.

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.

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).

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.

Neutral Red and Ferroin as Reversible and Rapid Redox Materials for Redox Flow Batteries.

PubMed

Hong, Jeehoon; Kim, Ketack

2018-06-11

Neutral red and ferroin are used as redox indicators (RINs) in potentiometric titrations. The rapid response and reversibility that are prerequisites for RINs are also desirable properties for the active materials in redox flow batteries (RFBs). This study describes the electrochemical properties of ferroin and neutral red as a redox pair. The rapid reaction rates of the RINs allow a cell to run at a rate of 4 C with 89 % capacity retention after the 100 th  cycle. The diffusion coefficients, electrode reaction rates, and solubilities of the RINs were determined. The electron-transfer rate constants of ferroin and neutral red are 0.11 and 0.027 cm s -1 , respectively, which are greater than those of the components of all-vanadium and Zn/Br 2 cells. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

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

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.

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.

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.

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.

Electrochemical behaviour of vanadium(V)/vanadium(IV) redox couple at graphite electrodes

NASA Astrophysics Data System (ADS)

Zhong, S.; Skyllas-Kazacos, M.

The electrochemical behaviour of the V(V)/V(IV) couple has been studied at a graphite disc electrode in sulfuric acid using both cyclic and rotating-disc voltammetry. The results from the latter technique have revealed that the cathodic and anodic characteristics of this redox couple are quite different. The diffusion coefficient for V(IV), 2.14×10-6 cm2 s-1, is independent of the vanadium concentration. For V(IV) oxidation, the electrode kinetic parameters i0 and α have values of 2.47×10-4 A cm-2 and 0.71, respectively. The exchange current density, i0, for the V(V)/V(IV) reaction has been obtained at both graphite felt and reticulated vitreous carbon electrodes.

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.

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.

Redox Species of Redox Flow Batteries: A Review.

PubMed

Pan, Feng; Wang, Qing

2015-11-18

Due to the capricious nature of renewable energy resources, such as wind and solar, large-scale energy storage devices are increasingly required to make the best use of the renewable power. The redox flow battery is considered suitable for large-scale applications due to its modular design, good scalability and flexible operation. The biggest challenge of the redox flow battery is the low energy density. The redox active species is the most important component in redox flow batteries, and the redox potential and solubility of redox species dictate the system energy density. This review is focused on the recent development of redox species. Different categories of redox species, including simple inorganic ions, metal complexes, metal-free organic compounds, polysulfide/sulfur and lithium storage active materials, are reviewed. The future development of redox species towards higher energy density is also suggested.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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).

Redox Flow Batteries, a Review

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

Knoxville, U. Tennessee; U. Texas Austin; U, McGill

2011-07-15

Redox flow batteries are enjoying a renaissance due to their ability to store large amounts of electrical energy relatively cheaply and efficiently. In this review, we examine the components of redox flow batteries with a focus on understanding the underlying physical processes. The various transport and kinetic phenomena are discussed along with the most common redox couples.

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

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.

Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide

DOE PAGES

Britto, Sylvia; Leskes, Michal; Hua, Xiao; ...

2015-06-08

Vanadium sulfide VS 4 in the patronite mineral structure, is a linear chain compound comprising vanadium atoms coordinated by disulfide anions [S 2] 2–. 51V NMR shows that the material, despite having V formally in the d 1 configuration, is diamagnetic, suggesting potential dimerization through metal-metal bonding associated with a Peierls distortion of the linear chains. This is supported by density functional calculations, and is also consistent with the observed alternation in V-V distances of 2.8 Å and 3.2 Å along the chains. Partial lithiation results in reduction of the disulfide ions to sulfide S 2–, including via an internalmore » redox process whereby an electron from V 4+ is transferred to [S 2] 2– resulting in oxidation of V 4+ to V 5+ and reduction of the [S 2] 2– to S 2- to form Li 3VS 4 containing tetrahedral [VS 4] 3– anions. On further lithiation this is followed by reduction of the V 5+ in Li 3VS 4 to form Li 3+xVS 4 (x=0.5-1), a mixed valent V 4+/V 5+ compound. Eventually reduction to Li 2S plus elemental V occurs. Despite the complex redox processes involving both the cation and the anion occurring in this material, the system is found to be partially reversible between 0 and 3 V. In conclusion, the unusual redox processes in this system are elucidated using a suite of short range characterization tools including 51V Nuclear Magnetic Resonance spectroscopy (NMR), S Kedge X-ray Absorption Near Edge Spectroscopy (XANES) and Pair Distribution Function (PDF) Analysis of X-ray data.« less

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.

High energy density redox flow device

DOEpatents

Chiang, Yet-Ming; Carter, W. Craig; Ho, Bryan Y; Duduta, Mihai; Limthongkul, Pimpa

2014-05-13

Redox flow devices are described in which at least one of the positive electrode or negative electrode-active materials is a semi-solid or is a condensed ion-storing electroactive material, and in which at least one of the electrode-active materials is transported to and from an assembly at which the electrochemical reaction occurs, producing electrical energy. The electronic conductivity of the semi-solid is increased by the addition of conductive particles to suspensions and/or via the surface modification of the solid in semi-solids (e.g., by coating the solid with a more electron conductive coating material to increase the power of the device). High energy density and high power redox flow devices are disclosed. The redox flow devices described herein can also include one or more inventive design features. In addition, inventive chemistries for use in redox flow devices are also described.

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.

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

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.

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.

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.

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.

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.

Coupling desalination and energy storage with redox flow electrodes.

PubMed

Hou, Xianhua; Liang, Qian; Hu, Xiaoqiao; Zhou, Yu; Ru, Qiang; Chen, Fuming; Hu, Shejun

2018-06-26

Both freshwater shortage and energy crisis are global issues. Herein, we present a double-function system of faradaic desalination and a redox flow battery consisting of VCl3|NaI redox flow electrodes and a feed stream. The system has a nominal cell potential (E0 = +0.79 V). During the discharge process, the salt ions in the feed are extracted by the redox reaction of the flow electrodes, which is indicated by salt removal. Stable and reversible salt removal capacity and electricity can be achieved up to 30 cycles. The energy consumption is as low as 10.27 kJ mol-1 salt. The energy efficiency is as high as 50% in the current aqueous redox flow battery. With energy recovery, the desalination energy consumption decreases greatly to 5.38 kJ mol-1; this is the lowest reported value to date. This "redox flow battery desalination generator" can be operated in a voltage range of 0.3-1.1 V. Our research provides a novel method for obtaining energy-saving desalination and redox flow batteries.

Redox active polymers and colloidal particles for flow batteries

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

Gavvalapalli, Nagarjuna; Moore, Jeffrey S.; Rodriguez-Lopez, Joaquin

The invention provides a redox flow battery comprising a microporous or nanoporous size-exclusion membrane, wherein one cell of the battery contains a redox-active polymer dissolved in the non-aqueous solvent or a redox-active colloidal particle dispersed in the non-aqueous solvent. The redox flow battery provides enhanced ionic conductivity across the electrolyte separator and reduced redox-active species crossover, thereby improving the performance and enabling widespread utilization. Redox active poly(vinylbenzyl ethylviologen) (RAPs) and redox active colloidal particles (RACs) were prepared and were found to be highly effective redox species. Controlled potential bulk electrolysis indicates that 94-99% of the nominal charge on different RAPsmore » is accessible and the electrolysis products are stable upon cycling. The high concentration attainable (>2.0 M) for RAPs in common non-aqueous battery solvents, their electrochemical and chemical reversibility, and their hindered transport across porous separators make them attractive materials for non-aqueous redox flow batteries based on size-selectivity.« less

Comparative analysis for various redox flow batteries chemistries using a cost performance model

NASA Astrophysics Data System (ADS)

Crawford, Alasdair; Viswanathan, Vilayanur; Stephenson, David; Wang, Wei; Thomsen, Edwin; Reed, David; Li, Bin; Balducci, Patrick; Kintner-Meyer, Michael; Sprenkle, Vincent

2015-10-01

The total energy storage system cost is determined by means of a robust performance-based cost model for multiple flow battery chemistries. Systems aspects such as shunt current losses, pumping losses and various flow patterns through electrodes are accounted for. The system cost minimizing objective function determines stack design by optimizing the state of charge operating range, along with current density and current-normalized flow. The model cost estimates are validated using 2-kW stack performance data for the same size electrodes and operating conditions. Using our validated tool, it has been demonstrated that an optimized all-vanadium system has an estimated system cost of < 350 kWh-1 for 4-h application. With an anticipated decrease in component costs facilitated by economies of scale from larger production volumes, coupled with performance improvements enabled by technology development, the system cost is expected to decrease to 160 kWh-1 for a 4-h application, and to 100 kWh-1 for a 10-h application. This tool has been shared with the redox flow battery community to enable cost estimation using their stack data and guide future direction.

Redox flow cell energy storage systems

NASA Technical Reports Server (NTRS)

Thaller, L. H.

1979-01-01

The redox flow cell energy storage system being developed by NASA for use in remote power systems and distributed storage installations for electric utilities is presented. The system under consideration is an electrochemical storage device which utilizes the oxidation and reduction of two fully soluble redox couples (acidified chloride solutions of chromium and iron) as active electrode materials separated by a highly selective ion exchange membrane. The reactants are contained in large storage tanks and pumped through a stack of redox flow cells where the electrochemical reactions take place at porous carbon felt electrodes. Redox equipment has allowed the incorporation of state of charge readout, stack voltage control and system capacity maintenance (rebalance) devices to regulate cells in a stack jointly. A 200 W, 12 V system with a capacity of about 400 Wh has been constructed, and a 2 kW, 10kWh system is planned.

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.

All-soluble all-iron aqueous redox-flow battery

DOE PAGES

Gong, Ke; Xu, Fei; Grunewald, Jonathan B.; ...

2016-05-03

The rapid growth of intermittent renewable energy (e.g., wind and solar) demands low-cost and large-scale energy storage systems for smooth and reliable power output, where redox-flow batteries (RFBs) could find their niche. In this work, we introduce the first all-soluble all-iron RFB based on iron as the same redox-active element but with different coordination chemistries in alkaline aqueous system. The adoption of the same redox-active element largely alleviates the challenging problem of cross-contamination of metal ions in RFBs that use two redox-active elements. An all-soluble all-iron RFB is constructed by combining an iron–triethanolamine redox pair (i.e., [Fe(TEOA)OH] –/[Fe(TEOA)(OH)] 2–) andmore » an iron–cyanide redox pair (i.e., Fe(CN) 6 3–/Fe(CN) 6 4–), creating 1.34 V of formal cell voltage. Furthermore, good performance and stability have been demonstrated, after addressing some challenges, including the crossover of the ligand agent. As exemplified by the all-soluble all-iron flow battery, combining redox pairs of the same redox-active element with different coordination chemistries could extend the spectrum of RFBs.« less

Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

PubMed Central

Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

2016-01-01

Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V. PMID:27966605

Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

NASA Astrophysics Data System (ADS)

Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

2016-12-01

Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V.

Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility.

PubMed

Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

2016-12-14

Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V.

Polyoxometalate active charge-transfer material for mediated redox flow battery

DOEpatents

Anderson, Travis Mark; Hudak, Nicholas; Staiger, Chad; Pratt, Harry

2017-01-17

Redox flow batteries including a half-cell electrode chamber coupled to a current collecting electrode are disclosed herein. In a general embodiment, a separator is coupled to the half-cell electrode chamber. The half-cell electrode chamber comprises a first redox-active mediator and a second redox-active mediator. The first redox-active mediator and the second redox-active mediator are circulated through the half-cell electrode chamber into an external container. The container includes an active charge-transfer material. The active charge-transfer material has a redox potential between a redox potential of the first redox-active mediator and a redox potential of the second redox-active mediator. The active charge-transfer material is a polyoxometalate or derivative thereof. The redox flow battery may be particularly useful in energy storage solutions for renewable energy sources and for providing sustained power to an electrical grid.

Control of a Vanadium Redox Battery and supercapacitor using a Three-Level Neutral Point Clamped converter

NASA Astrophysics Data System (ADS)

Etxeberria, A.; Vechiu, I.; Baudoin, S.; Camblong, H.; Kreckelbergh, S.

2014-02-01

The increasing use of distributed generators, which are mainly based on renewable sources, can create several issues in the operation of the electric grid. The microgrid is being analysed as a solution to the integration in the grid of the renewable sources at a high penetration level in a controlled way. The storage systems play a vital role in order to keep the energy and power balance of the microgrid. Due to the technical limitations of the currently available storage systems, it is necessary to use more than one storage technology to satisfy the requirements of the microgrid application. This work validates in simulations and experimentally the use of a Three-Level Neutral Point Clamped converter to control the power flow of a hybrid storage system formed by a SuperCapacitor and a Vanadium Redox Battery. The operation of the system is validated in two case studies in the experimental platform installed in ESTIA. The experimental results prove the validity of the proposed system as well as the designed control algorithm. The good agreement among experimental and simulation results also validates the simulation model, that can therefore be used to analyse the operation of the system in different case studies.

High-energy redox-flow batteries with hybrid metal foam electrodes.

PubMed

Park, Min-Sik; Lee, Nam-Jin; Lee, Seung-Wook; Kim, Ki Jae; Oh, Duk-Jin; Kim, Young-Jun

2014-07-09

A nonaqueous redox-flow battery employing [Co(bpy)3](+/2+) and [Fe(bpy)3](2+/3+) redox couples is proposed for use in large-scale energy-storage applications. We successfully demonstrate a redox-flow battery with a practical operating voltage of over 2.1 V and an energy efficiency of 85% through a rational cell design. By utilizing carbon-coated Ni-FeCrAl and Cu metal foam electrodes, the electrochemical reactivity and stability of the nonaqueous redox-flow battery can be considerably enhanced. Our approach intoduces a more efficient conversion of chemical energy into electrical energy and enhances long-term cell durability. The cell exhibits an outstanding cyclic performance of more than 300 cycles without any significant loss of energy efficiency. Considering the increasing demands for efficient energy storage, our achievement provides insight into a possible development pathway for nonaqueous redox-flow batteries with high energy densities.

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.

Arteriovenous oscillations of the redox potential: Is the redox state influencing blood flow?

PubMed

Poznanski, Jaroslaw; Szczesny, Pawel; Pawlinski, Bartosz; Mazurek, Tomasz; Zielenkiewicz, Piotr; Gajewski, Zdzislaw; Paczek, Leszek

2017-09-01

Studies on the regulation of human blood flow revealed several modes of oscillations with frequencies ranging from 0.005 to 1 Hz. Several mechanisms were proposed that might influence these oscillations, such as the activity of vascular endothelium, the neurogenic activity of vessel wall, the intrinsic activity of vascular smooth muscle, respiration, and heartbeat. These studies relied typically on non-invasive techniques, for example, laser Doppler flowmetry. Oscillations of biochemical markers were rarely coupled to blood flow. The redox potential difference between the artery and the vein was measured by platinum electrodes placed in the parallel homonymous femoral artery and the femoral vein of ventilated anesthetized pigs. Continuous measurement at 5 Hz sampling rate using a digital nanovoltmeter revealed fluctuating signals with three basic modes of oscillations: ∼ 1, ∼ 0.1 and ∼ 0.01 Hz. These signals clearly overlap with reported modes of oscillations in blood flow, suggesting coupling of the redox potential and blood flow. The amplitude of the oscillations associated with heart action was significantly smaller than for the other two modes, despite the fact that heart action has the greatest influence on blood flow. This finding suggests that redox potential in blood might be not a derivative but either a mediator or an effector of the blood flow control system.

Cascade redox flow battery systems

DOEpatents

Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

2014-07-22

A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

The Chemistry of Redox-Flow Batteries.

PubMed

Noack, Jens; Roznyatovskaya, Nataliya; Herr, Tatjana; Fischer, Peter

2015-08-17

The development of various redox-flow batteries for the storage of fluctuating renewable energy has intensified in recent years because of their peculiar ability to be scaled separately in terms of energy and power, and therefore potentially to reduce the costs of energy storage. This has resulted in a considerable increase in the number of publications on redox-flow batteries. This was a motivation to present a comprehensive and critical overview of the features of this type of batteries, focusing mainly on the chemistry of electrolytes and introducing a thorough systematic classification to reveal their potential for future development. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox flow batteries having multiple electroactive elements

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

Wang, Wei; Li, Liyu; Yang, Zhenguo

Introducing multiple redox reactions with a suitable voltage range can improve the energy density of redox flow battery (RFB) systems. One example includes RFB systems utilizing multiple redox pairs in the positive half cell, the negative half cell, or in both. Such RFB systems can have a negative electrolyte, a positive electrolyte, and a membrane between the negative electrolyte and the positive electrolyte, in which at least two electrochemically active elements exist in the negative electrolyte, the positive electrolyte, or both.

The impact of pH on side reactions for aqueous redox flow batteries based on nitroxyl radical compounds

NASA Astrophysics Data System (ADS)

Orita, A.; Verde, M. G.; Sakai, M.; Meng, Y. S.

2016-07-01

Electrochemical and UV-VIS measurements demonstrate that the pH value of a 4-hydroxy-2,2,6,6-tetramethyl-1-pipperidinyloxyl (TEMPOL) electrolyte significantly impacts its redox reversibility. The diffusion coefficient and kinetic rate constant of TEMPOL in neutral aqueous solution are determined and shown to be comparable to those of vanadium ions used for industrially utilized redox flow batteries (RFBs). RFBs that incorporate a TEMPOL catholyte and Zn-based anolyte have an average voltage of 1.46 V and an energy efficiency of 80.4% during the initial cycle, when subject to a constant current of 10 mA cm-2. We demonstrate several factors that significantly influence the concentration and capacity retention of TEMPOL upon cycling; namely, pH and atmospheric gases dissolved in electrolyte. We expand upon the known reactions of TEMPOL in aqueous electrolyte and propose several concepts to improve its electrochemical performance in a RFB. Controlling these factors will be the key to enable the successful implementation of this relatively inexpensive and environmentally friendly battery.

Performance Characterization and Optimization of Microgrid-Based Energy Generation and Storage Technologies

DTIC Science & Technology

2012-01-01

A. Rufer, “Multiphysics and energetic modeling of a vanadium redox flow battery ,” in Proc. 2008 IEEE International Conference on Sustainable...p. 81. [11] K.W. Knehr and E.C. Kumbur, "Open circuit voltage of vanadium redox flow batteries : Discrepancy between models and experiments...Blanc and A. Rufer, “Multiphysics and energetic modeling of a vanadium redox flow battery ,” in Proc. 2008 IEEE International Conference on Sustainable

Cost-driven materials selection criteria for redox flow battery electrolytes

NASA Astrophysics Data System (ADS)

Dmello, Rylan; Milshtein, Jarrod D.; Brushett, Fikile R.; Smith, Kyle C.

2016-10-01

Redox flow batteries show promise for grid-scale energy storage applications but are presently too expensive for widespread adoption. Electrolyte material costs constitute a sizeable fraction of the redox flow battery price. As such, this work develops a techno-economic model for redox flow batteries that accounts for redox-active material, salt, and solvent contributions to the electrolyte cost. Benchmark values for electrolyte constituent costs guide identification of design constraints. Nonaqueous battery design is sensitive to all electrolyte component costs, cell voltage, and area-specific resistance. Design challenges for nonaqueous batteries include minimizing salt content and dropping redox-active species concentration requirements. Aqueous battery design is sensitive to only redox-active material cost and cell voltage, due to low area-specific resistance and supporting electrolyte costs. Increasing cell voltage and decreasing redox-active material cost present major materials selection challenges for aqueous batteries. This work minimizes cost-constraining variables by mapping the battery design space with the techno-economic model, through which we highlight pathways towards low price and moderate concentration. Furthermore, the techno-economic model calculates quantitative iterations of battery designs to achieve the Department of Energy battery price target of 100 per kWh and highlights cost cutting strategies to drive battery prices down further.

The Redox Flow System for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Odonnell, P.; Gahn, R. F.; Pfeiffer, W.

1976-01-01

The interfacing of a Solar Photovoltaic System and a Redox Flow System for storage was workable. The Redox Flow System, which utilizes the oxidation-reduction capability of two redox couples, in this case iron and titanium, for its storage capacity, gave a relatively constant output regardless of solar activity so that a load could be run continually day and night utilizing the sun's energy. One portion of the system was connected to a bank of solar cells to electrochemically charge the solutions, while a separate part of the system was used to electrochemically discharge the stored energy.

A multi-electron redox mediator for redox-targeting lithium-sulfur flow batteries

NASA Astrophysics Data System (ADS)

Li, Guochun; Yang, Liuqing; Jiang, Xi; Zhang, Tianran; Lin, Haibin; Yao, Qiaofeng; Lee, Jim Yang

2018-02-01

The lithium-sulfur flow battery (LSFB) is a new addition to the rechargeable lithium flow batteries (LFBs) where sulfur or a sulfur compound is used as the cathode material against the lithium anode. We report here our evaluation of an organic sulfide - dimethyl trisulfide (DMTS), as 1) a catholyte of a LFB and 2) a multi-electron redox mediator for discharging and charging a solid sulfur cathode without any conductive additives. The latter configuration is also known as the redox-targeting lithium-sulfur flow battery (RTLSFB). The LFB provides an initial discharge capacity of 131.5 mAh g-1DMTS (1.66 A h L-1), which decreases to 59 mAh g-1DMTS (0.75 A h L-1) after 40 cycles. The RTLSFB delivers a significantly higher application performance - initial discharge capacity of 1225.3 mAh g-1sulfur (3.83 A h L-1), for which 1030.9 mAh g-1sulfur (3.23 A h L-1) is still available after 40 cycles. The significant increase in the discharge and charge duration of the LFB after sulfur addition indicates that DMTS is better used as a redox mediator in a RTLSFB than as a catholyte in a LFB.

A biomimetic redox flow battery based on flavin mononucleotide

PubMed Central

Orita, Akihiro; Verde, Michael G.; Sakai, Masanori; Meng, Ying Shirley

2016-01-01

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures. PMID:27767026

A biomimetic redox flow battery based on flavin mononucleotide

NASA Astrophysics Data System (ADS)

Orita, Akihiro; Verde, Michael G.; Sakai, Masanori; Meng, Ying Shirley

2016-10-01

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures.

A biomimetic redox flow battery based on flavin mononucleotide.

PubMed

Orita, Akihiro; Verde, Michael G; Sakai, Masanori; Meng, Ying Shirley

2016-10-21

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures.

Pumping power considerations in the designs of NASA-Redox flow cells

NASA Technical Reports Server (NTRS)

Hoberecht, M. A.

1981-01-01

Pressure drop data for six different cell geometries of various flow port, manifold, and cavity dimensions are presented. The redox/energy/storage system uses two fully soluble redox couples as anode and cathode fluids. Both fluids are pumped through a redox cell, or stack of cells, where the electrochemical reactions take place at porous carbon felt electrodes. Pressure drop losses are therefore associated with this system due to the continuous flow of reactant solutions. The exact pressure drop within a redox flow cell is directly dependent on the flow rate as well as the various cell dimensions. Pumping power requirements for a specific set of cell operating conditions are found for various cell geometries once the flow rate and pressure drop are determined. These pumping power requirements contribute to the overall system parasitic energy losses which must be minimized, the choice of cell geometry becomes critical.

Redox-Flow Batteries: From Metals to Organic Redox-Active Materials.

PubMed

Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

2017-01-16

Research on redox-flow batteries (RFBs) is currently experiencing a significant upturn, stimulated by the growing need to store increasing quantities of sustainably generated electrical energy. RFBs are promising candidates for the creation of smart grids, particularly when combined with photovoltaics and wind farms. To achieve the goal of "green", safe, and cost-efficient energy storage, research has shifted from metal-based materials to organic active materials in recent years. This Review presents an overview of various flow-battery systems. Relevant studies concerning their history are discussed as well as their development over the last few years from the classical inorganic, to organic/inorganic, to RFBs with organic redox-active cathode and anode materials. Available technologies are analyzed in terms of their technical, economic, and environmental aspects; the advantages and limitations of these systems are also discussed. Further technological challenges and prospective research possibilities are highlighted. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Unleashing the Power and Energy of LiFePO4-Based Redox Flow Lithium Battery with a Bifunctional Redox Mediator.

PubMed

Zhu, Yun Guang; Du, Yonghua; Jia, Chuankun; Zhou, Mingyue; Fan, Li; Wang, Xingzhu; Wang, Qing

2017-05-10

Redox flow batteries, despite great operation flexibility and scalability for large-scale energy storage, suffer from low energy density and relatively high cost as compared to the state-of-the-art Li-ion batteries. Here we report a redox flow lithium battery, which operates via the redox targeting reactions of LiFePO 4 with a bifunctional redox mediator, 2,3,5,6-tetramethyl-p-phenylenediamine, and presents superb energy density as the Li-ion battery and system flexibility as the redox flow battery. The battery has achieved a tank energy density as high as 1023 Wh/L, power density of 61 mW/cm 2 , and voltage efficiency of 91%. Operando X-ray absorption near-edge structure measurements were conducted to monitor the evolution of LiFePO 4 , which provides insightful information on the redox targeting process, critical to the device operation and optimization.

Long-Cycling Aqueous Organic Redox Flow Battery (AORFB) toward Sustainable and Safe Energy Storage.

PubMed

Hu, Bo; DeBruler, Camden; Rhodes, Zayn; Liu, T Leo

2017-01-25

Redox flow batteries (RFBs) are a viable technology to store renewable energy in the form of electricity that can be supplied to electricity grids. However, widespread implementation of traditional RFBs, such as vanadium and Zn-Br 2 RFBs, is limited due to a number of challenges related to materials, including low abundance and high costs of redox-active metals, expensive separators, active material crossover, and corrosive and hazardous electrolytes. To address these challenges, we demonstrate a neutral aqueous organic redox flow battery (AORFB) technology utilizing a newly designed cathode electrolyte containing a highly water-soluble ferrocene molecule. Specifically, water-soluble (ferrocenylmethyl)trimethylammonium chloride (FcNCl, 4.0 M in H 2 O, 107.2 Ah/L, and 3.0 M in 2.0 NaCl, 80.4 Ah/L) and N 1 -ferrocenylmethyl-N 1 ,N 1 ,N 2 ,N 2 ,N 2 -pentamethylpropane-1,2-diaminium dibromide, (FcN 2 Br 2 , 3.1 M in H 2 O, 83.1 Ah/L, and 2.0 M in 2.0 M NaCl, 53.5 Ah/L) were synthesized through structural decoration of hydrophobic ferrocene with synergetic hydrophilic functionalities including an ammonium cation group and a halide anion. When paired with methyl viologen (MV) as an anolyte, resulting FcNCl/MV and FcN 2 Br 2 /MV AORFBs were operated in noncorrosive neutral NaCl supporting electrolytes using a low-cost anion-exchange membrane. These ferrocene/MV AORFBs are characterized as having high theoretical energy density (45.5 Wh/L) and excellent cycling performance from 40 to 100 mA/cm 2 . Notably, the FcNCl/MV AORFBs (demonstrated at 7.0 and 9.9 Wh/L) exhibited unprecedented long cycling performance, 700 cycles at 60 mA/cm 2 with 99.99% capacity retention per cycle, and delivered power density up to 125 mW/cm 2 . These AORFBs are built from earth-abundant elements and are environmentally benign, thus representing a promising choice for sustainable and safe energy storage.

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

Recent developments in organic redox flow batteries: A critical review

NASA Astrophysics Data System (ADS)

Leung, P.; Shah, A. A.; Sanz, L.; Flox, C.; Morante, J. R.; Xu, Q.; Mohamed, M. R.; Ponce de León, C.; Walsh, F. C.

2017-08-01

Redox flow batteries (RFBs) have emerged as prime candidates for energy storage on the medium and large scales, particularly at the grid scale. The demand for versatile energy storage continues to increase as more electrical energy is generated from intermittent renewable sources. A major barrier in the way of broad deployment and deep market penetration is the use of expensive metals as the active species in the electrolytes. The use of organic redox couples in aqueous or non-aqueous electrolytes is a promising approach to reducing the overall cost in long-term, since these materials can be low-cost and abundant. The performance of such redox couples can be tuned by modifying their chemical structure. In recent years, significant developments in organic redox flow batteries has taken place, with the introduction of new groups of highly soluble organic molecules, capable of providing a cell voltage and charge capacity comparable to conventional metal-based systems. This review summarises the fundamental developments and characterization of organic redox flow batteries from both the chemistry and materials perspectives. The latest advances, future challenges and opportunities for further development are discussed.

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.

Redox flow cell energy storage systems

NASA Technical Reports Server (NTRS)

Thaller, L. H.

1979-01-01

NASA-Redox systems are electrochemical storage devices that use two fully soluble Redox couples, anode and cathode fluids, as active electrode materials separated by a highly selective ion exchange membrane. The reactants are contained in large storage tanks and pumped through a stack of Redox flow cells where the electrochemical reactions (reduction and oxidation) take place at porous carbon felt electrodes. A string or stack of these power producing cells is connected in series in a bipolar manner. Redox energy storage systems promise to be inexpensive and possess many features that provide for flexible design, long life, high reliability and minimal operation and maintenance costs. These features include independent sizing of power and storage capacity requirements and inclusion within the cell stack of a cell that monitors the state of charge of the system as a whole, and a rebalance cell which permits continuous correction to be made for minor side reactions that would tend to result in the anode fluid and cathode fluids becoming electrochemically out of balance. These system features are described and discussed.

Liquid Quinones for Solvent-Free Redox Flow Batteries.

PubMed

Shimizu, Akihiro; Takenaka, Keisuke; Handa, Naoyuki; Nokami, Toshiki; Itoh, Toshiyuki; Yoshida, Jun-Ichi

2017-11-01

Liquid benzoquinone and naphthoquinone having diethylene glycol monomethyl ether groups are designed and synthesized as redox active materials that dissolve supporting electrolytes. The Li-ion batteries based on the liquid quinones using LiBF 4 /PC show good performance in terms of voltage, capacity, energy efficiency, and cyclability in both static and flow modes. A battery is constructed without using intentionally added organic solvent, and its high energy density (264 W h L -1 ) demonstrates the potential of solvent-free organic redox flow batteries using liquid active materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

PubMed

Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

2015-06-11

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

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.

Double-membrane triple-electrolyte redox flow battery design

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

Yushan, Yan; Gu, Shuang; Gong, Ke

A redox flow battery is provided having a double-membrane (one cation exchange membrane and one anion exchange membrane), triple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and one electrolyte positioned between and in contact with the two membranes). The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolyte and the positive or negative electrolyte. This design physically isolates, but ionically connects, the negative electrolyte and positive electrolyte. The physical isolation offers greatmore » freedom in choosing redox pairs in the negative electrolyte and positive electrolyte, making high voltage of redox flow batteries possible. The ionic conduction drastically reduces the overall ionic crossover between negative electrolyte and positive one, leading to high columbic efficiency.« less

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.

Polyarene mediators for mediated redox flow battery

DOEpatents

Delnick, Frank M.; Ingersoll, David; Liang, Chengdu

2018-01-02

The fundamental charge storage mechanisms in a number of currently studied high energy redox couples are based on intercalation, conversion, or displacement reactions. With exception to certain metal-air chemistries, most often the active redox materials are stored physically in the electrochemical cell stack thereby lowering the practical gravimetric and volumetric energy density as a tradeoff to achieve reasonable power density. In a general embodiment, a mediated redox flow battery includes a series of secondary organic molecules that form highly reduced anionic radicals as reaction mediator pairs for the reduction and oxidation of primary high capacity redox species ex situ from the electrochemical cell stack. Arenes are reduced to stable anionic radicals that in turn reduce a primary anode to the charged state. The primary anode is then discharged using a second lower potential (more positive) arene. Compatible separators and solvents are also disclosed herein.

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.

Performance Mapping Studies in Redox Flow Cells

NASA Technical Reports Server (NTRS)

Hoberecht, M. A.; Thaller, L. H.

1981-01-01

Pumping power requirements in any flow battery system constitute a direct parasitic energy loss. It is therefore useful to determine the practical lower limit for reactant flow rates. Through the use of a theoretical framework based on electrochemical first principles, two different experimental flow mapping techniques were developed to evaluate and compare electrodes as a function of flow rate. For the carbon felt electrodes presently used in NASA-Lewis Redox cells, a flow rate 1.5 times greater than the stoichiometric rate seems to be the required minimum.

Electrochemically-Induced Redox Reactions in Basalt at High Pressure and Temperature: An Iron and Vanadium K-edge XANES Study

NASA Astrophysics Data System (ADS)

Kavner, A.; Walker, D.; Newville, M.; Sutton, S. R.

2005-12-01

An applied electric field across a silicate sample at high pressures and temperatures in a piston cylinder apparatus can generate a wide range of oxidation states of polyvalent cations within a single experiment. If two or more polyvalent cations are included, this technique can be used to cross-calibrate oxybarometers within a single experiment. The redox state of Fe and V within a partially melted basaltic silicate was manipulated in situ in a piston-cylinder experiment with a DC power supply providing a source and sink of electrons to the sample. A 1V electrical potential differential was applied across vanadium-doped and Fe-bearing synthetic basalt samples for 24 hrs. at 20 kbar and 1400°C in a specially-designed piston cylinder sample assembly. Three experiments were performed: a control sample with no applied voltage, one with bottom cathode and top anode, and a third with top cathode and bottom anode. Synchrotron-based x-ray absorption near edge structure (XANES) spectroscopy was used to provide spot analysis of iron and vanadium oxidation states with 5μm x 5μm spatial resolution throughout the recovered samples. Systematic spatial changes of increasing oxidation states of V and Fe were observed approaching the anode. The differences in oxidation states were mapped to a corresponding local effective oxygen fugacity by comparison and extension of a calibration of vanadium oxidation states as a function of controlled oxygen fugacity from a previous study (Sutton et al., 2005, GCA, vol. 69, pp. 2333-2348). The vanadium mapping indicates that a 1V potential drop across the sample induces effective oxygen fugacity perturbations in excess of ten orders of magnitude. The presence of both Fe and V within the same sample provides a wide range of oxygen fugacity cross-calibration in these recovered samples. A relationship between oxygen fugacity and electrochemical driving force is derived. The experimental results are in good agreement with the derived

Induction of apoptosis in human colorectal cancer cell line, HCT-116 by a vanadium- Schiff base complex.

PubMed

Sinha, Abhinaba; Banerjee, Kaushik; Banerjee, Arpita; Sarkar, Avijit; Ahir, Manisha; Adhikary, Arghya; Chatterjee, Mitali; Choudhuri, Soumitra Kumar

2017-08-01

Vanadium compounds are well known for their therapeutic interventions against several diseases. Various biochemical attributes of vanadium complexes inspired us to evaluate the cancer cell killing efficacy of the vanadium complex, viz., vanadyl N-(2-hydroxyacetophenone) glycinate [VO(NG) 2 ]. Previously we showed that VO(NG) 2 is an effective anticancer agent in in vitro and in vivo cancer models and imposed miniscule side effects. Herein we report that VO(NG) 2 is significantly cytotoxic to various cancer cell lines. Furthermore, this redox active vanadyl complex altered the redox homeostatsis of many human cancer cell lines significantly. VO(NG) 2 actuates programmed cell death in human colorectal carcinoma cells(HCT-116) through mitochondrial outer membrane permeabilization but in caspase independent manner, possibly by altering cellular redox status and by inflicting DNA damage. Thus, the present work is an attempt to provide many evidences regarding the potent and selective chemotherapeutic efficacy of the novel VO(NG) 2 . Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Multiple-membrane multiple-electrolyte redox flow battery design

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

Yan, Yushan; Gu, Shuang; Gong, Ke

A redox flow battery is provided. The redox flow battery involves multiple-membrane (at least one cation exchange membrane and at least one anion exchange membrane), multiple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and at least one electrolyte disposed between the two membranes) as the basic characteristic, such as a double-membrane, triple electrolyte (DMTE) configuration or a triple-membrane, quadruple electrolyte (TMQE) configuration. The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolytemore » and the positive or negative electrolyte.« less

Anthraquinone with tailored structure for a nonaqueous metal-organic redox flow battery.

PubMed

Wang, Wei; Xu, Wu; Cosimbescu, Lelia; Choi, Daiwon; Li, Liyu; Yang, Zhenguo

2012-07-07

A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of ~82% and a specific discharge energy density similar to those of aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

A solar rechargeable flow battery based on photoregeneration of two soluble redox couples.

PubMed

Liu, Ping; Cao, Yu-liang; Li, Guo-Ran; Gao, Xue-Ping; Ai, Xin-Ping; Yang, Han-Xi

2013-05-01

Storable sunshine, reusable rays: A solar rechargeable redox flow battery is proposed based on the photoregeneration of I(3)(-)/I(-) and [Fe(C(10)H(15))(2)](+)/Fe(C(10)H(15))(2) soluble redox couples, which can be regenerated by flowing from a discharged redox flow battery (RFB) into a dye-sensitized solar cell (DSSC) and then stored in tanks for subsequent RFB applications This technology enables effective solar-to-chemical energy conversion. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic non-aqueous cation-based redox flow batteries

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

Zhang, Lu; Huang, Jinhua; Burrell, Anthony

The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturatedmore » moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.« less

A novel iron-lead redox flow battery for large-scale energy storage

NASA Astrophysics Data System (ADS)

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

2017-04-01

The redox flow battery (RFB) is one of the most promising large-scale energy storage technologies for the massive utilization of intermittent renewables especially wind and solar energy. This work presents a novel redox flow battery that utilizes inexpensive and abundant Fe(II)/Fe(III) and Pb/Pb(II) redox couples as redox materials. Experimental results show that both the Fe(II)/Fe(III) and Pb/Pb(II) redox couples have fast electrochemical kinetics in methanesulfonic acid, and that the coulombic efficiency and energy efficiency of the battery are, respectively, as high as 96.2% and 86.2% at 40 mA cm-2. Furthermore, the battery exhibits stable performance in terms of efficiencies and discharge capacities during the cycle test. The inexpensive redox materials, fast electrochemical kinetics and stable cycle performance make the present battery a promising candidate for large-scale energy storage applications.

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 cell-in-series method: A technique for accelerated electrode degradation in redox flow batteries

DOE PAGES

Pezeshki, Alan M.; Sacci, Robert L.; Veith, Gabriel M.; ...

2015-11-21

Here, we demonstrate a novel method to accelerate electrode degradation in redox flow batteries and apply this method to the all-vanadium chemistry. Electrode performance degradation occurred seven times faster than in a typical cycling experiment, enabling rapid evaluation of materials. This method also enables the steady-state study of electrodes. In this manner, it is possible to delineate whether specific operating conditions induce performance degradation; we found that both aggressively charging and discharging result in performance loss. Post-mortem x-ray photoelectron spectroscopy of the degraded electrodes was used to resolve the effects of state of charge (SoC) and current on the electrodemore » surface chemistry. For the electrode material tested in this work, we found evidence that a loss of oxygen content on the negative electrode cannot explain decreased cell performance. Furthermore, the effects of decreased electrode and membrane performance on capacity fade in a typical cycling battery were decoupled from crossover; electrode and membrane performance decay were responsible for a 22% fade in capacity, while crossover caused a 12% fade.« less

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.

High-energy-density, aqueous, metal-polyiodide redox flow batteries

DOEpatents

Li, Bin; Nie, Zimin; Wang, Wei; Liu, Jun; Sprenkle, Vincent L.

2017-08-29

Improved metal-based redox flow batteries (RFBs) can utilize a metal and a divalent cation of the metal (M.sup.2+) as an active redox couple for a first electrode and electrolyte, respectively, in a first half-cell. For example, the metal can be Zn. The RFBs can also utilize a second electrolyte having I.sup.-, anions of I.sub.x (for x.gtoreq.3), or both in an aqueous solution, wherein the I.sup.- and the anions of I.sub.x (for x.gtoreq.3) compose an active redox couple in a second half-cell.

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.

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.

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage.

PubMed

Zhao, Yu; Ding, Yu; Li, Yutao; Peng, Lele; Byon, Hye Ryung; Goodenough, John B; Yu, Guihua

2015-11-21

Electrical energy storage system such as secondary batteries is the principle power source for portable electronics, electric vehicles and stationary energy storage. As an emerging battery technology, Li-redox flow batteries inherit the advantageous features of modular design of conventional redox flow batteries and high voltage and energy efficiency of Li-ion batteries, showing great promise as efficient electrical energy storage system in transportation, commercial, and residential applications. The chemistry of lithium redox flow batteries with aqueous or non-aqueous electrolyte enables widened electrochemical potential window thus may provide much greater energy density and efficiency than conventional redox flow batteries based on proton chemistry. This Review summarizes the design rationale, fundamentals and characterization of Li-redox flow batteries from a chemistry and material perspective, with particular emphasis on the new chemistries and materials. The latest advances and associated challenges/opportunities are comprehensively discussed.

A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery

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

Duan, Wentao; Vemuri, Rama S.; Hu, Dehong

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, nonaqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of nonaqueous electrolytes. However, significant technical hurdles exist currently limiting nonaqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we report a nonaqueous flow battery based on amore » highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox materials exhibits an ambipolar electrochemical property with two reversible redox pairs that are moderately separated by a voltage gap of ~1.7 V. Therefore, PTIO can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry, which affords the advantages such as high effective redox concentrations and low irreversible redox material crossover. The PTIO flow battery shows decent electrochemical cyclability under cyclic voltammetry and flow cell conditions; an improved redox concentration of 0.5 M PTIO and operational current density of 20 mA cm-2 were achieved in flow cell tests. Moreover, we show that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC) as cross-validated by electron spin resonance measurements. This study suggests FTIR can be used as a reliable online SOC sensor to monitor flow battery status and ensure battery operations stringently in a safe SOC range.« less

Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery.

PubMed

Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric; Lawrence, Chad; Vijayakumar, M; Henderson, Wesley A; Liu, Tianbiao; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent; Wang, Wei

2015-07-20

Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all-organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical-based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox flow cell development and demonstration project, calendar year 1977

NASA Technical Reports Server (NTRS)

1979-01-01

Research and development on the redox flow cell conducted from January 1, 1977, to December 31, 1977, are described in this report. The major focus of the effort during 1977 was the key technology issues that directly influence the fundamental feasibility of the overall redox concept. These issues were the development of a suitable ion exchange membrane for the system, the screening and study of candidate redox couples to achieve optimum cell performance, and the carrying out of systems analysis and modeling to develop system performance goals and cost estimates.

Hypothetical Modeling of Redox Conditions Within a Complex Ground-Water Flow Field in a Glacial Setting

USGS Publications Warehouse

Feinstein, Daniel T.; Thomas, Mary Ann

2009-01-01

This report describes a modeling approach for studying how redox conditions evolve under the influence of a complex ground-water flow field. The distribution of redox conditions within a flow system is of interest because of the intrinsic susceptibility of an aquifer to redox-sensitive, naturally occurring contaminants - such as arsenic - as well as anthropogenic contaminants - such as chlorinated solvents. The MODFLOW-MT3D-RT3D suite of code was applied to a glacial valley-fill aquifer to demonstrate a method for testing the interaction of flow patterns, sources of reactive organic carbon, and availability of electron acceptors in controlling redox conditions. Modeling results show how three hypothetical distributions of organic carbon influence the development of redox conditions in a water-supply aquifer. The distribution of strongly reduced water depends on the balance between the rate of redox reactions and the capability of different parts of the flow system to transmit oxygenated water. The method can take account of changes in the flow system induced by pumping that result in a new distribution of reduced water.

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials.

PubMed

Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D; Schubert, Ulrich S

2015-11-05

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials

NASA Astrophysics Data System (ADS)

Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D.; Schubert, Ulrich S.

2015-11-01

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

A Sustainable Redox-Flow Battery with an Aluminum-Based, Deep-Eutectic-Solvent Anolyte.

PubMed

Zhang, Changkun; Ding, Yu; Zhang, Leyuan; Wang, Xuelan; Zhao, Yu; Zhang, Xiaohong; Yu, Guihua

2017-06-19

Nonaqueous redox-flow batteries are an emerging energy storage technology for grid storage systems, but the development of anolytes has lagged far behind that of catholytes due to the major limitations of the redox species, which exhibit relatively low solubility and inadequate redox potentials. Herein, an aluminum-based deep-eutectic-solvent is investigated as an anolyte for redox-flow batteries. The aluminum-based deep-eutectic solvent demonstrated a significantly enhanced concentration of circa 3.2 m in the anolyte and a relatively low redox potential of 2.2 V vs. Li + /Li. The electrochemical measurements highlight that a reversible volumetric capacity of 145 Ah L -1 and an energy density of 189 Wh L -1 or 165 Wh kg -1 have been achieved when coupled with a I 3 - /I - catholyte. The prototype cell has also been extended to the use of a Br 2 -based catholyte, exhibiting a higher cell voltage with a theoretical energy density of over 200 Wh L -1 . The synergy of highly abundant, dendrite-free, multi-electron-reaction aluminum anodes and environmentally benign deep-eutectic-solvent anolytes reveals great potential towards cost-effective, sustainable redox-flow batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

First-principles molecular dynamics simulation study on electrolytes for use in redox flow battery

NASA Astrophysics Data System (ADS)

Choe, Yoong-Kee; Tsuchida, Eiji; Tokuda, Kazuya; Ootsuka, Jun; Saito, Yoshihiro; Masuno, Atsunobu; Inoue, Hiroyuki

2017-11-01

Results of first-principles molecular dynamics simulations carried out to investigate structural aspects of electrolytes for use in a redox flow battery are reported. The electrolytes studied here are aqueous sulfuric acid solutions where its property is of importance for dissolving redox couples in redox flow battery. The simulation results indicate that structural features of the acid solutions depend on the concentration of sulfuric acid. Such dependency arises from increase of proton dissociation from sulfuric acid.

High energy sodium based room temperature flow batteries

NASA Astrophysics Data System (ADS)

Shamie, Jack

As novel energy sources such as solar, wind and tidal energies are explored it becomes necessary to build energy storage facilities to load level the intermittent nature of these energy sources. Energy storage is achieved by converting electrical energy into another form of energy. Batteries have many properties that are attractive for energy storage including high energy and power. Among many different types of batteries, redox flow batteries (RFBs) offer many advantages. Unlike conventional batteries, RFBs store energy in a liquid medium rather than solid active materials. This method of storage allows for the separation of energy and power unlike conventional batteries. Additionally flow batteries may have long lifetimes because there is no expansion or contraction of electrodes. A major disadvantage of RFB's is its lower energy density when compared to traditional batteries. In this Thesis, a novel hybrid Na-based redox flow battery (HNFB) is explored, which utilizes a room temperature molten sodium based anode, a sodium ion conducting solid electrolyte and liquid catholytes. The sodium electrode leads to high voltages and energy and allows for the possibility of multi-electron transfer per molecule. Vanadium acetylacetonate (acac) and TEMPO have been investigated for their use as catholytes. In the vanadium system, 2 electrons transfers per vanadium atom were found leading to a doubling of capacity. In addition, degradation of the charged state was found to be reversible within the voltage range of the cell. Contamination by water leads to the formation of vanadyl acetylacetonate. Although it is believed that vanadyl complex need to be taken to low voltages to be reduced back to vanadium acac, a new mechanism is shown that begins at higher voltages (2.1V). Vanadyl complexes react with excess ligand and protons to reform the vanadium complex. During this reaction, water is reformed leading to the continuous cycle in which vanadyl is formed and then reduced back

Rebalancing electrolytes in redox flow battery systems

DOEpatents

Chang, On Kok; Pham, Ai Quoc

2014-12-23

Embodiments of redox flow battery rebalancing systems include a system for reacting an unbalanced flow battery electrolyte with a rebalance electrolyte in a first reaction cell. In some embodiments, the rebalance electrolyte may contain ferrous iron (Fe.sup.2+) which may be oxidized to ferric iron (Fe.sup.3+) in the first reaction cell. The reducing ability of the rebalance reactant may be restored in a second rebalance cell that is configured to reduce the ferric iron in the rebalance electrolyte back into ferrous iron through a reaction with metallic iron.

High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries

PubMed Central

2018-01-01

Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation while maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. These studies provide a template for the future design of other redox-active oligomers for this application. PMID:29532018

High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries

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

Hendriks, Koen H.; Robinson, Sophia G.; Braten, Miles N.

Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation whilemore » maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. Finally, these studies provide a template for the future design of other redox-active oligomers for this application.« less

High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries.

PubMed

Hendriks, Koen H; Robinson, Sophia G; Braten, Miles N; Sevov, Christo S; Helms, Brett A; Sigman, Matthew S; Minteer, Shelley D; Sanford, Melanie S

2018-02-28

Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation while maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. These studies provide a template for the future design of other redox-active oligomers for this application.

High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries

DOE PAGES

Hendriks, Koen H.; Robinson, Sophia G.; Braten, Miles N.; ...

2018-01-17

Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation whilemore » maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. Finally, these studies provide a template for the future design of other redox-active oligomers for this application.« less

Performance enhancement of iron-chromium redox flow batteries by employing interdigitated flow fields

NASA Astrophysics Data System (ADS)

Zeng, Y. K.; Zhou, X. L.; Zeng, L.; Yan, X. H.; Zhao, T. S.

2016-09-01

The catalyst for the negative electrode of iron-chromium redox flow batteries (ICRFBs) is commonly prepared by adding a small amount of Bi3+ ions in the electrolyte and synchronously electrodepositing metallic particles onto the electrode surface at the beginning of charge process. Achieving a uniform catalyst distribution in the porous electrode, which is closely related to the flow field design, is critically important to improve the ICRFB performance. In this work, the effects of flow field designs on catalyst electrodeposition and battery performance are investigated. It is found that compared to the serpentine flow field (SFF) design, the interdigitated flow field (IFF) forces the electrolyte through the porous electrode between the neighboring channels and enhances species transport during the processes of both the catalyst electrodeposition and iron/chromium redox reactions, thus enabling a more uniform catalyst distribution and higher mass transport limitation. It is further demonstrated that the energy efficiency of the ICRFB with the IFF reaches 80.7% at a high current density (320 mA cm-2), which is 8.2% higher than that of the ICRFB with the SFF. With such a high performance and intrinsically low-cost active materials, the ICRFB with the IFF offers a great promise for large-scale energy storage.

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.

Fe-V redox flow batteries

DOEpatents

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

2014-07-08

A redox flow battery having a supporting solution that includes Cl.sup.- anions is characterized by an anolyte having V.sup.2+ and V.sup.3+ in the supporting solution, a catholyte having Fe.sup.2+ and Fe.sup.3+ in the supporting solution, and a membrane separating the anolyte and the catholyte. The anolyte and catholyte can have V cations and Fe cations, respectively, or the anolyte and catholyte can each contain both V and Fe cations in a mixture. Furthermore, the supporting solution can contain a mixture of SO.sub.4.sup.2- and Cl.sup.- anions.

The Redox flow system for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Odonnell, P.; Gahn, R. F.

1976-01-01

A new method of storage was applied to a solar photovoltaic system. The storage method is a redox flow system which utilizes the oxidation-reduction capability of two soluble electrochemical redox couples for its storage capacity. The particular variant described separates the charging and discharging function of the system such that the electrochemical couples are simultaneously charged and discharged in separate parts of the system. The solar array had 12 solar cells; wired in order to give a range of voltages and currents. The system stored the solar energy so that a load could be run continually day and night. The main advantages of the redox system are that it can accept a charge in the low voltage range and produce a relatively constant output regardless of solar activity.

Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries.

PubMed

VanGelder, L E; Kosswattaarachchi, A M; Forrestel, P L; Cook, T R; Matson, E M

2018-02-14

Non-aqueous redox flow batteries have emerged as promising systems for large-capacity, reversible energy storage, capable of meeting the variable demands of the electrical grid. Here, we investigate the potential for a series of Lindqvist polyoxovanadate-alkoxide (POV-alkoxide) clusters, [V 6 O 7 (OR) 12 ] (R = CH 3 , C 2 H 5 ), to serve as the electroactive species for a symmetric, non-aqueous redox flow battery. We demonstrate that the physical and electrochemical properties of these POV-alkoxides make them suitable for applications in redox flow batteries, as well as the ability for ligand modification at the bridging alkoxide moieties to yield significant improvements in cluster stability during charge-discharge cycling. Indeed, the metal-oxide core remains intact upon deep charge-discharge cycling, enabling extremely high coulombic efficiencies (∼97%) with minimal overpotential losses (∼0.3 V). Furthermore, the bulky POV-alkoxide demonstrates significant resistance to deleterious crossover, which will lead to improved lifetime and efficiency in a redox flow battery.

An Ambient Temperature Molten Sodium-Vanadium Battery with Aqueous Flowing Catholyte.

PubMed

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

2016-01-20

In this study, we have investigated the key factors dictating the cyclic performance of a new type of hybrid sodium-based flow batteries (HNFBs) that can operate at room temperature with high cell voltages (>3 V), multiple electron transfer redox reactions per active ion, and decoupled design of power and energy. HNFBs are composed of a molten Na-Cs alloy anode, flowing aqueous catholyte, and a Na-β″-Al2O3 solid electrolyte as the separator. The surface functionalization of graphite felt electrodes for the flowing aqueous catholyte has been studied for its effectiveness in enhancing V(2+)/V(3+), V(3+)/V(4+), and V(4+)/V(5+) redox couples. The V(4+)/V(5+) redox reaction has been further investigated at different cell operation temperatures for its cyclic stability and how the properties of the solid electrolyte membrane play a role in cycling. These fundamental understandings provide guidelines for improving the cyclic performance and stability of HNFBs with aqueous catholytes. We show that the HNFB with aqueous V-ion catholyte can reach high storage capacity (∼70% of the theoretical capacity) with good Coulombic efficiency (90% ± 1% in 2-30 cycles) and cyclic performance (>99% capacity retention for 30 cycles). It demonstrates, for the first time, the potential of high capacity HNFBs with aqueous catholytes, good capacity retention and long cycling life. This is also the first demonstration that Na-β″-Al2O3 solid electrolyte can be used with aqueous electrolyte at near room temperature for more than 30 cycles.

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.

A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery.

PubMed

Duan, Wentao; Vemuri, Rama S; Hu, Dehong; Yang, Zheng; Wei, Xiaoliang

2017-02-13

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, non-aqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of non-aqueous electrolytes. However, significant technical hurdles exist currently limiting non-aqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we recently reported a non-aqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox material exhibits an ambipolar electrochemical property, and therefore can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry. Moreover, we demonstrated that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC), as cross-validated by electron spin resonance (ESR) measurements. Herein we present a video protocol for the electrochemical evaluation and SOC diagnosis of the PTIO symmetric flow battery. With a detailed description, we experimentally demonstrated the route to achieve such purposes. This protocol aims to spark more interests and insights on the safety and reliability in the field of non-aqueous redox flow batteries.

A redox-flow battery with an alloxazine-based organic electrolyte

NASA Astrophysics Data System (ADS)

Lin, Kaixiang; Gómez-Bombarelli, Rafael; Beh, Eugene S.; Tong, Liuchuan; Chen, Qing; Valle, Alvaro; Aspuru-Guzik, Alán; Aziz, Michael J.; Gordon, Roy G.

2016-09-01

Redox-flow batteries (RFBs) can store large amounts of electrical energy from variable sources, such as solar and wind. Recently, redox-active organic molecules in aqueous RFBs have drawn substantial attention due to their rapid kinetics and low membrane crossover rates. Drawing inspiration from nature, here we report a high-performance aqueous RFB utilizing an organic redox compound, alloxazine, which is a tautomer of the isoalloxazine backbone of vitamin B2. It can be synthesized in high yield at room temperature by single-step coupling of inexpensive o-phenylenediamine derivatives and alloxan. The highly alkaline-soluble alloxazine 7/8-carboxylic acid produces a RFB exhibiting open-circuit voltage approaching 1.2 V and current efficiency and capacity retention exceeding 99.7% and 99.98% per cycle, respectively. Theoretical studies indicate that structural modification of alloxazine with electron-donating groups should allow further increases in battery voltage. As an aza-aromatic molecule that undergoes reversible redox cycling in aqueous electrolyte, alloxazine represents a class of radical-free redox-active organics for use in large-scale energy storage.

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

A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR

DOE PAGES

Duan, Wentao; Vemuri, Rama Ses; Milshtein, Jarrod D.; ...

2016-03-10

Redox flow batteries have shown outstanding promise for grid-scale energy storage to promote utilization of renewable energy and improve grid stability. Nonaqueous battery systems can potentially achieve high energy density because of their broad voltage window. In this paper, we report a new organic redox-active material for use in a nonaqueous redox flow battery, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO) that has high solubility (>2.6 M) in organic solvents. PTIO exhibits electrochemically reversible disproportionation reactions and thus can serve as both anolyte and catholyte redox materials in a symmetric flow cell. The PTIO flow battery has a moderate cell voltage of ~1.7 V andmore » shows good cyclability under both cyclic voltammetry and flow cell conditions. Moreover, we demonstrate that FTIR can offer accurate estimation of the PTIO concentration in electrolytes and determine the state of charge of the PTIO flow cell, which suggests FTIR potentially as a powerful online battery status sensor. In conclusion, this study is expected to inspire more insights in this under-addressed area of state of charge analysis aiming at operational safety and reliability of flow batteries.« less

Iron-sulfide redox flow batteries

DOEpatents

Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

2016-06-14

Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

Iron-sulfide redox flow batteries

DOEpatents

Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

2013-12-17

Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

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).

Ab Initio Metadynamics Study of the VO2+/VO2+ Redox Reaction Mechanism at the Graphite Edge/Water Interface.

PubMed

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2018-06-20

Redox flow batteries (RFBs) are promising electrochemical energy storage systems, for which development is impeded by a poor understanding of redox reactions occurring at electrode/electrolyte interfaces. Even for the conventional all-vanadium RFB chemistry employing V 2+ /V 3+ and VO 2 + /VO 2+ couples, there is still no consensus about the reaction mechanism, electrode active sites, and rate-determining step. Herein, we perform Car-Parrinello molecular dynamics-based metadynamics simulations to unravel the mechanism of the VO 2 + /VO 2+ redox reaction in water at the oxygen-functionalized graphite (112̅0) edge surface serving as a representative carbon-based electrode. Our results suggest that during the battery discharge aqueous VO 2 + /VO 2+ species adsorb at the surface C-O groups as inner-sphere complexes, exhibiting faster adsorption/desorption kinetics than V 2+ /V 3+ , at least at low vanadium concentrations considered in our study. We find that this is because (i) VO 2 + /VO 2+ conversion does not involve the slow transfer of an oxygen atom, (ii) protonation of VO 2 + is spontaneous and coupled to interfacial electron transfer in acidic conditions to enable VO 2+ formation, and (iii) V 3+ found to be strongly bound to oxygen groups of the graphite surface features unfavorable desorption kinetics. In contrast, the reverse process taking place upon charging is expected to be more sluggish for the VO 2 + /VO 2+ redox couple because of both unfavorable deprotonation of the VO 2+ water ligands and adsorption/desorption kinetics.

Liquid Catholyte Molecules for Nonaqueous Redox Flow Batteries

DOE PAGES

Huang, Jinhua; Cheng, Lei; Assary, Rajeev S.; ...

2014-11-25

In this study, a series of dimethoxybenzene-based catholyte molecules, which are electrochemically reversible at high potential (4.0 V vs Li/Li +) and in the form of liquid, is developed. The liquid nature offers the molecules the possibility of being a solo or co-solvent for nonaqueous redox flow batteries. This could dramatically improve the energy density.

Stable Vanadium Isotopes as a Redox Proxy at High Temperatures?

NASA Astrophysics Data System (ADS)

Prytulak, J.; Sossi, P.; Halliday, A.; Plank, T. A.; Savage, P.; Woodhead, J. D.

2016-12-01

There is currently no consensus on the relative oxygen fugacity (fO2) of the mantle source of mid-ocean ridge basalts compared to the sub-arc mantle, the region that is central to the mediation of crust-mantle mass balances. Vanadium is a multivalent transition metal whose stable isotope fractionation may reflect oxygen fugacity (fO2). However, a direct link between V isotope composition and fO2 is currently far from convincingly demonstrated. Furthermore, differences in co-ordination environment also play a large role in causing stable isotope fractionation. Here we present V isotope measurements of two suites of co-genetic magmas from contrasting tectonic settings: the Mariana arc and Hekla volcano, Iceland. We use this data alongside the tightly constrained V isotope composition of MORB [1] to assess the effects of fO2 and crystal fractionation on stable vanadium isotopes. We show that, for a given MgO content, V isotopes are identical within analytical error between arc basalts from the Marianas, lavas from Hekla, and MORB. The most striking aspect of our igneous, high temperature V isotope data is the large isotope fractionation (on the order of 2 ‰) towards heavier values in magmatic suites from both Hekla and the Marianas with progressive differentiation. We use a self consistent model of fractionating cotectic phases in both igneous suites to match major, trace and V isotope data. Vanadium partition coefficients required for (titano)magnetite are significantly higher in Hekla (DVmag = 42) than Mariana lavas (DVmag = 32), consistent with a more oxidised source in the latter. Calculated Rayleigh fractionation factors are similar in both suites (Δ51Vmin-melt of -0.4 to -0.5‰) and strongly implicate co-ordination differences between oxides and melt are the dominant driving force for V isotope fractionation. Thus, although fO2likely has a second order effect on V isotopes, they are not a direct proxy for oxygen fugacity in magmatic systems. [1] Prytulak, et

Vanadium based materials as electrode materials for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Yan, Yan; Li, Bing; Guo, Wei; Pang, Huan; Xue, Huaiguo

2016-10-01

As a kind of supercapacitors, pseudocapacitors have attracted wide attention in recent years. The capacitance of the electrochemical capacitors based on pseudocapacitance arises mainly from redox reactions between electrolytes and active materials. These materials usually have several oxidation states for oxidation and reduction. Many research teams have focused on the development of an alternative material for electrochemical capacitors. Many transition metal oxides have been shown to be suitable as electrode materials of electrochemical capacitors. Among them, vanadium based materials are being developed for this purpose. Vanadium based materials are known as one of the best active materials for high power/energy density electrochemical capacitors due to its outstanding specific capacitance and long cycle life, high conductivity and good electrochemical reversibility. There are different kinds of synthetic methods such as sol-gel hydrothermal/solvothermal method, template method, electrospinning method, atomic layer deposition, and electrodeposition method that have been successfully applied to prepare vanadium based electrode materials. In our review, we give an overall summary and evaluation of the recent progress in the research of vanadium based materials for electrochemical capacitors that include synthesis methods, the electrochemical performances of the electrode materials and the devices.

Na-Ion Intercalation and Charge Storage Mechanism in 2D Vanadium Carbide

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

Bak, Seong-Min; Qiao, Ruimin; Yang, Wanli

Two-dimensional vanadium carbide MXene containing surface functional groups (denoted as V2CTx, where Tx are surface functional groups) was synthesized and studied as anode material for Na-ion batteries. V2CTx anode exhibits reversible charge storage with good cycling stability and high rate capability through electrochemical test. The charge storage mechanism of V2CTx material during Na+ intercalation/deintercalation and the redox reaction of vanadium were studied using a combination of synchrotron based X-ray diffraction (XRD), hard X-ray absorption near edge spectroscopy (XANES) and soft X-ray absorption spectroscopy (sXAS). Experimental evidence of a major contribution of redox reaction of vanadium to the charge storage andmore » the reversible capacity of V2CTx during sodiation/desodiation process have been provided through V K-edge XANES and V L2,3-edge sXAS results. A correlation between the CO32- content and Na+ intercalation/deintercalation states in the V2CTx electrode observed from C and O K-edge in sXAS results imply that some additional charge storage reactions may take place between the Na+-intercalated V2CTx and the carbonate based non-aqueous electrolyte. The results of this study will provide valuable information for the further studies on V2CTx as anode material for Na-ion batteries and capacitors.« less

Estimation of Transport and Kinetic Parameters of Vanadium Redox Batteries Using Static Cells

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

Lee, Seong Beom; Pratt, III, Harry D.; Anderson, Travis M.

Mathematical models of Redox Flow Batteries (RFBs) can be used to analyze cell performance, optimize battery operation, and control the energy storage system efficiently. Among many other models, physics-based electrochemical models are capable of predicting internal states of the battery, such as temperature, state-of-charge, and state-of-health. In the models, estimating parameters is an important step that can study, analyze, and validate the models using experimental data. A common practice is to determine these parameters either through conducting experiments or based on the information available in the literature. However, it is not easy to investigate all proper parameters for the modelsmore » through this way, and there are occasions when important information, such as diffusion coefficients and rate constants of ions, has not been studied. Also, the parameters needed for modeling charge-discharge are not always available. In this paper, an efficient way to estimate parameters of physics-based redox battery models will be proposed. Furthermore, this paper also demonstrates that the proposed approach can study and analyze aspects of capacity loss/fade, kinetics, and transport phenomena of the RFB system.« less

Estimation of Transport and Kinetic Parameters of Vanadium Redox Batteries Using Static Cells

DOE PAGES

Lee, Seong Beom; Pratt, III, Harry D.; Anderson, Travis M.; ...

2018-03-27

Mathematical models of Redox Flow Batteries (RFBs) can be used to analyze cell performance, optimize battery operation, and control the energy storage system efficiently. Among many other models, physics-based electrochemical models are capable of predicting internal states of the battery, such as temperature, state-of-charge, and state-of-health. In the models, estimating parameters is an important step that can study, analyze, and validate the models using experimental data. A common practice is to determine these parameters either through conducting experiments or based on the information available in the literature. However, it is not easy to investigate all proper parameters for the modelsmore » through this way, and there are occasions when important information, such as diffusion coefficients and rate constants of ions, has not been studied. Also, the parameters needed for modeling charge-discharge are not always available. In this paper, an efficient way to estimate parameters of physics-based redox battery models will be proposed. Furthermore, this paper also demonstrates that the proposed approach can study and analyze aspects of capacity loss/fade, kinetics, and transport phenomena of the RFB system.« less

Towards a thermally regenerative all-copper redox flow battery.

PubMed

Peljo, Pekka; Lloyd, David; Doan, Nguyet; Majaneva, Marko; Kontturi, Kyösti

2014-02-21

An all-copper redox flow battery based on strong complexation of Cu(+) with acetonitrile is demonstrated, exhibiting reasonable battery performance. More interestingly, the battery can be charged by heat sources of 100 °C, by distilling off the acetonitrile. This destabilizes the Cu(+) complex, leading to recovery of the starting materials.

Redox zonation for different groundwater flow paths during bank filtration: a case study at Liao River, Shenyang, northeastern China

NASA Astrophysics Data System (ADS)

Su, Xiaosi; Lu, Shuai; Yuan, Wenzhen; Woo, Nam Chil; Dai, Zhenxue; Dong, Weihong; Du, Shanghai; Zhang, Xinyue

2018-03-01

The spatial and temporal distribution of redox zones in an aquifer is important when designing groundwater supply systems. Redox zonation can have direct or indirect control of the biological and chemical reactions and mobility of pollutants. In this study, redox conditions are characterized by interpreting the hydrogeological conditions and water chemistry in groundwater during bank infiltration at a site in Shenyang, northeast China. The relevant redox processes and zonal differences in a shallow flow path and deeper flow path at the field scale were revealed by monitoring the redox parameters and chemistry of groundwater near the Liao River. The results show obvious horizontal and vertical components of redox zones during bank filtration. Variations in the horizontal extent of the redox zone were controlled by the different permeabilities of the riverbed sediments and aquifer with depth. Horizontally, the redox zone was situated within 17 m of the riverbank for the shallow flow path and within 200 m for the deep flow path. The vertical extent of the redox zone was affected by precipitation and seasonal river floods and extended to 10 m below the surface. During bank filtration, iron and manganese oxides or hydroxides were reductively dissolved, and arsenic that was adsorbed onto the medium surface or coprecipitated is released into the groundwater. This leads to increased arsenic content in groundwater, which poses a serious threat to water supply security.

Critical rate of electrolyte circulation for preventing zinc dendrite formation in a zinc-bromine redox flow battery

NASA Astrophysics Data System (ADS)

Yang, Hyeon Sun; Park, Jong Ho; Ra, Ho Won; Jin, Chang-Soo; Yang, Jung Hoon

2016-09-01

In a zinc-bromine redox flow battery, a nonaqueous and dense polybromide phase formed because of bromide oxidation in the positive electrolyte during charging. This formation led to complicated two-phase flow on the electrode surface. The polybromide and aqueous phases led to different kinetics of the Br/Br- redox reaction; poor mixing of the two phases caused uneven redox kinetics on the electrode surface. As the Br/Br- redox reaction was coupled with the zinc deposition reaction, the uneven redox reaction on the positive electrode was accompanied by nonuniform zinc deposition and zinc dendrite formation, which degraded battery stability. A single-flow cell was operated at varying electrolyte circulation rates and current densities. Zinc dendrite formation was observed after cell disassembly following charge-discharge testing. In addition, the flow behavior in the positive compartment was observed by using a transparent version of the cell. At low rate of electrolyte circulation, the polybromide phase clearly separated from the aqueous phase and accumulated at the bottom of the flow frame. In the corresponding area on the negative electrode, a large amount of zinc dendrites was observed after charge-discharge testing. Therefore, a minimum circulation rate should be considered to avoid poor mixing of the positive electrolyte.

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

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.

4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl as a model organic redox active compound for nonaqueous flow batteries

NASA Astrophysics Data System (ADS)

Milshtein, Jarrod D.; Barton, John L.; Darling, Robert M.; Brushett, Fikile R.

2016-09-01

Nonaqueous redox flow batteries (NAqRFBs) that utilize redox active organic molecules are an emerging energy storage concept with the possibility of meeting grid storage requirements. Sporadic and uneven advances in molecular discovery and development, however, have stymied efforts to quantify the performance characteristics of nonaqueous redox electrolytes and flow cells. A need exists for archetypal redox couples, with well-defined electrochemical properties, high solubility in relevant electrolytes, and broad availability, to serve as probe molecules. This work investigates the 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl (AcNH-TEMPO) redox pair for such an application. We report the physicochemical and electrochemical properties of the reduced and oxidized compounds at dilute concentrations for electroanalysis, as well as moderate-to-high concentrations for RFB applications. Changes in conductivity, viscosity, and UV-vis absorbance as a function of state-of-charge are quantified. Cyclic voltammetry investigates the redox potential, reversibility, and diffusion coefficients of dilute solutions, while symmetric flow cell cycling determines the stability of the AcNH-TEMPO redox pair over long experiment times. Finally, single electrolyte flow cell studies demonstrate the utility of this redox couple as a platform chemistry for benchmarking NAqRFB performance.

Systems and methods for rebalancing redox flow battery electrolytes

DOEpatents

Pham, Ai Quoc; Chang, On Kok

2015-03-17

Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

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.

Aqueous electrolytes for redox flow battery systems

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

Liu, Tianbiao; Li, Bin; Wei, Xiaoliang

An aqueous redox flow battery system includes an aqueous catholyte and an aqueous anolyte. The aqueous catholyte may comprise (i) an optionally substituted thiourea or a nitroxyl radical compound and (ii) a catholyte aqueous supporting solution. The aqueous anolyte may comprise (i) metal cations or a viologen compound and (ii) an anolyte aqueous supporting solution. The catholyte aqueous supporting solution and the anolyte aqueous supporting solution independently may comprise (i) a proton source, (ii) a halide source, or (iii) a proton source and a halide source.

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.

Na-Ion Intercalation and Charge Storage Mechanism in Two-Dimensional Vanadium Carbide

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

Bak, Seong -Min; Qiao, Ruimin; Yang, W.

We synthesized two-dimensional vanadium carbide MXene containing surface functional groups (denoted as V 2CT x, where T x are surface functional groups) and studied as anode material for Na-ion batteries. V 2CT x anode exhibits reversible charge storage with good cycling stability and high rate capability through electrochemical test. Furthermore, the charge storage mechanism of V 2CT x material during Na + intercalation/deintercalation and the redox reaction of vanadium were studied using a combination of synchrotron based X-ray diffraction (XRD), hard X-ray absorption near edge spectroscopy (XANES) and soft X-ray absorption spectroscopy (sXAS). Experimental evidence of a major contribution ofmore » redox reaction of vanadium to the charge storage and the reversible capacity of V 2CT x during sodiation/desodiation process have been provided through V K-edge XANES and V L2,3-edge sXAS results. A correlation between the CO 3 2- content and Na + intercalation/deintercalation states in the V 2CT x electrode observed from C and O K-edge in sXAS results imply that some additional charge storage reactions may take place between the Na +-intercalated V 2CT x and the carbonate based non-aqueous electrolyte. Our results of this study will provide valuable information for the further studies on V 2CT x as anode material for Na-ion batteries and capacitors.« less

Na-Ion Intercalation and Charge Storage Mechanism in Two-Dimensional Vanadium Carbide

DOE PAGES

Bak, Seong -Min; Qiao, Ruimin; Yang, W.; ...

2017-07-14

We synthesized two-dimensional vanadium carbide MXene containing surface functional groups (denoted as V 2CT x, where T x are surface functional groups) and studied as anode material for Na-ion batteries. V 2CT x anode exhibits reversible charge storage with good cycling stability and high rate capability through electrochemical test. Furthermore, the charge storage mechanism of V 2CT x material during Na + intercalation/deintercalation and the redox reaction of vanadium were studied using a combination of synchrotron based X-ray diffraction (XRD), hard X-ray absorption near edge spectroscopy (XANES) and soft X-ray absorption spectroscopy (sXAS). Experimental evidence of a major contribution ofmore » redox reaction of vanadium to the charge storage and the reversible capacity of V 2CT x during sodiation/desodiation process have been provided through V K-edge XANES and V L2,3-edge sXAS results. A correlation between the CO 3 2- content and Na + intercalation/deintercalation states in the V 2CT x electrode observed from C and O K-edge in sXAS results imply that some additional charge storage reactions may take place between the Na +-intercalated V 2CT x and the carbonate based non-aqueous electrolyte. Our results of this study will provide valuable information for the further studies on V 2CT x as anode material for Na-ion batteries and capacitors.« less

A comparative study on the solubility and stability of p-phenylenediamine-based organic redox couples for non-aqueous flow batteries

NASA Astrophysics Data System (ADS)

Kim, Hyun-seung; Lee, Keon-Joon; Han, Young-Kyu; Ryu, Ji Heon; Oh, Seung M.

2017-04-01

A methyl-substituted p-phenylenediamine (PD), N,N,N‧,N‧-tetramethyl-p-phenylenediamine (TMPD), is examined as a positive redox couple with high energy density for non-aqueous Li-flow batteries. Methyl substitution affects the solubility of the redox couple, as the solubility is increased by a factor of ten, to a maximum solubility of 5.0 M in 1.0 M lithium tetrafluoroborate-propylene carbonate supporting electrolyte due to elimination of the hydrogen bonding between the solute molecules. The methyl substitution also enhances the chemical stability of the cation radical and di-cation being generated from PD, as the redox center is shielded by the methyl groups. Furthermore, this organic redox couple demonstrate two-electron redox reactions at 3.2 and 3.8 V (vs. Li/Li+); therefore, the volumetric capacity is twice higher compared to conventional one-electron involved redox couples. In a non-flowing Li/TMPD coin-cell, this organic redox couple demonstrates very stable cycleability as a positive redox couple for non-aqueous flow batteries.

Reversible chemical delithiation/lithiation of LiFePO4: towards a redox flow lithium-ion battery.

PubMed

Huang, Qizhao; Li, Hong; Grätzel, Michael; Wang, Qing

2013-02-14

Reversible chemical delithiation/lithiation of LiFePO(4) was successfully demonstrated using ferrocene derivatives, based on which a novel energy storage system--the redox flow lithium-ion battery (RFLB), was devised by integrating the operation flexibility of a redox flow battery and high energy density of a lithium-ion battery. Distinct from the recent semi-solid lithium rechargeable flow battery, the energy storage materials of RFLB stored in separate energy tanks remain stationary upon operation, giving us a fresh perspective on building large-scale energy storage systems with higher energy density and improved safety.

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.

TEMPO-based catholyte for high-energy density nonaqueous redox flow batteries.

PubMed

Wei, Xiaoliang; Xu, Wu; Vijayakumar, Murugesan; Cosimbescu, Lelia; Liu, Tianbiao; Sprenkle, Vincent; Wang, Wei

2014-12-03

A TEMPO-based non-aqueous electrolyte with the TEMPO concentration as high as 2.0 m is demonstrated as a high-energy-density catholyte for redox flow battery applications. With a hybrid anode, Li|TEMPO flow cells using this electrolyte deliver an energy efficiency of ca. 70% and an impressively high energy density of 126 W h L(-1) . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery

PubMed Central

Li, Bin; Nie, Zimin; Vijayakumar, M.; Li, Guosheng; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-01-01

Redox flow batteries are receiving wide attention for electrochemical energy storage due to their unique architecture and advantages, but progress has so far been limited by their low energy density (~25 Wh l−1). Here we report a high-energy density aqueous zinc-polyiodide flow battery. Using the highly soluble iodide/triiodide redox couple, a discharge energy density of 167 Wh l−1 is demonstrated with a near-neutral 5.0 M ZnI2 electrolyte. Nuclear magnetic resonance study and density functional theory-based simulation along with flow test data indicate that the addition of an alcohol (ethanol) induces ligand formation between oxygen on the hydroxyl group and the zinc ions, which expands the stable electrolyte temperature window to from −20 to 50 °C, while ameliorating the zinc dendrite. With the high-energy density and its benign nature free from strong acids and corrosive components, zinc-polyiodide flow battery is a promising candidate for various energy storage applications. PMID:25709083

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery.

PubMed

Li, Bin; Nie, Zimin; Vijayakumar, M; Li, Guosheng; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-02-24

Redox flow batteries are receiving wide attention for electrochemical energy storage due to their unique architecture and advantages, but progress has so far been limited by their low energy density (~25 Wh l(-1)). Here we report a high-energy density aqueous zinc-polyiodide flow battery. Using the highly soluble iodide/triiodide redox couple, a discharge energy density of 167 Wh l(-1) is demonstrated with a near-neutral 5.0 M ZnI2 electrolyte. Nuclear magnetic resonance study and density functional theory-based simulation along with flow test data indicate that the addition of an alcohol (ethanol) induces ligand formation between oxygen on the hydroxyl group and the zinc ions, which expands the stable electrolyte temperature window to from -20 to 50 °C, while ameliorating the zinc dendrite. With the high-energy density and its benign nature free from strong acids and corrosive components, zinc-polyiodide flow battery is a promising candidate for various energy storage applications.

Multicomponent transport in membranes for redox flow batteries

NASA Astrophysics Data System (ADS)

Monroe, Charles

2015-03-01

Redox flow batteries (RFBs) incorporate separator membranes, which ideally prevent mixing of electrochemically active species while permitting crossover of inactive supporting ions. Understanding crossover and membrane selectivity may require multicomponent transport models that account for solute/solute interactions within the membrane, as well as solute/membrane interactions. Application of the Onsager-Stefan-Maxwell formalism allows one to account for all the dissipative phenomena that may accompany component fluxes through RFB membranes. The magnitudes of dissipative interactions (diffusional drag forces) are quantified by matching experimentally established concentration transients with theory. Such transients can be measured non-invasively using DC conductometry, but the accuracy of this method requires precise characterization of the bulk RFB electrolytes. Aqueous solutions containing both vanadyl sulfate (VOSO4) and sulfuric acid (H2SO4) are relevant to RFB technology. One of the first precise characterizations of aqueous vanadyl sulfate has been implemented and will be reported. To assess the viability of a separator for vanadium RFB applications with cell-level simulations, it is critical to understand the tendencies of various classes of membranes to absorb (uptake) active species, and to know the relative rates of active-species and supporting-electrolyte diffusion. It is also of practical interest to investigate the simultaneous diffusion of active species and supports, because interactions between solutes may ultimately affect the charge efficiency and power efficiency of the RFB system as a whole. A novel implementation of Barnes's classical model of dialysis-cell diffusion [Physics 5:1 (1934) 4-8] is developed to measure the binary diffusion coefficients and sorption equilibria for single solutes (VOSO4 or H2SO4) in porous membranes and cation-exchange membranes. With the binary diffusion and uptake measurement in hand, a computer simulation that

Hybrid anodes for redox flow batteries

DOEpatents

Wang, Wei; Xiao, Jie; Wei, Xiaoliang; Liu, Jun; Sprenkle, Vincent L.

2015-12-15

RFBs having solid hybrid electrodes can address at least the problems of active material consumption, electrode passivation, and metal electrode dendrite growth that can be characteristic of traditional batteries, especially those operating at high current densities. The RFBs each have a first half cell containing a first redox couple dissolved in a solution or contained in a suspension. The solution or suspension can flow from a reservoir to the first half cell. A second half cell contains the solid hybrid electrode, which has a first electrode connected to a second electrode, thereby resulting in an equipotential between the first and second electrodes. The first and second half cells are separated by a separator or membrane.

Mass transport enhancement in redox flow batteries with corrugated fluidic networks

NASA Astrophysics Data System (ADS)

Lisboa, Kleber Marques; Marschewski, Julian; Ebejer, Neil; Ruch, Patrick; Cotta, Renato Machado; Michel, Bruno; Poulikakos, Dimos

2017-08-01

We propose a facile, novel concept of mass transfer enhancement in flow batteries based on electrolyte guidance in rationally designed corrugated channel systems. The proposed fluidic networks employ periodic throttling of the flow to optimally deflect the electrolytes into the porous electrode, targeting enhancement of the electrolyte-electrode interaction. Theoretical analysis is conducted with channels in the form of trapezoidal waves, confirming and detailing the mass transport enhancement mechanism. In dilute concentration experiments with an alkaline quinone redox chemistry, a scaling of the limiting current with Re0.74 is identified, which compares favourably against the Re0.33 scaling typical of diffusion-limited laminar processes. Experimental IR-corrected polarization curves are presented for high concentration conditions, and a significant performance improvement is observed with the narrowing of the nozzles. The adverse effects of periodic throttling on the pumping power are compared with the benefits in terms of power density, and an improvement of up to 102% in net power density is obtained in comparison with the flow-by case employing straight parallel channels. The proposed novel concept of corrugated fluidic networks comes with facile fabrication and contributes to the improvement of the transport characteristics and overall performance of redox flow battery systems.

Measurement of the Structure and Molecular Dynamics of Ionic Solutions for Redox Flow Battery

NASA Astrophysics Data System (ADS)

Li, Zhixia; Robertson, Lily; Moore, Jeffery; Zhang, Yang

Redox flow battery (RFB) is a promising electrical energy storage technology with great potential to finally realize alternative energy sources for the next-generation vehicles and at grid scales. The design of RFB is unique as the power scales separately from the energy capacity. The latter depends on the size of storage tanks and the concentration of the active materials. Redox-active organic molecules are excellent candidates with high synthetic tunability for both redox properties as well as, importantly, solubility. However, upon increasing concentrations, the flow cell has less cycling stability and more capacity fade. Further, after charging the battery, the viscosity increases while the ionic conductivity decreases, and thus the cell becomes overall ineffective. To understand the mechanism of the increased viscosity, we performed differential scanning calorimetry, wide and small angle X-rays scattering, and quasi-elastic neutron scattering measurements. Herein, we will present the measurement results and relative analysis.

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.; 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

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.

A high-energy-density redox flow battery based on zinc/polyhalide chemistry.

PubMed

Zhang, Liqun; Lai, Qinzhi; Zhang, Jianlu; Zhang, Huamin

2012-05-01

Zn and the Art of Battery Development: A zinc/polyhalide redox flow battery employs Br(-) /ClBr(2-) and Zn/Zn(2+) redox couples in its positive and negative half-cells, respectively. The performance of the battery is evaluated by charge-discharge cycling tests and reveals a high energy efficiency of 81%, based on a Coulombic efficiency of 96% and voltage efficiency of 84%. The new battery technology can provide high performance and energy density at an acceptable cost. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High energy density redox flow device

DOEpatents

Chiang, Yet -Ming; Carter, W. Craig; Duduta, Mihai; Limthongkul, Pimpa

2015-10-06

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

High energy density redox flow device

DOEpatents

Chiang, Yet-Ming; Carter, William Craig; Duduta, Mihai; Limthongkul, Pimpa

2014-05-13

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

Anticancer activity of metal complexes: involvement of redox processes.

PubMed

Jungwirth, Ute; Kowol, Christian R; Keppler, Bernhard K; Hartinger, Christian G; Berger, Walter; Heffeter, Petra

2011-08-15

Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of "activation by reduction" as well as the "hard and soft acids and bases" theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology.

Anticancer Activity of Metal Complexes: Involvement of Redox Processes

PubMed Central

Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

2012-01-01

Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

Integrating a dual-silicon photoelectrochemical cell into a redox flow battery for unassisted photocharging

PubMed Central

Liao, Shichao; Zong, Xu; Seger, Brian; Pedersen, Thomas; Yao, Tingting; Ding, Chunmei; Shi, Jingying; Chen, Jian; Li, Can

2016-01-01

Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient photoelectrochemical reactions. Here we report an efficient SRFC based on a dual-silicon photoelectrochemical cell and a quinone/bromine redox flow battery for in situ solar energy conversion and storage. Using narrow bandgap silicon for efficient photon collection and fast redox couples for rapid interface charge injection, our device shows an optimal solar-to-chemical conversion efficiency of ∼5.9% and an overall photon–chemical–electricity energy conversion efficiency of ∼3.2%, which, to our knowledge, outperforms previously reported SRFCs. The proposed SRFC can be self-photocharged to 0.8 V and delivers a discharge capacity of 730 mAh l−1. Our work may guide future designs for highly efficient solar rechargeable devices. PMID:27142885

Integrating a dual-silicon photoelectrochemical cell into a redox flow battery for unassisted photocharging.

PubMed

Liao, Shichao; Zong, Xu; Seger, Brian; Pedersen, Thomas; Yao, Tingting; Ding, Chunmei; Shi, Jingying; Chen, Jian; Li, Can

2016-05-04

Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient photoelectrochemical reactions. Here we report an efficient SRFC based on a dual-silicon photoelectrochemical cell and a quinone/bromine redox flow battery for in situ solar energy conversion and storage. Using narrow bandgap silicon for efficient photon collection and fast redox couples for rapid interface charge injection, our device shows an optimal solar-to-chemical conversion efficiency of ∼5.9% and an overall photon-chemical-electricity energy conversion efficiency of ∼3.2%, which, to our knowledge, outperforms previously reported SRFCs. The proposed SRFC can be self-photocharged to 0.8 V and delivers a discharge capacity of 730 mAh l(-1). Our work may guide future designs for highly efficient solar rechargeable devices.

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

Vijayakumar, M.; Nie, Zimin; Walter, Eric D.

Redox flow battery (RFB) is a promising candidate for energy storage component in designing resilient grid scale power supply due to the advantage of the separation of power and energy. However, poorly understood chemical and thermal stability issues of electrolytes currently limit the performance of RFB. Designing of high performance stable electrolytes requires comprehensive knowledge about the molecular level solvation structure and dynamics of their redox active species. The molecular level understanding of detrimental V2O5 precipitation process led to successful designing of mixed acid based electrolytes for vanadium redox flow batteries (VRFB). The higher stability of mixed acid based electrolytesmore » is attributed to the choice of hydrochloric acid as optimal co-solvent, which provides chloride anions for ligand exchange process in vanadium solvation structure. The role of chloride counter anion on solvation structure and dynamics of vanadium species were studied using combined magnetic resonance spectroscopy and DFT based theoretical methods. Finally, the solvation phenomenon of multiple vanadium species and their impact on VRFB electrolyte chemical stability were discussed.« less

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.

Reductive transformation of V(iii) precursors into vanadium(ii) oxide nanowires.

PubMed

Ojelere, Olusola; Graf, David; Ludwig, Tim; Vogt, Nicholas; Klein, Axel; Mathur, Sanjay

2018-05-15

Vanadium(ii) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium(iii) complexes with bi-dentate O,N-chelating heteroarylalkenol ligands (DmoxCH[double bond, length as m-dash]COCF3, PyCH[double bond, length as m-dash]COCF3 and PyN[double bond, length as m-dash]COCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. The chemical identity of V(iii) complexes and their redox behaviour were unambiguously established by single crystal X-ray diffraction studies, cyclic voltammetry, spectrometric studies and DFT calculations. Transformation into the metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures, respectively.

High energy density redox flow device

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

Carter, W. Craig; Chiang, Yet-Ming; Duduta, Mihai

2017-04-04

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % ofmore » the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.« less

Rapid and Automated Analytical Methods for Redox Species Based on Potentiometric Flow Injection Analysis Using Potential Buffers

PubMed Central

Ohura, Hiroki; Imato, Toshihiko

2011-01-01

Two analytical methods, which prove the utility of a potentiometric flow injection technique for determining various redox species, based on the use of some redox potential buffers, are reviewed. The first is a potentiometric flow injection method in which a redox couple such as Fe(III)-Fe(II), Fe(CN)6 3−-Fe(CN)(CN)6 4−, and bromide-bromine and a redox electrode or a combined platinum-bromide ion selective electrode are used. The analytical principle and advantages of the method are discussed, and several examples of its application are reported. Another example is a highly sensitive potentiometric flow injection method, in which a large transient potential change due to bromine or chlorine as an intermediate, generated during the reaction of the oxidative species with an Fe(III)-Fe(II) potential buffer containing bromide or chloride, is utilized. The analytical principle and details of the proposed method are described, and examples of several applications are described. The determination of trace amounts of hydrazine, based on the detection of a transient change in potential caused by the reaction with a Ce(IV)-Ce(III) potential buffer, is also described. PMID:21584280

Improved radical stability of viologen anolytes in aqueous organic redox flow batteries.

PubMed

Hu, Bo; Tang, Yijie; Luo, Jian; Grove, Grant; Guo, Yisong; Liu, T Leo

2018-05-09

A high voltage (1.38 V) total organic aqueous redox flow battery is reported using 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium tetrachloride ((NPr)2V) as an anolyte and 4-trimethylammonium-TEMPO chloride (NMe-TEMPO) as a catholyte. The exceptional radical stability of [(NPr)2V]+˙ enabled the flow battery in achieving 97.48% capacity retention for 500 cycles and a power density of 128.2 mW cm-2.

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.

Improvement and analysis of the hydrogen-cerium redox flow cell

NASA Astrophysics Data System (ADS)

Tucker, Michael C.; Weiss, Alexandra; Weber, Adam Z.

2016-09-01

The H2-Ce redox flow cell is optimized using commercially-available cell materials. Cell performance is found to be sensitive to the upper charge cutoff voltage, membrane boiling pretreatment, methanesulfonic-acid concentration, (+) electrode surface area and flow pattern, and operating temperature. Performance is relatively insensitive to membrane thickness, Cerium concentration, and all features of the (-) electrode including hydrogen flow. Cell performance appears to be limited by mass transport and kinetics in the cerium (+) electrode. Maximum discharge power of 895 mW cm-2 was observed at 60 °C; an energy efficiency of 90% was achieved at 50 °C. The H2-Ce cell is promising for energy storage assuming one can optimize Ce reaction kinetics and electrolyte.

Role of Bismuth in the Electrokinetics of Silicon Photocathodes for Solar Rechargeable Vanadium Redox Flow Batteries.

PubMed

Flox, Cristina; Murcia-López, Sebastián; Carretero, Nina M; Ros, Carles; Morante, Juan R; Andreu, Teresa

2018-01-10

The ability of crystalline silicon to photoassist the V 3+ /V 2+ cathodic reaction under simulated solar irradiation, combined with the effect of bismuth have led to important electrochemical improvements. Besides the photovoltage supplied by the photovoltaics, additional decrease in the onset potentials, high reversibility of the V 3+ /V 2+ redox pair, and improvement in the electrokinetics were attained thanks to the addition of bismuth. In fact, Bi 0 deposition has shown to slightly decrease the photocurrent, but the significant enhancement in the charge transfer, reflected in the overall electrochemical performance clearly justifies its use as additive in a photoassisted system for maximizing the efficiency of solar charge to battery. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring electrolyte concentrations in redox flow battery systems

DOEpatents

Chang, On Kok; Sopchak, David Andrew; Pham, Ai Quoc; Kinoshita, Kimio

2015-03-17

Methods, systems and structures for monitoring, managing electrolyte concentrations in redox flow batteries are provided by introducing a first quantity of a liquid electrolyte into a first chamber of a test cell and introducing a second quantity of the liquid electrolyte into a second chamber of the test cell. The method further provides for measuring a voltage of the test cell, measuring an elapsed time from the test cell reaching a first voltage until the test cell reaches a second voltage; and determining a degree of imbalance of the liquid electrolyte based on the elapsed time.

Direct Solar Charging of an Organic–Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode

PubMed Central

Wedege, Kristina; Azevedo, João; Khataee, Amirreza

2016-01-01

Abstract The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone‐2,7‐disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide‐hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron–hole recombination. PMID:27151516

Improvement and analysis of the hydrogen-cerium redox flow cell

DOE PAGES

Tucker, Michael C.; Weiss, Alexandra; Weber, Adam Z.

2016-08-03

In this paper, the H 2-Ce redox flow cell is optimized using commercially-available cell materials. Cell performance is found to be sensitive to the upper charge cutoff voltage, membrane boiling pretreatment, methanesulfonic-acid concentration, (+) electrode surface area and flow pattern, and operating temperature. Performance is relatively insensitive to membrane thickness, Cerium concentration, and all features of the (-) electrode including hydrogen flow. Cell performance appears to be limited by mass transport and kinetics in the cerium (+) electrode. Maximum discharge power of 895 mW cm -2 was observed at 60 °C; an energy efficiency of 90% was achieved at 50more » °C. Finally, the H 2-Ce cell is promising for energy storage assuming one can optimize Ce reaction kinetics and electrolyte.« less

Ediacaran Redox Fluctuations

NASA Astrophysics Data System (ADS)

Sahoo, S. K.; Jiang, G.; Planavsky, N. J.; Kendall, B.; Owens, J. D.; Anbar, A. D.; Lyons, T. W.

2013-12-01

Evidence for pervasive oxic conditions, and likely even deep ocean oxygenation has been documented at three intervals in the lower (ca. 632 Ma), middle (ca. 580 Ma) and upper (ca. 551 Ma) Ediacaran. The Doushantuo Formation in South China hosts large enrichments of redox-sensitive trace element (e.g., molybdenum, vanadium and uranium) in anoxic shales, which are indicative of a globally oxic ocean-atmosphere system. However, ocean redox conditions between these periods continue to be a topic of debate and remain elusive. We have found evidence for widespread anoxic conditions through much of the Ediacaran in the deep-water Wuhe section in South China. During most of the Ediacaran-early Cambrian in basinal sections is characterized by Fe speciation data and pyrite morphologies that indicate deposition under euxinic conditions with near-crustal enrichments of redox-sensitive element and positive pyrite-sulfur isotope values, which suggest low levels of marine sulfate and widespread euxinia. Our work reinforces an emerging view that the early Earth, including the Ediacaran, underwent numerous rises and falls in surface oxidation state, rather than a unidirectional rise as originally imagined. The Ediacaran ocean thus experienced repetitive expansion and contraction of marine chalcophilic trace-metal levels that may have had fundamental impact on the slow evolution of early animals and ecosystems. Further, this framework forces us to re-examine the relationship between Neoproterozoic oxygenation and metazoan diversification. Varying redox conditions through the Cryogenian and Ediacaran may help explain molecular clock and biomarker evidence for an early appearance and initial diversification of metazoans but with a delay in the appearance of most major metazoan crown groups until close to Ediacaran-Cambrian boundary.

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.

Direct Solar Charging of an Organic-Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode.

PubMed

Wedege, Kristina; Azevedo, João; Khataee, Amirreza; Bentien, Anders; Mendes, Adélio

2016-06-13

The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone-2,7-disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide-hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron-hole recombination. © 2016 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

A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries

NASA Astrophysics Data System (ADS)

Hollas, Aaron; Wei, Xiaoliang; Murugesan, Vijayakumar; Nie, Zimin; Li, Bin; Reed, David; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2018-06-01

Aqueous soluble organic (ASO) redox-active materials have recently attracted significant attention as alternatives to traditional transition metal ions in redox flow batteries (RFB). However, reported reversible capacities of ASO are often substantially lower than their theoretical values based on the reported maximum solubilities. Here, we describe a phenazine-based ASO compound with an exceptionally high reversible capacity that exceeds 90% of its theoretical value. By strategically modifying the phenazine molecular structure, we demonstrate an increased solubility from near-zero with pristine phenazine to as much as 1.8 M while also shifting its redox potential by more than 400 mV. An RFB based on a phenazine derivative (7,8-dihydroxyphenazine-2-sulfonic acid) at its near-saturation concentration exhibits an operating voltage of 1.4 V with a reversible anolyte capacity of 67 Ah l-1 and a capacity retention of 99.98% per cycle over 500 cycles.

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

Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

PubMed Central

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

2015-01-01

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

A low-cost iron-cadmium redox flow battery for large-scale energy storage

NASA Astrophysics Data System (ADS)

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

2016-10-01

The redox flow battery (RFB) is one of the most promising large-scale energy storage technologies that offer a potential solution to the intermittency of renewable sources such as wind and solar. The prerequisite for widespread utilization of RFBs is low capital cost. In this work, an iron-cadmium redox flow battery (Fe/Cd RFB) with a premixed iron and cadmium solution is developed and tested. It is demonstrated that the coulombic efficiency and energy efficiency of the Fe/Cd RFB reach 98.7% and 80.2% at 120 mA cm-2, respectively. The Fe/Cd RFB exhibits stable efficiencies with capacity retention of 99.87% per cycle during the cycle test. Moreover, the Fe/Cd RFB is estimated to have a low capital cost of 108 kWh-1 for 8-h energy storage. Intrinsically low-cost active materials, high cell performance and excellent capacity retention equip the Fe/Cd RFB to be a promising solution for large-scale energy storage systems.

Room temperature, hybrid sodium-based flow batteries with multi-electron transfer redox reactions

DOE PAGES

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; ...

2015-06-11

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volumemore » of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. Furthermore, the critical barriers to mature this new HNFBs have also been explored.« less

Redox flow batteries with serpentine flow fields: Distributions of electrolyte flow reactant penetration into the porous carbon electrodes and effects on performance

NASA Astrophysics Data System (ADS)

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

2018-04-01

Redox flow batteries with flow field designs have been demonstrated to boost their capacities to deliver high current density and power density in medium and large-scale energy storage applications. Nevertheless, the fundamental mechanisms involved with improved current density in flow batteries with serpentine flow field designs have been not fully understood. Here we report a three-dimensional model of a serpentine flow field over a porous carbon electrode to examine the distributions of pressure driven electrolyte flow penetrations into the porous carbon electrodes. We also estimate the maximum current densities associated with stoichiometric availability of electrolyte reactant flow penetrations through the porous carbon electrodes. The results predict reasonably well observed experimental data without using any adjustable parameters. This fundamental work on electrolyte flow distributions of limiting reactant availability will contribute to a better understanding of limits on electrochemical performance in flow batteries with serpentine flow field designs and should be helpful to optimizing flow batteries.

Computational design of molecules for an all-quinone redox flow battery.

PubMed

Er, Süleyman; Suh, Changwon; Marshak, Michael P; Aspuru-Guzik, Alán

2015-02-01

Inspired by the electron transfer properties of quinones in biological systems, we recently showed that quinones are also very promising electroactive materials for stationary energy storage applications. Due to the practically infinite chemical space of organic molecules, the discovery of additional quinones or other redox-active organic molecules for energy storage applications is an open field of inquiry. Here, we introduce a high-throughput computational screening approach that we applied to an accelerated study of a total of 1710 quinone (Q) and hydroquinone (QH 2 ) ( i.e. , two-electron two-proton) redox couples. We identified the promising candidates for both the negative and positive sides of organic-based aqueous flow batteries, thus enabling an all-quinone battery. To further aid the development of additional interesting electroactive small molecules we also provide emerging quantitative structure-property relationships.

Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries.

PubMed

Doris, Sean E; Ward, Ashleigh L; Baskin, Artem; Frischmann, Peter D; Gavvalapalli, Nagarjuna; Chénard, Etienne; Sevov, Christo S; Prendergast, David; Moore, Jeffrey S; Helms, Brett A

2017-02-01

Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. Here we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the rate of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm -2  day -1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. This strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries

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

Doris, Sean E.; Ward, Ashleigh L.; Baskin, Artem

Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. In this paper, we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the ratemore » of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm -2 day -1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. Finally, this strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.« less

Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries

DOE PAGES

Doris, Sean E.; Ward, Ashleigh L.; Baskin, Artem; ...

2017-01-10

Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. In this paper, we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the ratemore » of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm -2 day -1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. Finally, this strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.« less

Electrochemical cell for rebalancing REDOX flow system

NASA Technical Reports Server (NTRS)

Thaller, L. H. (Inventor)

1979-01-01

An electrically rechargeable REDOX cell or battery system including one of more rebalancing cells is described. Each rebalancing cell is divided into two chambers by an ion permeable membrane. The first chamber is fed with gaseous hydrogen and a cathode fluid which is circulated through the cathode chamber of the REDOX cell is also passed through the second chamber of the rebalancing cell. Electrochemical reactions take place on the surface of insert electrodes in the first and second chambers to rebalance the electrochemical capacity of the anode and cathode fluids of the REDOX system.

Vanadium Oxide Deposited on Strontium Titanate and Related Supports: Structural, Redox, and Catalytic Properties in Oxidative Dehydrogenation Reactions

NASA Astrophysics Data System (ADS)

McCarthy, James A.

The field of heterogeneous catalysis has advanced largely through the understanding of structure-function relationships, and novel support materials constitute one possible strategy to further this knowledge through the determination of support effects. To this end, the synthesis, characterization, and reactivity of a new catalytic system are reported herein. Vanadium oxide supported on SrTiO3 (VOx/STO) was prepared by atomic layer deposition, and its activity was investigated in various oxidative dehydrogenation (ODH) reactions. In cyclohexane and propane ODH experiments at 500 °C, selectivity toward COx was found to decrease with greater VOx density and minimal STO surface exposure. This indicates that the support itself is an effective total oxidation catalyst, which complicates VOx performance measurements. In the propane studies, VOx/STO achieved lower turnover frequency (TOF) and propylene yield compared to conventional supported VO x materials. The lower activity of VOx/STO catalysts was correlated with their VOx species being less easily reducible, as determined by temperature-programmed reduction (TPR). The suppressed reducibility is attributed to the stronger surface basicity of STO, which is induced by the presence of relatively electropositive Sr2+ within the perovskite lattice. Studies of cyclohexene ODH at 300 °C were conducted to minimize intrinsic conversion from the supports. The VOx/STO catalysts were mostly found to be less active than VOx/TiO2 and VOx/Al 2O3, in accordance with reducibility measurements. However, one sample containing 0.75% vanadium on STO was particularly active, achieving a TOF greater than 0.01 s-1, while maintaining almost 90% dehydrogenation selectivity. In general, VOx/STO materials were found to be more selective for 1,3-cyclohexadiene compared to traditional catalysts. Other titanates of the form A2+TiO3 were also investigated as supports, and the reducibility of VOx was found to trend with the electronegativity of the

Cyclic electron flow is redox-controlled but independent of state transition.

PubMed

Takahashi, Hiroko; Clowez, Sophie; Wollman, Francis-André; Vallon, Olivier; Rappaport, Fabrice

2013-01-01

Photosynthesis is the biological process that feeds the biosphere with reduced carbon. The assimilation of CO2 requires the fine tuning of two co-existing functional modes: linear electron flow, which provides NADPH and ATP, and cyclic electron flow, which only sustains ATP synthesis. Although the importance of this fine tuning is appreciated, its mechanism remains equivocal. Here we show that cyclic electron flow as well as formation of supercomplexes, thought to contribute to the enhancement of cyclic electron flow, are promoted in reducing conditions with no correlation with the reorganization of the thylakoid membranes associated with the migration of antenna proteins towards Photosystems I or II, a process known as state transition. We show that cyclic electron flow is tuned by the redox power and this provides a mechanistic model applying to the entire green lineage including the vast majority of the cases in which state transition only involves a moderate fraction of the antenna.

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.

Arsenic, vanadium, iron, and manganese biogeochemistry in a deltaic wetland, southern Louisiana, USA

DOE PAGES

Telfeyan, Katherine; Breaux, Alexander; Kim, Jihyuk; ...

2017-04-05

Geochemical cycling of the redox-sensitive trace elements arsenic (As) and vanadium (V) was examined in shallow pore waters from a marsh in an interdistributary embayment of the lower Mississippi River Delta. In particular, we explore how redox changes with depth and distance from the Mississippi River affect As and V cycling in the marsh pore waters. Previous geophysical surveys and radon mass balance calculations suggested that Myrtle Grove Canal and bordering marsh receive fresh groundwater, derived in large part from seepage of the Mississippi River, which subsequently mixes with brackish waters of Barataria Bay. In addition, the redox geochemistry ofmore » pore waters in the wetlands is affected by Fe and S cycling in the shallow subsurface (0-20 cm). Sediments with high organic matter content undergo SO 4 2- reduction, a process ubiquitous in the shallow subsurface but largely absent at greater depths (~3 m). Instead, at depth, in the absence of organic-rich sediments, Fe concentrations are elevated, suggesting that reduction of Fe(III) oxides/oxyhydroxides buffers redox conditions. Arsenic and V cycling in the shallow subsurface are decoupled from their behavior at depth, where both V and As appear to be removed from solution by either diffusion or adsorption onto, or co-precipitation with, authigenic minerals within the deeper aquifer sediments. Pore water As concentrations are greatest in the shallow subsurface (e.g., up to 315 nmol kg -1 in the top ~20 cm of the sediment) but decrease with depth, reaching values <30 nmol kg -1 at depths between 3 and 4 m. Vanadium concentrations appear to be tightly coupled to Fe cycling in the shallow subsurface, but at depth, V may be adsorbed to clay or sedimentary organic matter (SOM). Diffusive fluxes are calculated to examine the export of trace elements from the shallow marsh pore waters to the overlying canal water that floods the marsh. The computed fluxes suggest that the shallow sediment serves as a source of

Arsenic, vanadium, iron, and manganese biogeochemistry in a deltaic wetland, southern Louisiana, USA

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

Telfeyan, Katherine; Breaux, Alexander; Kim, Jihyuk

Geochemical cycling of the redox-sensitive trace elements arsenic (As) and vanadium (V) was examined in shallow pore waters from a marsh in an interdistributary embayment of the lower Mississippi River Delta. In particular, we explore how redox changes with depth and distance from the Mississippi River affect As and V cycling in the marsh pore waters. Previous geophysical surveys and radon mass balance calculations suggested that Myrtle Grove Canal and bordering marsh receive fresh groundwater, derived in large part from seepage of the Mississippi River, which subsequently mixes with brackish waters of Barataria Bay. In addition, the redox geochemistry ofmore » pore waters in the wetlands is affected by Fe and S cycling in the shallow subsurface (0-20 cm). Sediments with high organic matter content undergo SO 4 2- reduction, a process ubiquitous in the shallow subsurface but largely absent at greater depths (~3 m). Instead, at depth, in the absence of organic-rich sediments, Fe concentrations are elevated, suggesting that reduction of Fe(III) oxides/oxyhydroxides buffers redox conditions. Arsenic and V cycling in the shallow subsurface are decoupled from their behavior at depth, where both V and As appear to be removed from solution by either diffusion or adsorption onto, or co-precipitation with, authigenic minerals within the deeper aquifer sediments. Pore water As concentrations are greatest in the shallow subsurface (e.g., up to 315 nmol kg -1 in the top ~20 cm of the sediment) but decrease with depth, reaching values <30 nmol kg -1 at depths between 3 and 4 m. Vanadium concentrations appear to be tightly coupled to Fe cycling in the shallow subsurface, but at depth, V may be adsorbed to clay or sedimentary organic matter (SOM). Diffusive fluxes are calculated to examine the export of trace elements from the shallow marsh pore waters to the overlying canal water that floods the marsh. The computed fluxes suggest that the shallow sediment serves as a source of

All-Fullerene-Based Cells for Nonaqueous Redox Flow Batteries.

PubMed

Friedl, Jochen; Lebedeva, Maria A; Porfyrakis, Kyriakos; Stimming, Ulrich; Chamberlain, Thomas W

2018-01-10

Redox flow batteries have the potential to revolutionize our use of intermittent sustainable energy sources such as solar and wind power by storing the energy in liquid electrolytes. Our concept study utilizes a novel electrolyte system, exploiting derivatized fullerenes as both anolyte and catholyte species in a series of battery cells, including a symmetric, single species system which alleviates the common problem of membrane crossover. The prototype multielectron system, utilizing molecular based charge carriers, made from inexpensive, abundant, and sustainable materials, principally, C and Fe, demonstrates remarkable current and energy densities and promising long-term cycling stability.

An All-vanadium Continuous-flow Photoelectrochemical Cell for Extending State-of-charge in Solar Energy Storage.

PubMed

Wei, Zi; Shen, Yi; Liu, Dong; Liu, Fuqiang

2017-04-04

Greater levels of solar energy storage provide an effective solution to the inherent nature of intermittency, and can substantially improve reliability, availability, and quality of the renewable energy source. Here we demonstrated an all-vanadium (all-V) continuous-flow photoelectrochemical storage cell (PESC) to achieve efficient and high-capacity storage of solar energy, through improving both photocurrent and photocharging depth. It was discovered that forced convective flow of electrolytes greatly enhanced the photocurrent by 5 times comparing to that with stagnant electrolytes. Electrochemical impedance spectroscopy (EIS) study revealed a great reduction of charge transfer resistance with forced convective flow of electrolytes as a result of better mass transport at U-turns of the tortuous serpentine flow channel of the cell. Taking advantage of the improved photocurrent and diminished charge transfer resistance, the all-V continuous-flow PESC was capable of producing ~20% gain in state of charge (SOC) under AM1.5 illumination for ca. 1.7 hours without any external bias. This gain of SOC was surprisingly three times more than that with stagnant electrolytes during a 25-hour period of photocharge.

Bioelectrocatalytic NAD+/NADH inter-conversion: transformation of an enzymatic fuel cell into an enzymatic redox flow battery.

PubMed

Quah, Timothy; Milton, Ross D; Abdellaoui, Sofiene; Minteer, Shelley D

2017-07-25

Diaphorase and a benzylpropylviologen redox polymer were combined to create a bioelectrode that can both oxidize NADH and reduce NAD + . We demonstrate how bioelectrocatalytic NAD + /NADH inter-conversion can transform a glucose/O 2 enzymatic fuel cell (EFC) with an open circuit potential (OCP) of 1.1 V into an enzymatic redox flow battery (ERFB), which can be rapidly recharged by operation as an EFC.

Microwave-assisted preparation of carbon nanofiber-functionalized graphite felts as electrodes for polymer-based redox-flow batteries

NASA Astrophysics Data System (ADS)

Schwenke, A. M.; Janoschka, T.; Stolze, C.; Martin, N.; Hoeppener, S.; Schubert, U. S.

2016-12-01

A simple and fast microwave-assisted protocol to functionalize commercially available graphite felts (GFs) with carbon nanofibers (CNFs) for the application as electrode materials in redox-flow batteries (RFB) is demonstrated. As catalyst for the CNF synthesis nickel acetate is applied and ethanol serves as the carbon source. By the in-situ growth of CNFs, the active surface of the electrodes is increased by a factor of 50, which is determined by the electrochemical double layer capacities of the obtained materials. Furthermore, the morphology of the CNF-coating is investigated by scanning electron microscopy. Subsequently, the functionalized electrodes are applied in a polymer-based redox-flow battery (pRFB) using a TEMPO- and a viologen polymer as active materials. Due to the increased surface area as compared to an untreated graphite felt electrode, the current rating is improved by about 45% at 80 mA cm-2 and, furthermore, a decrease in overpotentials is observed. Thus, using this microwave-assisted synthesis approach, CNF-functionalized composite electrodes are prepared with a very simple protocol suitable for real life applications and an improvement of the overall performance of the polymer-based redox-flow battery is demonstrated.

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.

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.

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

Bi-functional effects of lengthening aliphatic chain of phthalimide-based negative redox couple and its non-aqueous flow battery performance at stack cell

NASA Astrophysics Data System (ADS)

Kim, Hyun-seung; Hwang, Seunghae; Kim, Youngjin; Ryu, Ji Heon; Oh, Seung M.; Kim, Ki Jae

2018-04-01

Effects of lengthening an aliphatic chain of a phthalimide-based negative redox couple for non-aqueous flow batteries are examined. The working voltage and solubility of N-butylphthalimide are 0.1 V lower and four times greater (2.0 M) than those of methyl-substituted phthalimide. These enhanced properties are attributed to a lower packing density. Consequently, the energy density of the proposed redox couple is greatly enhanced from butyl substitution. Furthermore, the results of the stack flow cell test with N,N,N',N'-tetramethyl-p-phenylenediamine positive redox couple show advantageous features of this non-aqueous flow battery system: a stable Coulombic efficiency and high working voltage.

The lightest organic radical cation for charge storage in redox flow batteries.

PubMed

Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S; Su, Liang; Brushett, Fikile R; Cheng, Lei; Liao, Chen; Ferrandon, Magali S; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K; Curtiss, Larry A; Shkrob, Ilya A; Moore, Jeffrey S; Zhang, Lu

2016-08-25

In advanced electrical grids of the future, electrochemically rechargeable fluids of high energy density will capture the power generated from intermittent sources like solar and wind. To meet this outstanding technological demand there is a need to understand the fundamental limits and interplay of electrochemical potential, stability, and solubility in low-weight redox-active molecules. By generating a combinatorial set of 1,4-dimethoxybenzene derivatives with different arrangements of substituents, we discovered a minimalistic structure that combines exceptional long-term stability in its oxidized form and a record-breaking intrinsic capacity of 161 mAh/g. The nonaqueous redox flow battery has been demonstrated that uses this molecule as a catholyte material and operated stably for 100 charge/discharge cycles. The observed stability trends are rationalized by mechanistic considerations of the reaction pathways.

A highly reversible anthraquinone-based anolyte for alkaline aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Cao, Jianyu; Tao, Meng; Chen, Hongping; Xu, Juan; Chen, Zhidong

2018-05-01

The development of electroactive organic materials for use in aqueous redox flow battery (RFB) electrolytes is highly attractive because of their structural flexibility, low cost and sustainability. Here, we report on a highly reversible anthraquinone-based anolyte (1,8-dihydroxyanthraquinone, 1,8-DHAQ) for alkaline aqueous RFB applications. Electrochemical measurements reveal the substituent position of hydroxyl groups for DHAQ isomers has a significant impact on the redox potential, electrochemical reversibility and water-solubility. 1,8-DHAQ shows the highest redox reversibility and rapidest mass diffusion among five isomeric DHAQs. The alkaline aqueous RFB using 1,8-DHAQ as the anolyte and potassium ferrocyanide as the catholyte yields open-circuit voltage approaching 1.1 V and current efficiency and capacity retention exceeding 99.3% and 99.88% per cycle, respectively. This aqueous RFB produces a maximum power density of 152 mW cm-2 at 100% SOC and 45 °C. Choline hydroxide was used as a hydrotropic agent to enhance the water-solubility of 1,8-DHAQ. 1,8-DHAQ has a maximum solubility of 3 M in 1 M KOH with 4 M choline hydroxide.

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.

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.

Characterization of a BODIPY Dye as an Active Species for Redox Flow Batteries.

PubMed

Kosswattaarachchi, Anjula M; Friedman, Alan E; Cook, Timothy R

2016-12-08

An all-organic redox flow battery (RFB) employing a fluorescent boron-dipyrromethene (BODIPY) dye (PM567) was investigated. In a RFB, the stability of the electrolyte in all charged states is critically linked to coulombic efficiency. To evaluate stability, bulk electrolysis and cyclic voltammetry (CV) experiments were performed. Oxidized and reduced, PM567 does not remain intact; however, the products of bulk electrolysis evolve over time to show stable redox behavior, making the dye a precursor for the active species of an RFB. A theoretical cell potential of 2.32 V was predicted from CV experiments with a working discharge voltage of approximately 1.6 V in a static test cell. Mass spectrometry was used to identify the products of bulk electrolysis. Related experiments were carried out using ferrocene and cobaltocenium hexafluorophosphate as redox-stable benchmarks to further explain the stability results. The coulombic efficiency of a model cell using PM567 as a precursor for charge carriers stabilized around 73 %. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructured Electrocatalysts for PEM Fuel Cells and Redox Flow Batteries: A Selected Review

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

Shao, Yuyan; Cheng, Yingwen; Duan, Wentao

2015-12-04

PEM fuel cells and redox flow batteries are two very similar technologies which share common component materials and device design. Electrocatalysts are the key components in these two devices. In this Review, we discuss recent progress of electrocatalytic materials for these two technologies with a focus on our research activities at Pacific Northwest National Laboratory (PNNL) in the past years. This includes (1) nondestructive functionalization of graphitic carbon as Pt support to improve its electrocatalytic performance, (2) triple-junction of metal–carbon–metal oxides to promote Pt performance, (3) nitrogen-doped carbon and metal-doped carbon (i.e., metal oxides) to improve redox reactions in flowmore » batteries. A perspective on future research and the synergy between the two technologies are also discussed.« less

The lightest organic radical cation for charge storage in redox flow batteries

PubMed Central

Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S.; Su, Liang; Brushett, Fikile R.; Cheng, Lei; Liao, Chen; Ferrandon, Magali S.; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K.; Curtiss, Larry A.; Shkrob, Ilya A.; Moore, Jeffrey S.; Zhang, Lu

2016-01-01

In advanced electrical grids of the future, electrochemically rechargeable fluids of high energy density will capture the power generated from intermittent sources like solar and wind. To meet this outstanding technological demand there is a need to understand the fundamental limits and interplay of electrochemical potential, stability, and solubility in low-weight redox-active molecules. By generating a combinatorial set of 1,4-dimethoxybenzene derivatives with different arrangements of substituents, we discovered a minimalistic structure that combines exceptional long-term stability in its oxidized form and a record-breaking intrinsic capacity of 161 mAh/g. The nonaqueous redox flow battery has been demonstrated that uses this molecule as a catholyte material and operated stably for 100 charge/discharge cycles. The observed stability trends are rationalized by mechanistic considerations of the reaction pathways. PMID:27558638

The lightest organic radical cation for charge storage in redox flow batteries

DOE PAGES

Huang, Jinhua; Pan, Baofei; Duan, Wentao; ...

2016-08-25

In advanced electrical grids of the future, electrochemically rechargeable fluids of high energy density will capture the power generated from intermittent sources like solar and wind. To meet this outstanding technological demand there is a need to understand the fundamental limits and interplay of electrochemical potential, stability, and solubility in low-weight redox-active molecules. By generating a combinatorial set of 1,4-dimethoxybenzene derivatives with different arrangements of substituents, we discovered a mini-malistic structure that combines exceptional long-term stability in its oxidized form and a record-breaking intrinsic capacity of 161 mAh/g. The nonaqueous redox flow battery has been demonstrated that uses this moleculemore » as a catholyte material and operated stably for 100 charge/discharge cycles. Furthermore, the observed stability trends are rationalized by mechanistic considerations of the reaction pathways.« less

Screening of redox couples and electrode materials

NASA Technical Reports Server (NTRS)

Giner, J.; Swette, L.; Cahill, K.

1976-01-01

Electrochemical parameters of selected redox couples that might be potentially promising for application in bulk energy storage systems were investigated. This was carried out in two phases: a broad investigation of the basic characteristics and behavior of various redox couples, followed by a more limited investigation of their electrochemical performance in a redox flow reactor configuration. In the first phase of the program, eight redox couples were evaluated under a variety of conditions in terms of their exchange current densities as measured by the rotating disk electrode procedure. The second phase of the program involved the testing of four couples in a redox reactor under flow conditions with a varity of electrode materials and structures.

Spatial distribution pattern of vanadium in hydric landscapes

NASA Astrophysics Data System (ADS)

Fiedler, Sabine; Breuer, Jörn; Palmer, Iris; Berger, Jochen

2010-05-01

The geochemical behavior of the trace element vanadium (V) is strongly influenced by its oxidation state (+2 to +5). Consequently, oxidation/reduction reactions play an important role in controlling the mobilization and immobilization of V in soils. Translocation processes of V within soil profiles (pedons), including podzolization and clay illuviation, are well-documented. With regard to its lateral redistribution in landscapes, V is widely regarded as being immobile. Our investigation focused on the fate of V along a moisture gradient in different temperate humid spruce forest ecosystems in Southwest Germany (MAP 1,200-1,600 mm, MAT 6°C). The areas under investigation are characterized by lateral water flow, caused by a physically pre-weathered periglacial layer with poor water-permeability characteristics at the interface between pedo- and lithosphere. We selected different catenas derived from sandstone, gneiss, and granite, respectively. The soil associations occur along moderately inclined slopes and include common forest soils of three redox categories: an anaerobic Histosol, oxic Cambisols, and Stagnosols with an intermediate redox state. The soils are linked to each other by the lateral subsurface transport of solutes, which allows the investigation of the horizontal (i.e. within pedons) and lateral redistribution (i.e. between pedons) of the redox-sensitive elements V and iron (Fe). The redox potential of V and Fe in different soil depths along the hydrological pathway was both measured in the field and subsequently analyzed in 48 soil horizons to deduce the total content of V and Fe using aqua-regia digestion and element spectrometry (ICP-OES and ICP-MS). The different parent materials result in significant differences in V content. The V content in the sandstone soils (0.2 - 30 mg kg-1) was lower than the V content in granite and gneiss soils (up to 75 and 100 mg kg-1, respectively). Our results demonstrate that V is a highly mobile element in hydric

Metal-Organic Frameworks as Highly Active Electrocatalysts for High-Energy Density, Aqueous Zinc-Polyiodide Redox Flow Batteries.

PubMed

Li, Bin; Liu, Jian; Nie, Zimin; Wang, Wei; Reed, David; Liu, Jun; McGrail, Pete; Sprenkle, Vincent

2016-07-13

The new aqueous zinc-polyiodide redox flow battery (RFB) system with highly soluble active materials as well as ambipolar and bifunctional designs demonstrated significantly enhanced energy density, which shows great potential to reduce RFB cost. However, the poor kinetic reversibility and electrochemical activity of the redox reaction of I3(-)/I(-) couples on graphite felts (GFs) electrode can result in low energy efficiency. Two nanoporous metal-organic frameworks (MOFs), MIL-125-NH2 and UiO-66-CH3, that have high surface areas when introduced to GF surfaces accelerated the I3(-)/I(-) redox reaction. The flow cell with MOF-modified GFs serving as a positive electrode showed higher energy efficiency than the pristine GFs; increases of about 6.4% and 2.7% occurred at the current density of 30 mA/cm(2) for MIL-125-NH2 and UiO-66-CH3, respectively. Moreover, UiO-66-CH3 is more promising due to its excellent chemical stability in the weakly acidic electrolyte. This letter highlights a way for MOFs to be used in the field of RFBs.

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

Luo, Qingtao; Li, Liyu; Nie, Zimin

We will show a new method to differentiate the vanadium transport from concentration gradient and that from electric field. Flow batteries with vanadium and iron redox couples as the electro-active species were employed to investigate the transport behavior of vanadium ions in the presence of electric field. It was shown that electric field accelerated the positive-to-negative and reduced the negative-to-positive vanadium ions transport in charge process and affected the vanadium ions transport in an opposite way in discharge process. In addition, a method was designed to differentiate the concentration gradient-driven vanadium ions diffusion and electric field-driven vanadium ions migration. Simplifiedmore » mathematical model was established to simulate the vanadium ions transport in real charge-discharge operation of flow battery. The concentration gradient diffusion coefficients and electric-migration coefficients of V2+, V3+, VO2+, and VO2+ across Nafion membrane were obtained by fitting the experimental data.« less

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

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.

Redox Flow Batteries, Hydrogen and Distributed Storage.

PubMed

Dennison, C R; Vrubel, Heron; Amstutz, Véronique; Peljo, Pekka; Toghill, Kathryn E; Girault, Hubert H

2015-01-01

Social, economic, and political pressures are causing a shift in the global energy mix, with a preference toward renewable energy sources. In order to realize widespread implementation of these resources, large-scale storage of renewable energy is needed. Among the proposed energy storage technologies, redox flow batteries offer many unique advantages. The primary limitation of these systems, however, is their limited energy density which necessitates very large installations. In order to enhance the energy storage capacity of these systems, we have developed a unique dual-circuit architecture which enables two levels of energy storage; first in the conventional electrolyte, and then through the formation of hydrogen. Moreover, we have begun a pilot-scale demonstration project to investigate the scalability and technical readiness of this approach. This combination of conventional energy storage and hydrogen production is well aligned with the current trajectory of modern energy and mobility infrastructure. The combination of these two means of energy storage enables the possibility of an energy economy dominated by renewable resources.

Vanadium K Xanes Studies of EET79001 Impact-Melt Glasses Revisited

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Rao, M. N.; Nyquist, L. E.; Ross, D. K.

2016-01-01

Some impact-melt glasses in shergottites are rich in Martian atmospheric noble gases and sulfur suggesting a possible association with regolith-derived secondary mineral assemblages in the shocked samples. Previously, we studied two glasses, # 506 (Lith C in Lith A) and # 507 (Lith C in Lith B) from EET79001 [1,2] and suggested that sulfur initially existed as sulfate in the glass precursor materials and, on shock-melting of the precursors, the sulfate was reduced to sulfides in the shock glasses. To examine the validity of this hypothesis, we used V K microXANES techniques to measure the valence states of vanadium in the Lith C glasses from Lith A and Lith B in EET79001 [3] to complement and com-pare with previous analogous measurements on,78 glass (Lith C in Lith A) [4,5]. We reported the preliminary results in [3]. Vanadium is ideal for addressing the redox issue because it has multiple valence states and is a well-studied element. Vanadium in basalts exists mostly as V(sup 3+), V(sup 4+) and V(sup 5+) in terrestrial samples, mainly as V(sup 3+) with minor V(sup 2+) and minor V(sup 4+) in lunar samples and as roughly equal mixtures of V(sup 3+) and V(sup 4+) in Martian meteorites. In this report, we discuss the application of the V K XANES results to decipher the nature of shock reduction occurring in the silicate glasses during the impact process.

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.

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.

Diels Alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

DOE PAGES

Small, Leo J.; Pratt, III, Harry D.; Fujimoto, Cy H.; ...

2015-10-23

Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3–10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediatemore » ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. As a result, improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.« less

Porphyrin-Based Symmetric Redox-Flow Batteries towards Cold-Climate Energy Storage.

PubMed

Ma, Ting; Pan, Zeng; Miao, Licheng; Chen, Chengcheng; Han, Mo; Shang, Zhenfeng; Chen, Jun

2018-03-12

Electrochemical energy storage with redox-flow batteries (RFBs) under subzero temperature is of great significance for the use of renewable energy in cold regions. However, RFBs are generally used above 10 °C. Herein we present non-aqueous organic RFBs based on 5,10,15,20-tetraphenylporphyrin (H 2 TPP) as a bipolar redox-active material (anode: [H 2 TPP] 2- /H 2 TPP, cathode: H 2 TPP/[H 2 TPP] 2+ ) and a Y-zeolite-poly(vinylidene fluoride) (Y-PVDF) ion-selective membrane with high ionic conductivity as a separator. The constructed RFBs exhibit a high volumetric capacity of 8.72 Ah L -1 with a high voltage of 2.83 V and excellent cycling stability (capacity retention exceeding 99.98 % per cycle) in the temperature range between 20 and -40 °C. Our study highlights principles for the design of RFBs that operate at low temperatures, thus offering a promising approach to electrochemical energy storage under cold-climate conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

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

Xiao, Jie; Liu, Jun; Pan, Huilin

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li 2S x electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Flavin redox bifurcation as a mechanism for controlling the direction of electron flow during extracellular electron transfer.

PubMed

Okamoto, Akihiro; Hashimoto, Kazuhito; Nealson, Kenneth H

2014-10-06

The iron-reducing bacterium Shewanella oneidensis MR-1 has a dual directional electronic conduit involving 40 heme redox centers in flavin-binding outer-membrane c-type cytochromes (OM c-Cyts). While the mechanism for electron export from the OM c-Cyts to an anode is well understood, how the redox centers in OM c-Cyts take electrons from a cathode has not been elucidated at the molecular level. Electrochemical analysis of live cells during switching from anodic to cathodic conditions showed that altering the direction of electron flow does not require gene expression or protein synthesis, but simply redox potential shift about 300 mV for a flavin cofactor interacting with the OM c-Cyts. That is, the redox bifurcation of the riboflavin cofactor in OM c-Cyts switches the direction of electron conduction in the biological conduit at the cell-electrode interface to drive bacterial metabolism as either anode or cathode catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Redox non-innocent bis(2,6-diimine-pyridine) ligand-iron complexes as anolytes for flow battery applications.

PubMed

Duarte, Gabriel M; Braun, Jason D; Giesbrecht, Patrick K; Herbert, David E

2017-12-21

Diiminepyridines are a well-known class of "non-innocent" ligands that confer additional redox activity to coordination complexes beyond metal-centred oxidation/reduction. Here, we demonstrate that metal coordination complexes (MCCs) of diiminepyridine (DIP) ligands with iron are suitable anolytes for redox-flow battery applications, with enhanced capacitance and stability compared with bipyridine analogs, and access to storage of up to 1.6 electron equivalents. Substitution of the ligand is shown to be a key factor in the cycling stability and performance of MCCs based on DIP ligands, opening the door to further optimization.

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.

Electron flow in multicenter enzymes: theory, applications, and consequences on the natural design of redox chains.

PubMed

Léger, Christophe; Lederer, Florence; Guigliarelli, Bruno; Bertrand, Patrick

2006-01-11

In protein film voltammetry, a redox enzyme is directly connected to an electrode; in the presence of substrate and when the driving force provided by the electrode is appropriate, a current flow reveals the steady-state turnover. We show that, in the case of a multicenter enzyme, this signal reports on the energetics and kinetics of electron transfer (ET) along the redox chain that wires the active site to the electrode, and this provides a new strategy for studying intramolecular ET. We propose a model which takes into account all the enzyme's redox microstates, and we prove it useful to interpret data for various enzymes. Several general ideas emerge from this analysis. Considering the reversibility of ET is a requirement: the usual picture, where ET is depicted as a series of irreversible steps, is oversimplified and lacks the important features that we emphasize. We give justification to the concept of apparent reduction potential on the time scale of turnover and we explain how the value of this potential relates to the thermodynamic and kinetic properties of the system. When intramolecular ET does not limit turnover, the redox chain merely mediates the driving force provided by the electrode or the soluble redox partner, whereas when intramolecular ET is slow, the enzyme behaves as if its active active site had apparent redox properties which depend on the reduction potentials of the relays. This suggests an alternative to the idea that redox chains are optimized in terms of speed: evolutionary pressure may have resulted in slowing down intramolecular ET in order to tune the enzyme's "operating potential".

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

Performance evaluation of the sulfur-redox-reaction-activated up-flow anaerobic sludge blanket and down-flow hanging sponge anaerobic/anoxic sequencing batch reactor system for municipal sewage treatment.

PubMed

Hatamoto, Masashi; Ohtsuki, Kota; Maharjan, Namita; Ono, Shinya; Dehama, Kazuya; Sakamoto, Kenichi; Takahashi, Masanobu; Yamaguchi, Takashi

2016-03-01

A sulfur-redox-reaction-activated up-flow anaerobic sludge blanket (UASB) and down-flow hanging sponge (DHS) system, combined with an anaerobic/anoxic sequencing batch reactor (A2SBR), has been used for municipal sewage treatment for over 2 years. The present system achieved a removal rate of 95±14% for BOD, 74±22% for total nitrogen, and 78±25% for total phosphorus, including low water temperature conditions. Sludge conversion rates during the operational period were 0.016 and 0.218 g-VSS g-COD-removed(-1) for the UASB, and DHS, respectively, which are similar to a conventional UASB-DHS system, which is not used of sulfur-redox-reaction, for sewage treatment. Using the sulfur-redox reaction made advanced treatment of municipal wastewater with minimal sludge generation possible, even in winter. Furthermore, the occurrence of a unique phenomenon, known as the anaerobic sulfur oxidation reaction, was confirmed in the UASB reactor under the winter season. Copyright © 2016. Published by Elsevier Ltd.

[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.

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.

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

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.

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.

Component-cost and performance based comparison of flow and static batteries

NASA Astrophysics Data System (ADS)

Hopkins, Brandon J.; Smith, Kyle C.; Slocum, Alexander H.; Chiang, Yet-Ming

2015-10-01

Flow batteries are a promising grid-storage technology that is scalable, inherently flexible in power/energy ratio, and potentially low cost in comparison to conventional or ;static; battery architectures. Recent advances in flow chemistries are enabling significantly higher energy density flow electrodes. When the same battery chemistry can arguably be used in either a flow or static electrode design, the relative merits of either design choice become of interest. Here, we analyze the costs of the electrochemically active stack for both architectures under the constraint of constant energy efficiency and charge and discharge rates, using as case studies the aqueous vanadium-redox chemistry, widely used in conventional flow batteries, and aqueous lithium-iron-phosphate (LFP)/lithium-titanium-phosphate (LTP) suspensions, an example of a higher energy density suspension-based electrode. It is found that although flow batteries always have a cost advantage (kWh-1) at the stack level modeled, the advantage is a strong function of flow electrode energy density. For the LFP/LTP case, the cost advantages decreases from ∼50% to ∼10% over experimentally reasonable ranges of suspension loading. Such results are important input for design choices when both battery architectures are viable options.

An FeIII Azamacrocyclic Complex as a pH-Tunable Catholyte and Anolyte for Redox-Flow Battery Applications.

PubMed

Tsitovich, Pavel B; Kosswattaarachchi, Anjula M; Crawley, Matthew R; Tittiris, Timothy Y; Cook, Timothy R; Morrow, Janet R

2017-11-02

A reversible Fe 3+ /Fe 2+ redox couple of an azamacrocyclic complex is evaluated as an electrolyte with a pH-tunable potential range for aqueous redox-flow batteries (RFBs). The Fe III complex is formed by 1,4,7-triazacyclononane (TACN) appended with three 2-methyl-imidazole donors, denoted as Fe(Tim). This complex exhibits pH-sensitive redox couples that span E 1/2 (Fe 3+ /Fe 2+ )=317 to -270 mV vs. NHE at pH 3.3 and pH 12.8, respectively. The 590 mV shift in potential and kinetic inertness are driven by ionization of the imidazoles at various pH values. The Fe 3+ /Fe 2+ redox is proton-coupled at alkaline conditions, and bulk electrolysis is non-destructive. The electrolyte demonstrates high charge/discharge capacities at both acidic and alkaline conditions throughout 100 cycles. Given its tunable redox, fast electrochemical kinetics, exceptional stability/cyclability, this complex is promising for the design of aqueous RFB catholytes and anolytes that utilize the earth-abundant element iron. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

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.

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

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.

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.

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

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.

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.

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.

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.

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.

[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.

Redox properties of vanadium ions in SBA-15-supported vanadium oxide: an FTIR spectroscopic study.

PubMed

Venkov, Tzvetomir V; Hess, Christian; Jentoft, Friederike C

2007-02-13

The state of vanadium ions in VxOy/SBA-15 (2.7 wt % V) was studied with FTIR spectroscopy using CO and NO as probe molecules. Neither CO (at 85 K) nor NO (at RT) adsorb on the oxidized sample because of the coordinative saturation of V5+ ions and the covalent character of the V5+=O bond. After treatment of the sample in 50 kPa H2 at 673 K, the V5+ ions are reduced to two different types of V3+ sites, as manifested by carbonyl bands at 2189 and 2177 cm-1. In the presence of O2 at 85 K, thus formed V3+ ions are partly oxidized to V4+ sites showing carbonylic bands at 2202 and 2190 cm-1. When the reduced sample is exposed to O2 at room temperature, the V3+ ions are fully oxidized to V5+. The adsorption of NO on the reduced VxOy/SBA-15 shows that the V3+ and V4+ ions possess two effective coordinative vacancies and as a result can adsorb two NO molecules forming the respective V3+(NO)2 and V4+(NO)2 dinitrosyls. The introduction of O2 to the VxOy/SBA-15-NO system leads to reoxidation of the V3+ and V4+ ions to V5+ and formation of bridged (1639 cm-1) and bidentate (1573 cm-1) surface nitrates. After coadsorption of CO and NO on the reduced sample the formation of surface mixed carbonyl-nitrosyls (2108 and 1723 cm-1) was observed for the first time.

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.

Flowable Conducting Particle Networks in Redox-Active Electrolytes for Grid Energy Storage

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

Hatzell, K. B.; Boota, M.; Kumbur, E. C.

2015-01-01

This study reports a new hybrid approach toward achieving high volumetric energy and power densities in an electrochemical flow capacitor for grid energy storage. The electrochemical flow capacitor suffers from high self-discharge and low energy density because charge storage is limited to the available surface area (electric double layer charge storage). Here, we examine two carbon materials as conducting particles in a flow battery electrolyte containing the VO2+/VO2+ redox couple. Highly porous activated carbon spheres (CSs) and multi-walled carbon nanotubes (MWCNTs) are investigated as conducting particle networks that facilitate both faradaic and electric double layer charge storage. Charge storage contributionsmore » (electric double layer and faradaic) are distinguished for flow-electrodes composed of MWCNTs and activated CSs. A MWCNT flow-electrode based in a redox-active electrolyte containing the VO2+/VO2+ redox couple demonstrates 18% less self-discharge, 10 X more energy density, and 20 X greater power densities (at 20 mV s-1) than one based on a non-redox active electrolyte. Furthermore, a MWCNT redox-active flow electrode demonstrates 80% capacitance retention, and >95% coulombic efficiency over 100 cycles, indicating the feasibility of utilizing conducting networks with redox chemistries for grid energy storage.« less

Flowable conducting particle networks in redox-active electrolytes for grid energy storage

DOE PAGES

Hatzell, K. B.; Boota, M.; Kumbur, E. C.; ...

2015-01-09

This paper reports a new hybrid approach toward achieving high volumetric energy and power densities in an electrochemical flow capacitor for grid energy storage. The electrochemical flow capacitor suffers from high self-discharge and low energy density because charge storage is limited to the available surface area (electric double layer charge storage). Here, we examine two carbon materials as conducting particles in a flow battery electrolyte containing the VO 2+/VO 2 + redox couple. Highly porous activated carbon spheres (CSs) and multi-walled carbon nanotubes (MWCNTs) are investigated as conducting particle networks that facilitate both faradaic and electric double layer charge storage.more » Charge storage contributions (electric double layer and faradaic) are distinguished for flow-electrodes composed of MWCNTs and activated CSs. A MWCNT flow-electrode based in a redox-active electrolyte containing the VO 2+/VO 2 + redox couple demonstrates 18% less self-discharge, 10 X more energy density, and 20 X greater power densities (at 20 mV s -1) than one based on a non-redox active electrolyte. Additionally, a MWCNT redox-active flow electrode demonstrates 80% capacitance retention, and >95% coulombic efficiency over 100 cycles, indicating the feasibility of utilizing conducting networks with redox chemistries for grid energy storage.« less

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.

Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc05295b

PubMed Central

VanGelder, L. E.; Kosswattaarachchi, A. M.; Forrestel, P. L.

2018-01-01

Non-aqueous redox flow batteries have emerged as promising systems for large-capacity, reversible energy storage, capable of meeting the variable demands of the electrical grid. Here, we investigate the potential for a series of Lindqvist polyoxovanadate-alkoxide (POV-alkoxide) clusters, [V6O7(OR)12] (R = CH3, C2H5), to serve as the electroactive species for a symmetric, non-aqueous redox flow battery. We demonstrate that the physical and electrochemical properties of these POV-alkoxides make them suitable for applications in redox flow batteries, as well as the ability for ligand modification at the bridging alkoxide moieties to yield significant improvements in cluster stability during charge–discharge cycling. Indeed, the metal–oxide core remains intact upon deep charge–discharge cycling, enabling extremely high coulombic efficiencies (∼97%) with minimal overpotential losses (∼0.3 V). Furthermore, the bulky POV-alkoxide demonstrates significant resistance to deleterious crossover, which will lead to improved lifetime and efficiency in a redox flow battery. PMID:29675217

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

Wei, Xiaoliang; Nie, Zimin; Luo, Qingtao

Redox flow batteries (RFBs) are capable of reversible conversion between electricity and chemical energy. Potential RFB applications resolve around mitigating the discrepancy between electricity production and consumption to improve the stability and utilization of the power infrastructure and tackling the intermittency of renewables such as photovoltaics or wind turbines to enable their reliable integration [1, 2]. Because the energy is stored in externally contained liquid electrolytes and the energy conversion reactions take place at the electrodes, RFBs hold a unique capability to separate energy and power and thus possess considerable design flexibility to meet either energy management driven or powermore » rating oriented grid applications, which is considered to be a unparalleled advantage over conventional solid-state secondary batteries [3]. Other advantages of RFBs include fast response to load changes, high round-trip efficiency, long calender and cycle lives, safe operations, tolerance to deep discharge, etc. [4]. Among various flow battery chemistries, all-vanadium redox flow battery (VRB) was invented by Maria Skyllas-Kazacos at the University of New South Wales in the 1980s [5, 6] and have attracted substantial attention in both research and industrial communities today [7, 8]. A well-recognized advantage that makes VRB stands out among other redox chemistries is the reduced crossover contamination ascribed to employing four different oxidation states of the same vanadium element as the two redox couples. Recently, great progress has led to remarkably improved energy density of VRB by using sulfuric-chloric mixed acid supporting electrolytes that were stable at 2.5M vanadium and had wider operational temperature window of -5~50oC [9], compared with the traditional sulfuric acid VRB system [10].« less

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.

Direct Conversion of Wheat Straw into Electricity with a Biomass Flow Fuel Cell Mediated by Two Redox Ion Pairs.

PubMed

Gong, Jian; Liu, Wei; Du, Xu; Liu, Congmin; Zhang, Zhe; Sun, Feifei; Yang, Le; Xu, Dong; Guo, Hua; Deng, Yulin

2017-02-08

In this paper, a biomass flow fuel cell to directly convert wheat straw to electricity at low temperature (80-90 °C) and atmospheric pressure is presented. Two redox ion pairs, Fe 3+ /Fe 2+ and VO 2 + /VO 2+ , acting as redox catalysts and charge carriers, were used in the anode and cathode flow tanks, respectively. The wheat straw was first oxidized by Fe 3+ in the anode tank at approximately 100 °C. The reduced Fe 2+ in the anode was used to construct a fuel cell with VO 2 + in the cathode. The VO 2 + ions were reduced to VO 2+ and regenerated to VO 2 + by oxygen oxidation. The wheat straw flow fuel cell showed a power output of 100 mW cm -2 . Mediated with liquid Fe 3+ carriers, the solid powder of wheat straw could be gradually degraded into low-molecular-weight organic molecules and even oxidized to CO 2 at the anode without using noble-metal catalysts. The overpotential for the electrodes of the flow fuel cell was examined and the energy cost was estimated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Design Flexibility of Redox Flow Systems. [for energy storage applications

NASA Technical Reports Server (NTRS)

Hagedorn, N. H.; Thaller, L. H.

1982-01-01

The characteristics inherent in Redox flow systems permit considerable latitude in designing systems for specific storage applications. The first of these characteristics is the absence of plating/deplating reactions with their attendant morphology changes at the electrodes. This permits a given Redox system to operate over a wide range of depths of discharge and charge/discharge rates. The second characteristic is the separation of power generating components (stacks) from the energy storage components (tanks). This results in cost effective system design, ease of system growth via modularization, and freedom from sizing restraints so that the whole spectrum of applications, from utilities down to single residence can be considered. The final characteristic is the commonality of the reactant fluids which assures that all cells at all times are receiving reactants at the same state of charge. Since no cell can be out of balance with respect to any other cell, it is possible for some cells to be charged while others are discharging, in effect creating a DC to DC transformer. It is also possible for various groups of cells to be connected to separate loads, thus supplying a range of output voltages. Also, trim cells can be used to maintain constant bus voltage as the load is changed or as the depth of discharge increases. The commonality of reactant fluids also permits any corrective measures such as rebalancing to occur at the system level instead of at the single cell level.

Recent advances in redox flow cell storage systems

NASA Technical Reports Server (NTRS)

Thaller, L. H.

1979-01-01

Several features which were conceived and incorporated into complete redox systems that greatly enhanced its ability to be kept in proper charge balance, to be capable of internal voltage regulation, and in general be treated as a true multicell electrochemical system rather than an assembly of single cells that were wired together, were discussed. The technology status as it relates to the two application areas of solar photovoltaic/wind and distributed energy storage for electric utility applications was addressed. The cost and life advantages of redox systems were also covered.

Performance and cost characteristics of multi-electron transfer, common ion exchange non-aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Laramie, Sydney M.; Milshtein, Jarrod D.; Breault, Tanya M.; Brushett, Fikile R.; Thompson, Levi T.

2016-09-01

Non-aqueous redox flow batteries (NAqRFBs) have recently received considerable attention as promising high energy density, low cost grid-level energy storage technologies. Despite these attractive features, NAqRFBs are still at an early stage of development and innovative design techniques are necessary to improve performance and decrease costs. In this work, we investigate multi-electron transfer, common ion exchange NAqRFBs. Common ion systems decrease the supporting electrolyte requirement, which subsequently improves active material solubility and decreases electrolyte cost. Voltammetric and electrolytic techniques are used to study the electrochemical performance and chemical compatibility of model redox active materials, iron (II) tris(2,2‧-bipyridine) tetrafluoroborate (Fe(bpy)3(BF4)2) and ferrocenylmethyl dimethyl ethyl ammonium tetrafluoroborate (Fc1N112-BF4). These results help disentangle complex cycling behavior observed in flow cell experiments. Further, a simple techno-economic model demonstrates the cost benefits of employing common ion exchange NAqRFBs, afforded by decreasing the salt and solvent contributions to total chemical cost. This study highlights two new concepts, common ion exchange and multi-electron transfer, for NAqRFBs through a demonstration flow cell employing model active species. In addition, the compatibility analysis developed for asymmetric chemistries can apply to other promising species, including organics, metal coordination complexes (MCCs) and mixed MCC/organic systems, enabling the design of low cost NAqRFBs.

An Inexpensive Aqueous Flow Battery for Large-Scale Electrical Energy Storage Based on Water-Soluble Organic Redox Couples

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

Yang, B; Hoober-Burkhardt, L; Wang, F

We introduce a novel Organic Redox Flow Battery (ORBAT), for Meeting the demanding requirements of cost, eco-friendliness, and durability for large-scale energy storage. ORBAT employs two different water-soluble organic redox couples on the positive and negative side of a flow battery. Redox couples such as quinones are particularly attractive for this application. No precious metal catalyst is needed because of the fast proton-coupled electron transfer processes. Furthermore, in acid media, the quinones exhibit good chemical stability. These properties render quinone-based redox couples very attractive for high-efficiency metal-free rechargeable batteries. We demonstrate the rechargeability of ORBAT with anthraquinone-2-sulfonic acid or anthraquinone-2,6-disulfonicmore » acid on the negative side, and 1,2-dihydrobenzoquinone- 3,5-disulfonic acid on the positive side. The ORBAT cell uses a membrane-electrode assembly configuration similar to that used in polymer electrolyte fuel cells. Such a battery can be charged and discharged multiple times at high faradaic efficiency without any noticeable degradation of performance. We show that solubility and mass transport properties of the reactants and products are paramount to achieving high current densities and high efficiency. The ORBAT configuration presents a unique opportunity for developing an inexpensive and sustainable metal-free rechargeable battery for large-scale electrical energy storage. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.orgilicenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.« less

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.

Synthetic Design of Polysulfone Membranes: Morphological Effect on Property and Performance in Flow Batteries

NASA Astrophysics Data System (ADS)

Gindt, Brandon

This dissertation outlines a novel path towards improved understanding and function of proton exchange membranes (PEMs) for redox flow batteries, a large-scale battery storage device. This research uses synthetic methods and nanotechnology through two different approaches to prepare tailored polymer membranes: 1) Ion exchange membranes with enhanced chemical structures to promote membrane morphology on the nano-scale were prepared. Specifically, functional polysulfones (PSUs) were synthesized from different pre-sulfonated monomers. These PSUs have controlled placement and content of unique sulfonic acid moieties. PEMs were fabricated and characterized. The new PEMs showed desirable physical properties and performance in a vanadium redox flow battery (VRFB) cell. 2) Nanoporous PSU membranes were fabricated via post-hydrolysis of polylactide (PLA) from PLA-PSU-PLA triblock copolymer membranes. The controlled morphology and pore size of the resulting nanoporous membranes were evaluated by different microscopy and scattering techniques to understand structure-property relationships. Further, the resulting nanopore surface was chemically modified with sulfonic acid moieties. Membranes were analyzed and evaluated as separators for a VRFB. The chemically modified nanoporous PEMs exhibited unique behavior with respect to their ion conductivity when exposed to solutions of increasing acid concentration. In addition, the hierarchical micro-nanoporous membranes developed further showed promising structure and properties.

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.

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.

Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction

NASA Astrophysics Data System (ADS)

Ge, Zhijun; Wang, Ling; He, Zhangxing; Li, Yuehua; Jiang, Yingqiao; Meng, Wei; Dai, Lei

2018-04-01

A novel strategy for improving the electro-catalytic properties of graphite felt (GF) electrode in vanadium redox flow battery (VRFB) is designed by depositing cobalt phosphide (CoP) onto GF surface. The CoP powder is synthesized by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Cyclic voltammetry results confirm that the CoP-modified graphite felt (GF-CoP) electrode has excellent reversibility and electro-catalytic activity to the VO2+/VO2+ cathodic reaction compared with the pristine GF electrode. The cell using GF-CoP electrode shows apparently higher discharge capacity over that based on GF electrode. The cell using GF-CoP electrode has the capacity of 67.2 mA h at 100 mA cm-2, 32.7 mA h larger than that using GF electrode. Compared with cell using GF electrode, the voltage efficiency of the cell based on GF-CoP electrode increases by 5.9% and energy efficiency by 5.4% at a current density of 100 mA cm-2. The cell using GF-CoP electrode can reach 94.31% capacity retention after 50 cycles at a current density of 30 mA cm-2. The results show that the CoP can effectively promote the VO2+/VO2+ redox reaction, implying that metal phosphides are a new kind of potential catalytic materials for VRFB.

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.

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.

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.

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.

Application of carbon materials in redox flow batteries

NASA Astrophysics Data System (ADS)

Chakrabarti, Barun Kumar; Brandon, N. P.; Hajimolana, S. A.; Tariq, F.; Yufit, V.; Hashim, M. A.; Hussain, M. A.; Low, C. T. J.; Aravind, P. V.

2014-05-01

The redox flow battery (RFB) has been the subject of state-of-the-art research by several groups around the world. Most work commonly involves the application of various low-cost carbon-polymer composites, carbon felts, cloth, paper and their different variations for the electrode materials of the RFB. Usually, the carbon-polymer composite electrode has relatively high bulk resistivity and can be easily corroded when the polarised potential on the anode is more positive than that of oxygen evolution and this kind of heterogeneous corrosion may lead to battery failure due to electrolyte leakage. Therefore, carbon electrodes with high electrical conductivity, acid-resistance and electrochemical stability are highly desirable. This review discusses such issues in depth and presents an overview on future research directions that may help commercialise RFB technology. A comprehensive discussion is provided on the advances made using nanotechnology and it is envisaged that if this is combined with ionic liquid technology, major advantages could be realised. In addition the identification of RFB failure mechanisms by means of X-ray computed nano tomography is expected to bring added benefits to the technology.

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.

Subcellular Redox Targeting: Bridging in Vitro and in Vivo Chemical Biology.

PubMed

Long, Marcus J C; Poganik, Jesse R; Ghosh, Souradyuti; Aye, Yimon

2017-03-17

Networks of redox sensor proteins within discrete microdomains regulate the flow of redox signaling. Yet, the inherent reactivity of redox signals complicates the study of specific redox events and pathways by traditional methods. Herein, we review designer chemistries capable of measuring flux and/or mimicking subcellular redox signaling at the cellular and organismal level. Such efforts have begun to decipher the logic underlying organelle-, site-, and target-specific redox signaling in vitro and in vivo. These data highlight chemical biology as a perfect gateway to interrogate how nature choreographs subcellular redox chemistry to drive precision redox biology.

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).

An Aqueous Redox-Flow Battery with High Capacity and Power: The TEMPTMA/MV System.

PubMed

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

2016-11-07

Redox-flow batteries (RFB) can easily store large amounts of electric energy and thereby mitigate the fluctuating output of renewable power plants. They are widely discussed as energy-storage solutions for wind and solar farms to improve the stability of the electrical grid. Most common RFB concepts are based on strongly acidic metal-salt solutions or poorly performing organics. Herein we present a battery which employs the highly soluble N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride (TEMPTMA) and the viologen derivative N,N'-dimethyl-4,4-bipyridinium dichloride (MV) in a simple and safe aqueous solution as redox-active materials. The resulting battery using these electrolyte solutions has capacities of 54 Ah L -1 , giving a total energy density of 38 Wh L -1 at a cell voltage of 1.4 V. With peak current densities of up to 200 mA cm -2 the TEMPTMA/MV system is a suitable candidate for compact high-capacity and high-power applications. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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.

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

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.

Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

NASA Astrophysics Data System (ADS)

Sossi, Paolo A.; Prytulak, Julie; O'Neill, Hugh St. C.

2018-04-01

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities ({f_{{{O}2}}}), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V3+ and V4+ in magnetite, and a mixture of IV- and VI-fold V5+ and V4+ in the melt. The magnitude of the fractionation factor systematically increases with increasing log{f_{{{O}2}}} relative to the Fayalite-Magnetite-Quartz buffer (FMQ), from Δ51Vmag-gl = - 0.63 ± 0.09‰ at FMQ - 1 to - 0.92 ± 0.11‰ (SD) at ≈ FMQ + 5, reflecting constant V3+/V4+ in magnetite but increasing V5+/V4+ in the melt with increasing log{f_{{{O}2}}}. These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.

Effect of oxygen plasma treatment on the electrochemical performance of the rayon and polyacrylonitrile based carbon felt for the vanadium redox flow battery application

NASA Astrophysics Data System (ADS)

Dixon, D.; Babu, D. J.; Langner, J.; Bruns, M.; Pfaffmann, L.; Bhaskar, A.; Schneider, J. J.; Scheiba, F.; Ehrenberg, H.

2016-11-01

Oxygen plasma treatment was applied on commercially available graphite felt electrodes based on rayon (GFA) and polyacrylonitrile (GFD). The formation of functional groups on the surface of the felt was confirmed by X-ray photoelectron spectroscopy measurements. The BET studies of the plasma treated electrodes showed no significant increase in surface area for both the rayon as well as the PAN based felts. Both plasma treated electrodes showed significantly enhanced V3+/V2+ redox activity compared to the pristine electrodes. Since an increase of the surface area has been ruled out for plasma treated electrode the enhanced activity could be attributed to surface functional groups. Interestingly, plasma treated GFD felts showed less electrochemical activity towards V5+/V4+ compared to the pristine electrode. Nevertheless, an overall increase of the single cell performance was still observed as the negative electrode is known to be the performance limiting electrode. Thus, to a great extent the present work helps to preferentially understand the importance of functional groups on the electrochemical activity of negative and positive redox reaction. The study emphasizes the need of highly active electrodes especially at the negative electrode side as inactive electrodes can still facilitate hydrogen evolution and degrade the electrolyte in VRFBs.

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.

3D Graphene-Ni Foam as an Advanced Electrode for High-Performance Nonaqueous Redox Flow Batteries.

PubMed

Lee, Kyubin; Lee, Jungkuk; Kwon, Kyoung Woo; Park, Min-Sik; Hwang, Jin-Ha; Kim, Ki Jae

2017-07-12

Electrodes composed of multilayered graphene grown on a metal foam (GMF) were prepared by directly growing multilayer graphene sheets on a three-dimensional (3D) Ni-foam substrate via a self-catalyzing chemical vapor deposition process. The multilayer graphene sheets are successfully grown on the Ni-foam substrate surface, maintaining the unique 3D macroporous structure of the Ni foam. The potential use of GMF electrodes in nonaqueous redox flow batteries (RFBs) is carefully examined using [Co(bpy) 3 ] +/2+ and [Fe(bpy) 3 ] 2+/3+ redox couples. The GMF electrodes display a much improved electrochemical activity and enhanced kinetics toward the [Co(bpy) 3 ] +/2+ (anolyte) and [Fe(bpy) 3 ] 2+/3+ (catholyte) redox couples, compared with the bare Ni metal foam electrodes, suggesting that the 2D graphene sheets having lots of interdomain defects provide sufficient reaction sites and secure electric-conduction pathways. Consequently, a nonaqueous RFB cell assembled with GMF electrodes exhibits high Coulombic and voltage efficiencies of 87.2 and 90.9%, respectively, at the first cycle. This performance can be maintained up to the 50th cycle without significant efficiency loss. Moreover, the importance of a rational electrode design for improving electrochemical performance is addressed.

Redox flow cell development and demonstration project, calendar year 1976

NASA Technical Reports Server (NTRS)

1977-01-01

The major focus of the effort was the key technology issues that directly influence the fundamental feasibility of the overall redox concept. These issues were the development of a suitable semipermeable separator membrane for the system, the screening and study of candidate redox couples to achieve optimum cell performance, and the carrying out of systems analysis and modeling to develop system performance goals and cost estimates.

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.

Composite separators and redox flow batteries based on porous separators

DOEpatents

Li, Bin; Wei, Xiaoliang; Luo, Qingtao; Nie, Zimin; Wang, Wei; Sprenkle, Vincent L.

2016-01-12

Composite separators having a porous structure and including acid-stable, hydrophilic, inorganic particles enmeshed in a substantially fully fluorinated polyolefin matrix can be utilized in a number of applications. The inorganic particles can provide hydrophilic characteristics. The pores of the separator result in good selectivity and electrical conductivity. The fluorinated polymeric backbone can result in high chemical stability. Accordingly, one application of the composite separators is in redox flow batteries as low cost membranes. In such applications, the composite separator can also enable additional property-enhancing features compared to ion-exchange membranes. For example, simple capacity control can be achieved through hydraulic pressure by balancing the volumes of electrolyte on each side of the separator. While a porous separator can also allow for volume and pressure regulation, in RFBs that utilize corrosive and/or oxidizing compounds, the composite separators described herein are preferable for their robustness in the presence of such compounds.

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.