Polyoxometalate active charge-transfer material for mediated redox flow battery

Energy Technology Data Exchange (ETDEWEB)

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.

Techno-Economic Modeling and Analysis of Redox Flow Battery Systems

Directory of Open Access Journals (Sweden)

Jens Noack

2016-08-01

Full Text Available A techno-economic model was developed to investigate the influence of components on the system costs of redox flow batteries. Sensitivity analyses were carried out based on an example of a 10 kW/120 kWh vanadium redox flow battery system, and the costs of the individual components were analyzed. Particular consideration was given to the influence of the material costs and resistances of bipolar plates and energy storage media as well as voltages and electric currents. Based on the developed model, it was possible to formulate statements about the targeted optimization of a developed non-commercial vanadium redox flow battery system and general aspects for future developments of redox flow batteries.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

OpenAIRE

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

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 ...

Cascade redox flow battery systems

Science.gov (United States)

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.

Bifunctional electrode performance for zinc-air flow cells with pulse charging

International Nuclear Information System (INIS)

Pichler, Birgit; Weinberger, Stephan; Reščec, Lucas; Grimmer, Ilena; Gebetsroither, Florian; Bitschnau, Brigitte; Hacker, Viktor

2017-01-01

Highlights: •Manufacture of bi-catalyzed bifunctional air electrodes via scalable process. •Direct synthesis of NiCo 2 O 4 on carbon nanofibers or nickel powder support. •450 charge and discharge cycles over 1000 h at 50 mA cm −2 demonstrated. •Pulse charging with 150 mA cm −2 is successfully applied on air electrodes. •Charge and discharge ΔV of <0.8 V at 50 mA cm −2 when supplied with O 2. -- Abstract: Bifunctional air electrodes with tuned composition consisting of two precious metal-free oxide catalysts are manufactured for application in rechargeable zinc-air flow batteries and electrochemically tested via long-term pulse charge and discharge cycling experiments at 50 mA cm −2 (mean). NiCo 2 O 4 spinel, synthesized via direct impregnation on carbon nanofibers or nickel powder and characterized by energy dispersive X-ray spectroscopy and X-ray diffraction experiments, shows high activity toward oxygen evolution reaction with low charge potentials of < 2.0 V vs. Zn/Zn 2+ . La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 perovskite exhibits bifunctional activity and outperforms the NiCo 2 O 4 spinel in long-term stability tenfold. By combining the catalysts in one bi-catalyzed bifunctional air electrode, stable performances of more than 1000 h and 450 cycles are achieved when supplied with oxygen and over 650 h and 300 cycles when supplied with synthetic air. In addition, the pulse charging method, which is beneficial for compact zinc deposition, is successfully tested on air electrodes during long-term operation. The oxygen evolution potentials during pulse, i.e. at tripled charge current density of 150 mA cm −2 , are only 0.06–0.08 V higher compared to constant charging current densities. Scanning electron microscopy confirms that mechanical degradation caused by bubble formation during oxygen evolution results in slowly decreasing discharge potentials.

Redox flow batteries having multiple electroactive elements

Energy Technology Data Exchange (ETDEWEB)

Wang, Wei; Li, Liyu; Yang, Zhenguo; Nie, Zimin

2018-05-01

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.

Assessment of the development of a battery charging infrastructure for a redox flow battery based electromobility concept; Bewertung des Aufbaus einer Ladeinfrastruktur fuer eine Redox-Flow-Batteriebasierte Elektromobilitaet

Energy Technology Data Exchange (ETDEWEB)

Arpad Funke, Simon; Wietschel, Martin [Fraunhofer-Institut fuer System- und Innovationsforschung (ISI), Karlsruhe (Germany). Competence Center Energietechnologien und Energiesysteme

2012-07-01

Apart from the high acquisition cost, the major obstacles to widespread use of electric-powered vehicles today are long battery charging times and limited mileage. Rechargeable batteries might be a solution. The publication investigates a potential infrastructure for electric-powered vehicles based on so-called redox flow batteries. Redox flow batteries are characterized in that active materials are dissolved in liquid electrolyte and are stored outside the cell. Batteries are recharged by exchanging charged electrolyte for discharged electrolyte, which can be done in fuel stations. Redox flow batteries have the drawback of low energy and power density and were hardly ever considered for mobile applications so far. A technical analysis of RFB technology identified the vanadium oxygen redox flow fuel cell (VOFC) as a promising version. It provides higher energy density than conventional redox flow batteries, but development is still in an early stage. Assuming a 'best case' scenario, a refuelling infrastructure for VOFC vehicles was developed and compared with battery-powered vehicles (BEV) and fuel cell vehicles (FVEV). It was found that electromobility based on VOFC may be a promising alternative to current electromobility concepts. (orig./AKB) [German] Neben den Anschaffungsausgaben stehen lange Ladezeiten und eine beschraenkte Reichweite dem heutigen Einsatz von Elektrofahrzeugen oft entgegen. Eine moegliche Abhilfe koennten betankbare Batterien leisten. In der vorliegenden Arbeit soll ein moeglicher Infrastrukturaufbau fuer Elektrofahrzeuge mit sogenannten Redox-Flow-Batterien untersucht werden. Redox-Flow-Batterien besitzen die Eigenschaft, dass aktive Materialien geloest in Fluessigelektrolyten ausserhalb der Zelle gespeichert werden. Dieser Aufbau ermoeglicht das Aufladen der Batterie, indem der entladene Elektrolyt durch geladenen ausgetauscht wird. Dieser Tausch kann an einer Tankstelle durchgefuehrt werden. Ein wesentlicher Nachteil von Redox-Flow

A biomimetic redox flow battery based on flavin mononucleotide

OpenAIRE

Orita, A; Verde, MG; Sakai, M; Meng, YS

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 reactio...

Cost-driven materials selection criteria for redox flow battery electrolytes

Science.gov (United States)

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

Science.gov (United States)

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

Science.gov (United States)

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.

Science.gov (United States)

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.

A biomimetic redox flow battery based on flavin mononucleotide

Science.gov (United States)

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.

Membrane development for vanadium redox flow batteries.

Science.gov (United States)

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

2011-10-17

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

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

Science.gov (United States)

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.

Numerical modeling of an all vanadium redox flow battery.

Energy Technology Data Exchange (ETDEWEB)

Clausen, Jonathan R.; Brunini, Victor E.; Moffat, Harry K.; Martinez, Mario J.

2014-01-01

We develop a capability to simulate reduction-oxidation (redox) flow batteries in the Sierra Multi-Mechanics code base. Specifically, we focus on all-vanadium redox flow batteries; however, the capability is general in implementation and could be adopted to other chemistries. The electrochemical and porous flow models follow those developed in the recent publication by [28]. We review the model implemented in this work and its assumptions, and we show several verification cases including a binary electrolyte, and a battery half-cell. Then, we compare our model implementation with the experimental results shown in [28], with good agreement seen. Next, a sensitivity study is conducted for the major model parameters, which is beneficial in targeting specific features of the redox flow cell for improvement. Lastly, we simulate a three-dimensional version of the flow cell to determine the impact of plenum channels on the performance of the cell. Such channels are frequently seen in experimental designs where the current collector plates are borrowed from fuel cell designs. These designs use a serpentine channel etched into a solid collector plate.

Organic non-aqueous cation-based redox flow batteries

Science.gov (United States)

Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai; Zhang, Lu; Brushett, Fikile R.

2016-03-29

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 unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.

Estimating the system price of redox flow batteries for grid storage

Science.gov (United States)

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.

Evaluation of electrolytes for redox flow battery applications

International Nuclear Information System (INIS)

Chakrabarti, M.H.; Dryfe, R.A.W.; Roberts, E.P.L.

2007-01-01

A number of redox systems have been investigated in this work with the aim of identifying electrolytes suitable for testing redox flow battery cell designs. The criteria for the selection of suitable systems were fast electrochemical kinetics and minimal cross-contamination of active electrolytes. Possible electrolyte systems were initially selected based on cyclic voltammetry data. Selected systems were then compared by charge/discharge experiments using a simple H-type cell. The all-vanadium electrolyte system has been developed as a commercial system and was used as the starting point in this study. The performance of the all-vanadium system was significantly better than an all-chromium system which has recently been reported. Some metal-organic and organic redox systems have been reported as possible systems for redox flow batteries, with cyclic voltammetry data suggesting that they could offer near reversible kinetics. However, Ru(acac) 3 in acetonitrile could only be charged efficiently to 9.5% of theoretical charge, after which irreversible side reactions occurred and [Fe(bpy) 3 ](ClO 4 ) 2 in acetonitrile was found to exhibit poor charge/discharge performance

Double-membrane triple-electrolyte redox flow battery design

Science.gov (United States)

Yushan, Yan; Gu, Shuang; Gong, Ke

2018-03-13

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 great 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.

Recent developments in organic redox flow batteries: A critical review

Science.gov (United States)

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.

Liquid Quinones for Solvent-Free Redox Flow Batteries.

Science.gov (United States)

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.

Science.gov (United States)

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.

Anthraquinone with Tailored Structure for Nonaqueous Metal-Organic Redox Flow Battery

Energy Technology Data Exchange (ETDEWEB)

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

2012-06-08

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

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

Science.gov (United States)

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

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

Polyarene mediators for mediated redox flow battery

Science.gov (United States)

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.

Chloride supporting electrolytes for all-vanadium redox flow batteries.

Science.gov (United States)

Kim, Soowhan; Vijayakumar, M; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Chen, Feng; Hu, Jianzhi; Li, Liyu; Yang, Zhenguo

2011-10-28

This paper examines vanadium chloride solutions as electrolytes for an all-vanadium redox flow battery. The chloride solutions were capable of dissolving more than 2.3 M vanadium at varied valence states and remained stable at 0-50 °C. The improved stability appeared due to the formation of a vanadium dinuclear [V(2)O(3)·4H(2)O](4+) or a dinuclear-chloro complex [V(2)O(3)Cl·3H(2)O](3+) in the solutions over a wide temperature range. The all-vanadium redox flow batteries with the chloride electrolytes demonstrated excellent reversibility and fairly high efficiencies. Only negligible, if any, gas evolution was observed. The improved energy capacity and good performance, along with the ease in heat management, would lead to substantial reduction in capital cost and life-cycle cost, making the vanadium chloride redox flow battery a promising candidate for stationary applications. This journal is © the Owner Societies 2011

Investigating improvements on redox flow batteries

CSIR Research Space (South Africa)

Swartbooi, AM

2006-09-01

Full Text Available storage devices coupled to most of their applications. Lead-acid batteries have long been used as the most economical option to store electricity in many small scale applications, but lately more interest have been shown in redox flow batteries. The low...

Multiple-membrane multiple-electrolyte redox flow battery design

Science.gov (United States)

Yan, Yushan; Gu, Shuang; Gong, Ke

2017-05-02

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 electrolyte and the positive or negative electrolyte.

Organic non-aqueous cation-based redox flow batteries

Science.gov (United States)

Zhang, Lu; Huang, Jinhua; Burrell, Anthony

2018-05-08

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 unsaturated 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.

A High-Current, Stable Nonaqueous Organic Redox Flow Battery

Energy Technology Data Exchange (ETDEWEB)

Wei, Xiaoliang; Duan, Wentao; Huang, Jinhua; Zhang, Lu; Li, Bin; Reed, David; Xu, Wu; Sprenkle, Vincent; Wang, Wei

2016-10-14

Nonaqueous redox flow batteries are promising in pursuit of high-energy storage systems owing to the broad voltage window, but currently are facing key challenges such as poor cycling stability and lack of suitable membranes. Here we report a new nonaqueous all-organic flow chemistry that demonstrates an outstanding cell cycling stability primarily because of high chemical persistency of the organic radical redox species and their good compatibility with the supporting electrolyte. A feasibility study shows that Daramic® and Celgard® porous separators can lead to high cell conductivity in flow cells thus producing remarkable cell efficiency and material utilization even at high current operations. This result suggests that the thickness and pore size are the key performance-determining factors for porous separators. With the greatly improved flow cell performance, this new flow system largely addresses the above mentioned challenges and the findings may greatly expedite the development of durable nonaqueous flow batteries.

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

Science.gov (United States)

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.

Science.gov (United States)

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.

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

Science.gov (United States)

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.

A coupled three dimensional model of vanadium redox flow battery for flow field designs

International Nuclear Information System (INIS)

Yin, Cong; Gao, Yan; Guo, Shaoyun; Tang, Hao

2014-01-01

A 3D (three-dimensional) model of VRB (vanadium redox flow battery) with interdigitated flow channel design is proposed. Two different stack inlet designs, single-inlet and multi-inlet, are structured in the model to study the distributions of fluid pressure, electric potential, current density and overpotential during operation of VRB cell. Electrolyte flow rate and stack channel dimension are proved to be the critical factors affecting flow distribution and cell performance. The model developed in this paper can be employed to optimize both VRB stack design and system operation conditions. Further improvements of the model concerning current density and electrode properties are also suggested in the paper. - Highlights: • A coupled three-dimensional model of vanadium redox flow cell is proposed. • Interdigitated flow channels with two different manifold designs are simulated. • Manifold structure affects uniformity of distribution patterns significantly. • Increased electrolyte flow rate improves cell performance for both designs. • Decreased channel size and enlarged land width enhance cell voltage

Electrochemical Switching of Conductance with Diarylethene-Based Redox-Active Polymers

DEFF Research Database (Denmark)

Logtenberg, Hella; van der Velde, Jasper H. M.; de Mendoza, Paula

2012-01-01

Reversible switching of conductance using redox triggered switching of a polymer-modified electrode is demonstrated. A bifunctional monomer comprising a central electroswitchable core and two bithiophene units enables formation of a film through anodic electropolymerization. The conductivity...... of the polymer can be switched electrochemically in a reversible manner by redox triggered opening and closing of the diarylethene unit. In the closed state, the conductivity of the modified electrode is higher than in the open state....

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

2018-06-01

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

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

Carbon-free Solid Dispersion LiCoO2 Redox Couple Characterization and Electrochemical Evaluation for All Solid Dispersion Redox Flow Batteries

International Nuclear Information System (INIS)

Qi, Zhaoxiang; Liu, Aaron L.; Koenig, Gary M.

2017-01-01

Highlights: • LiCoO 2 particles can be cycled in carbon-free and binder-free coin cells. • A carbon-free LiCoO 2 suspension is electrochemically oxidized and reduced. • Comparable size LiCoO 2 and Li 4 Ti 5 O 12 suspensions have similar rheological properties. • First demonstration of redox couples with solid suspensions for both electrodes. - Abstract: Semi-solid flow batteries have been reported to have among the highest energy densities for redox flow batteries, however, they rely on percolated carbon networks which increase the electrolyte viscosity significantly. We report the first demonstration of carbon-free redox flow couples comprised of dispersed lithium-ion battery active material suspensions, with sub-micrometer LiCoO 2 (LCO) particles at the cathode and Li 4 Ti 5 O 12 (LTO) particles at the anode. Both electrochemical and rheological properties of the LCO suspensions are reported and compared to previous reports for LTO dispersed electrochemical redox couples. An LTO anode and LCO cathode full cell was constructed and reversible electrochemical redox reaction of the dispersed particles was successfully demonstrated. This carbon-free dispersed lithium-ion active material full cell provides a proof-of-concept for a system that lies between the relatively high viscosity semi-solid flow cells with percolated carbon networks and the relatively low energy density conventional flow cells comprised of dissolved transition metals, providing a system for future study of the trade-off between energy density and viscosity for electrochemical flow cells that rely on solid active materials.

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

Science.gov (United States)

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-01-01

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 a 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.

Redox flow batteries. Already an alternative storage solution for hybrid PV mini-grids?

Energy Technology Data Exchange (ETDEWEB)

Vetter, Matthias; Dennenmoser, Martin; Schwunk, Simon; Smolinka, Tom [Fraunhofer Institute for Solar Energy Systems (ISE), Freiburg (Germany); Doetsch, Christian; Berthold, Sascha [Fraunhofer Institute for Environmental, Safety and Energy Technology (UMSICHT), Oberhausen (Germany); Tuebke, Jens; Noack, Jens [Fraunhofer Institute for Chemical Technology (ICT), Karlsruhe (Germany)

2010-07-01

Due to the flexible scalability of the power to energy ratio redox flow batteries are a suitable solution for quite a lot of decentralized applications. E.g. the autonomy time of a stand-alone system or mini-grid can be raised by increasing the tank size of the redox flow battery. In this paper the test site ''Rappenecker Hof'' in the black forest is used as an example for simulation based life cycle cost analyses of a vanadium redox flow battery integrated in an autonomous hybrid PV system. Two cases with lead acid batteries are considered as benchmarks for economic viability of the redox flow battery solution in such applications. At the moment a 1 KW / 6 kWh system for decentralized solutions is developed and will be installed in the ''Solarhaus'' in Freiburg. The main results of the cell stack and system design as well as performance data are presented. Furthermore simulation models and the model based development of the ''Smart Redox flow Control'' are described. For the optimized integration of the storage unit in the energy system a communication interface for exchanging data with the supervisory energy management system is introduced. On this basis a SOC forecast according to a given demand profile can be determined. (orig.)

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

Science.gov (United States)

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.

Evaluation of in situ sulfate reduction as redox buffer capacity in groundwater flow path

International Nuclear Information System (INIS)

Ioka, Seiichiro; Iwatsuki, Teruki; Amano, Yuki; Furue, Ryoji

2007-01-01

For safety assessment of geological isolation, it is important to evaluate in situ redox buffer capacity in high-permeability zone as groundwater flow path. The study evaluated in situ sulfate reduction as redox buffer capacity in the conglomerate bedding in Toki Lignite-bearing Formation, which occurs at the lowest part of sedimentary rocks overlying basement granite. The bedding plays an important role as the main groundwater flow path. The result showed that in situ redox buffer capacity in the conglomerate bedding has been identified on first nine months, whereas in the following period the redox buffer capacity has not been identified for about fifteen months. This will be caused by the bedding became inappropriate for microbial survival as the organic matter which is needfuel for microbial activity was consumed. Thus, there will be limited redox buffer capacity in groundwater flow path even in formation including organic matter-bearing layer. (author)

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

DEFF Research Database (Denmark)

Liao, Shichao; Zong, Xu; Seger, Brian

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 photoelect......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...

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

Science.gov (United States)

Hong, Jeehoon; Kim, Ketack

2018-04-17

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.

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

Science.gov (United States)

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.

Redox flow batteries based on supporting solutions containing chloride

Science.gov (United States)

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

Energy Technology Data Exchange (ETDEWEB)

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.

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

Science.gov (United States)

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.

Materials and Systems for Organic Redox Flow Batteries: Status and Challenges

Energy Technology Data Exchange (ETDEWEB)

Wei, Xiaoliang [Joint Center for Energy Storage Research (JCESR), Argonne, Illinois 60439, United States; Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Pan, Wenxiao [Department; Duan, Wentao [Joint Center for Energy Storage Research (JCESR), Argonne, Illinois 60439, United States; Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Hollas, Aaron [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Yang, Zheng [Joint Center for Energy Storage Research (JCESR), Argonne, Illinois 60439, United States; Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Li, Bin [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Nie, Zimin [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Liu, Jun [Joint Center for Energy Storage Research (JCESR), Argonne, Illinois 60439, United States; Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Reed, David [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Wang, Wei [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Sprenkle, Vincent [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States

2017-08-14

Redox flow batteries are propitious stationary energy storage technologies with exceptional scalability and flexibility to improve the stability, efficiency and sustainability of our power grid. The redox-active materials are the central component to RFBs for achieving high energy density and good cyclability. Traditional inorganic-based materials encounter critical technical and economic limitations such as low solubility, inferior electrochemical activity, and high cost. Redox-active organic materials (ROMs) are promising alternative “green” candidates to push the boundaries of energy storage because of the significant advantages of molecular diversity, structural tailorability, and natural abundance. Here the recent development of a variety of ROM families and associated battery designs in both aqueous and nonaqueous electrolytes are reviewed. Moreover, the critical challenges and potential research opportunities for developing practically relevant organic flow batteries are discussed.

Rebalancing electrolytes in redox flow battery systems

Science.gov (United States)

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.

An application of actinide elements for a redox flow battery

International Nuclear Information System (INIS)

Shiokawa, Yoshinobu; Yamana, Hajimu; Moriyama, Hirotake

2000-01-01

The electrochemical properties of U, Np, Pu and Am were discussed from the viewpoint of cell active materials. From the thermodynamic properties and the kinetics of electrode reactions, it is found that neptunium in the aqueous system can be utilized as an active material of the redox flow battery for the electric power storage. A new neptunium redox battery is proposed in the present article: the galvanic cell is expressed by (-)|Np 3+ , Np 4+ |NpO 2 + , NpO 2 2+ |(+). The neptunium battery is expected to have more excellent charge and discharge performance than the current vanadium battery, whereas the thermodynamic one of the former is comparable to the latter. For the development of a uranium redox battery, the application of the redox reactions in the non-aqueous solvents is essential. (author)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Critical transport issues for improving the performance of aqueous redox flow batteries

Science.gov (United States)

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.

Advanced porous electrodes with flow channels for vanadium redox flow battery

Science.gov (United States)

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.

Fe-V redox flow batteries

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Science.gov (United States)

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.

Iron-sulfide redox flow batteries

Science.gov (United States)

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.

Multi-physics Model for the Aging Prediction of a Vanadium Redox Flow Battery System

International Nuclear Information System (INIS)

Merei, Ghada; Adler, Sophie; Magnor, Dirk; Sauer, Dirk Uwe

2015-01-01

Highlights: • Present a multi-physics model of vanadium redox-flow battery. • This model is essential for aging prediction. • It is applicable for VRB system of different power and capacity ratings. • Good results comparing with current research in this field. - Abstract: The all-vanadium redox-flow battery is an attractive candidate to compensate the fluctuations of non-dispatchable renewable energy generation. While several models for vanadium redox batteries have been described yet, no model has been published, which is adequate for the aging prediction. Therefore, the present paper presents a multi-physics model which determines all parameters that are essential for an aging prediction. In a following paper, the corresponding aging model of vanadium redox flow battery (VRB) is described. The model combines existing models for the mechanical losses and temperature development with new approaches for the batteries side reactions. The model was implemented in Matlab/Simulink. The modeling results presented in the paper prove to be consistent with the experimental results of other research groups

Elucidating effects of cell architecture, electrode material, and solution composition on overpotentials in redox flow batteries

International Nuclear Information System (INIS)

Pezeshki, Alan M.; Sacci, Robert L.; Delnick, Frank M.; Aaron, Douglas S.; Mench, Matthew M.

2017-01-01

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 ohmic 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.

Performance of a vanadium redox flow battery with and without flow fields

International Nuclear Information System (INIS)

Xu, Q.; Zhao, T.S.; Zhang, C.

2014-01-01

Highlights: • The performances of a VRFB with/without flow fields are compared. • The respective maximum power efficiency occurs at different flow rates. • The battery with flow fields Exhibits 5% higher energy efficiency. - Abstract: A flow field is an indispensable component for fuel cells to macroscopically distribute reactants onto electrodes. However, it is still unknown whether flow fields are also required in all-vanadium redox flow batteries (VRFBs). In this work, the performance of a VRFB with flow fields is analyzed and compared with the performance of a VRFB without flow fields. It is demonstrated that the battery with flow fields has a higher discharge voltage at higher flow rates, but exhibits a larger pressure drop. The maximum power-based efficiency occurs at different flow rates for the both batteries with and without flow fields. It is found that the battery with flow fields Exhibits 5% higher energy efficiency than the battery without flow fields, when operating at the flow rates corresponding to each battery's maximum power-based efficiency. Therefore, the inclusion of flow fields in VRFBs can be an effective approach for improving system efficiency

Graphite-graphite oxide composite electrode for vanadium redox flow battery

International Nuclear Information System (INIS)

Li Wenyue; Liu Jianguo; Yan Chuanwei

2011-01-01

Highlights: → A new composite electrode is designed for vanadium redox flow battery (VRB). → The graphite oxide (GO) is used as electrode reactions catalyst. → The excellent electrode activity is attributed to the oxygen-containing groups attached on the GO surface. → A catalytic mechanism of the GO towards the redox reactions is presumed. - Abstract: A graphite/graphite oxide (GO) composite electrode for vanadium redox battery (VRB) was prepared successfully in this paper. The materials were characterized with X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The specific surface area was measured by the Brunauer-Emmett-Teller method. The redox reactions of [VO 2 ] + /[VO] 2+ and V 3+ /V 2+ were studied with cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the electrochemical performances of the electrode were improved greatly when 3 wt% GO was added into graphite electrode. The redox peak currents of [VO 2 ] + /[VO] 2+ and V 3+ /V 2+ couples on the composite electrode were increased nearly twice as large as that on the graphite electrode, and the charge transfer resistances of the redox pairs on the composite electrode are also reduced. The enhanced electrochemical activity could be ascribed to the presence of plentiful oxygen functional groups on the basal planes and sheet edges of the GO and large specific surface areas introduced by the GO.

Towards a thermally regenerative all-copper redox flow battery

OpenAIRE

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

2014-01-01

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 degrees C, by distilling off the acetonitrile. This destabilizes the Cu+ complex, leading to recovery of the starting materials.

Towards a thermally regenerative all-copper redox flow battery.

Science.gov (United States)

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.

Elucidating effects of cell architecture, electrode material, and solution composition on overpotentials in redox flow batteries

Energy Technology Data Exchange (ETDEWEB)

Pezeshki, Alan M. [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sacci, Robert L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Delnick, Frank M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Aaron, Douglas S. [Univ. of Tennessee, Knoxville, TN (United States); Mench, Matthew M. [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2017-01-16

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 V²⁺/V³⁺ redox couple on carbon felt and carbon paper electrodes in the vanadium redox flow battery. Carbon felt was limited by both charge transfer and ohmic 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.

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

Science.gov (United States)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

High Performance Hydrogen/Bromine Redox Flow Battery for Grid-Scale Energy Storage

Energy Technology Data Exchange (ETDEWEB)

Cho, KT; Ridgway, P; Weber, AZ; Haussener, S; Battaglia, V; Srinivasan, V

2012-01-01

The electrochemical behavior of a promising hydrogen/bromine redox flow battery is investigated for grid-scale energy-storage application with some of the best redox-flow-battery performance results to date, including a peak power of 1.4 W/cm(2) and a 91% voltaic efficiency at 0.4 W/cm(2) constant-power operation. The kinetics of bromine on various materials is discussed, with both rotating-disk-electrode and cell studies demonstrating that a carbon porous electrode for the bromine reaction can conduct platinum-comparable performance as long as sufficient surface area is realized. The effect of flow-cell designs and operating temperature is examined, and ohmic and mass-transfer losses are decreased by utilizing a flow-through electrode design and increasing cell temperature. Charge/discharge and discharge-rate tests also reveal that this system has highly reversible behavior and good rate capability. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.018211jes] All rights reserved.

Systems and methods for rebalancing redox flow battery electrolytes

Science.gov (United States)

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.

Titanium nitride as an electrocatalyst for V(II)/V(III) redox couples in all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Yang, Chunmei; Wang, Haining; Lu, Shanfu; Wu, Chunxiao; Liu, Yiyang; Tan, Qinglong; Liang, Dawei; Xiang, Yan

2015-01-01

Titanium nitride nanoparticles (TiN NPs) are proposed as a novel catalyst towards the V(II)/V(III) redox pair for the negative electrode in vanadium redox flow batteries (VRFB). Electrochemical properties of TiN NPs were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that TiN NPs demonstrate better electrochemical activity and reversibility for the processes of V(II)/V(III) redox couples as compared with the graphite NPs. TiN NPs facilitate the charge transfer in the V(II)/V(III) redox reaction. Performance of a VRFB using a TiN NPs coated carbon paper as a negative electrode is much higher than that of a VRFB with a raw carbon paper electrode. The columbic efficiency (CE), the voltage efficiency (VE) and the energy efficiency (EE) of the VRFB single cell at charge-discharge current density of 30 mA/cm 2 are 91.74%, 89.11% and 81.74%, respectively. During a 50 charge-discharge cycles test, the CE values of VRFB with TiN NPs consistently remain higher than 90%.

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

Science.gov (United States)

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.

Investigation of local environments in Nafion-SiO(2) composite membranes used in vanadium redox flow batteries.

Science.gov (United States)

Vijayakumar, M; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Thevuthasan, S; Liu, Jun; Graff, Gordon L; Hu, Jianzhi

2012-04-01

Proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, polymer composite membranes, such as SiO(2) incorporated Nafion membranes, are recently reported as highly promising for the use in redox flow batteries. However, there is conflicting reports regarding the performance of this type of Nafion-SiO(2) composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO(2) composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transform Infra Red (FTIR) spectroscopy, and ultraviolet-visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the (19)F and (29)Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The (29)Si NMR shows that the silica particles interact via hydrogen bonds with the sulfonic groups of Nafion and the diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO(2) composite membrane materials in vanadium redox flow batteries. Copyright © 2011 Elsevier Inc. All rights reserved.

Aqueous electrolytes for redox flow battery systems

Science.gov (United States)

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

2017-10-17

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.

Optimal scheduling for distribution network with redox flow battery storage

International Nuclear Information System (INIS)

Hosseina, Majid; Bathaee, Seyed Mohammad Taghi

2016-01-01

Highlights: • A novel method for optimal scheduling of storages in radial network is presented. • Peak shaving and load leveling are the main objectives. • Vanadium redox flow battery is considered as the energy storage unit. • Real data is used for simulation. - Abstract: There are many advantages to utilize storages in electric power system. Peak shaving, load leveling, load frequency control, integration of renewable, energy trading and spinning reserve are the most important of them. Batteries, especially redox flow batteries, are one of the appropriate storages for utilization in distribution network. This paper presents a novel, heuristic and practical method for optimal scheduling in distribution network with flow battery storage. This heuristic method is more suitable for scheduling and operation of distribution networks which require installation of storages. Peak shaving and load leveling is considered as the main objective in this paper. Several indices are presented in this paper for determine the place of storages and also scheduling for optimal use of energy in them. Simulations of this paper are based on real information of distribution network substation that located in Semnan, Iran.

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

Science.gov (United States)

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.

1,3-Dioxolane, tetrahydrofuran, acetylacetone and dimethyl sulfoxide as solvents for non-aqueous vanadium acetylacetonate redox-flow-batteries

International Nuclear Information System (INIS)

Herr, T.; Noack, J.; Fischer, P.; Tübke, J.

2013-01-01

Highlights: • Four solvents were employed in a non-aqueous redox flow battery system. • Coulombic efficiencies of 85.9–98.5% and energy efficiencies of 26.6–43.6% were achieved. • Discharge power density was enhanced up to 0.080 mW cm −2 . • Solubility of V(acac) 3 was increased to 0.8 M compared to the acetonitrile system. -- Abstract: A non-aqueous vanadium acetylacetonate redox flow battery with different organic solvents and tetrabutylammonium hexafluorophosphate has been investigated. Cyclic voltammograms show three redox couples in 1,3-dioxolane, tetrahydrofuran, acetylacetone and two redox couples in dimethyl sulfoxide. Cell potentials between 2.21 and 2.61 V are measured, depending on the solvent used. Impedance Spectroscopy has been used to determine rate limiting step in the non-aqueous redox flow battery. Experiments in a charge–discharge test cell yielded coulombic and energy efficiencies of 85.9–98.5% and 26.6–43.6%, respectively

Electrochemical investigation of tetravalent uranium β-diketones for active materials of all-uranium redox flow battery

International Nuclear Information System (INIS)

Yamamura, Tomoo; Shiokawa, Yoshinobu; Ikeda, Yasuhisa

2002-01-01

For active materials of the all-uranium redox flow battery for the power storage, tetravalent uranium β-diketones were investigated. The electrode reactions of U(ba) 4 and U(btfa) 4 were examined in comparison with that of U(acac) 4 , where ba denotes benzoylacetone, btfa benzoyltrifluoroacetone and acac acetylacetone. The cyclic voltammograms of U(ba) 4 and U(btfa) 4 solutions indicate that there are two series of redox reactions corresponding to the complexes with different coordination numbers of four and three. The electrode kinetics of the U(IV)/U(III) redox reactions for btfa complexes is examined. The obtained result supports that the uranium β-diketone complexes examined in the present study will serve as excellent active materials for negative electrolyte in the redox flow battery. (author)

Zelle und Zellstack einer Redox-Flow-Batterie

OpenAIRE

Seipp, Thorsten; Berthold, Sascha; Burfeind, Jens; Kopietz, Lukas

2015-01-01

Source: WO15007543A1 [EN] The invention illustrates and describes a cell (1) of a redox flow battery, having at least one cell frame element (2, 3, 4), a diaphragm (15) and two electrodes (5), wherein the at least one cell frame element (2, 3, 4), the diaphragm (15) and the two electrodes (5) surround two cell interior spaces (10) which are separate from one another, wherein at least four separate channels (6, 7, 8, 9) are provided in the at least one cell frame element (2, 3, 4) such that di...

High Performance Redox Flow Batteries: An Analysis of the Upper Performance Limits of Flow Batteries Using Non-aqueous Solvents

International Nuclear Information System (INIS)

Sun, C.-N.; Mench, M.M.; Zawodzinski, T.A.

2017-01-01

Redox Flow Batteries (RFBs) are a promising technology for grid-scale electrochemical energy storage. In this work, we use a recently achieved high-performance flow battery performance curve as a basis to assess the maximum achievable performance of a RFB employing non-aqueous solutions as active materials. First we show high performance in a vanadium redox flow battery (VRFB), specifically a limiting situation in which the cell losses are ohmic in nature and derive from electrolyte conductance. Based on that case, we analyze the analogous limiting behavior of non-aqueous (NA) systems using a series of calculations assuming similar ohmic losses, scaled by the relative electrolyte resistances, with a higher voltage redox couple assumed for the NA battery. The results indicate that the NA battery performance is limited by the low electrolyte conductivity to a fraction of the performance of the VRFB. Given the narrow window in which the NARFB offers advantages, even for the most generous limiting assumptions related to performance while ignoring the numerous other disadvantageous aspects of these systems, we conclude that this technology is unlikely under present circumstances to provide practical large-scale energy storage solutions.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

Science.gov (United States)

Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

2015-12-21

Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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.

Science.gov (United States)

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.

Hybrid anodes for redox flow batteries

Science.gov (United States)

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.

Ferrocene and cobaltocene derivatives for non-aqueous redox flow batteries.

Science.gov (United States)

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.

Ruthenium based redox flow battery for solar energy storage

International Nuclear Information System (INIS)

Chakrabarti, Mohammed Harun; Roberts, Edward Pelham Lindfield; Bae, Chulheung; Saleem, Muhammad

2011-01-01

Research highlights: → Undivided redox flow battery employing porous graphite felt electrodes was used. → Ruthenium acetylacetonate dissolved in acetonitrile was the electrolyte. → Charge/discharge conditions were determined for both 0.02 M and 0.1 M electrolytes. → Optimum power output of 0.180 W was also determined for 0.1 M electrolyte. → 55% voltage efficiency was obtained when battery was full of electrolytes. -- Abstract: The technical performance for the operation of a stand alone redox flow battery system for solar energy storage is presented. An undivided reactor configuration has been employed along with porous graphite felt electrodes and ruthenium acetylacetonate as electrolyte in acetonitrile solvent. Limiting current densities are determined for concentrations of 0.02 M and 0.1 M ruthenium acetylacetonate. Based on these, operating conditions for 0.02 M ruthenium acetylacetonate are determined as charging current density of 7 mA/cm 2 , charge electrolyte superficial velocity of 0.0072 cm/s (through the porous electrodes), discharge current density of 2 mA/cm 2 and discharge electrolyte superficial velocity of 0.0045 cm/s. An optimum power output of 35 mW is also obtained upon discharge at 2.1 mA/cm 2 . With an increase in the concentration of ruthenium species from 0.02 M to 0.1 M, the current densities and power output are higher by a factor of five approximately (at same superficial velocities) due to higher mass transport phenomenon. Moreover at 0.02 M concentration the voltage efficiency is better for battery full of electrolytes prior to charging (52.1%) in comparison to an empty battery (40.5%) due to better mass transport phenomenon. Voltage efficiencies are higher as expected at concentrations of 0.1 M ruthenium acetylacetonate (55% when battery is full of electrolytes and 48% when empty) showing that the all-ruthenium redox flow battery has some promise for future applications in solar energy storage. Some improvements for the

The quasi-steady state of all-vanadium redox flow batteries: A scale analysis

International Nuclear Information System (INIS)

Sharma, A.K.; Vynnycky, M.; Ling, C.Y.; Birgersson, E.; Han, M.

2014-01-01

Highlights: • We present a transient 2D model for a VRFB (conservation of species and charge); • Carry out scale analysis of the species conservation equation; • Derive the condition characterizing the quasi-steadiness of VRFB operation; • Verify it by comparing charge-discharge curve with transient simulations. - Abstract: In general, mathematical models for all-vanadium redox flow batteries (VRFB) that seek to capture the transport phenomena are transient in nature. In this paper, we carry out scale analysis of VRFB operation and derive the conditions when it can be assumed to be quasi-steady state in nature, i.e., time-dependence only through a boundary condition. We find that it is true for typical tank volume and flow rate employed for VRFBs. The proposed analysis is generic and can also be employed for other types of redox flow batteries

Evaluation of heart tissue viability under redox-magnetohydrodynamics conditions: toward fine-tuning flow in biological microfluidics applications.

Science.gov (United States)

Cheah, Lih Tyng; Fritsch, Ingrid; Haswell, Stephen J; Greenman, John

2012-07-01

A microfluidic system containing a chamber for heart tissue biopsies, perfused with Krebs-Henseleit buffer containing glucose and antibiotic (KHGB) using peristaltic pumps and continuously stimulated, was used to evaluate tissue viability under redox-magnetohydrodynamics (redox-MHD) conditions. Redox-MHD possesses unique capabilities to control fluid flow using ionic current from oxidation and reduction processes at electrodes in a magnetic field, making it attractive to fine-tune fluid flow around tissues for "tissue-on-a-chip" applications. The manuscript describes a parallel setup to study two tissue samples simultaneously, and 6-min static incubation with Triton X100. Tissue viability was subsequently determined by assaying perfusate for lactate dehydrogenase (LDH) activity, where LDH serves as an injury marker. Incubation with KHGB containing 5 mM hexaammineruthenium(III) (ruhex) redox species with and without a pair of NdFeB magnets (∼ 0.39 T, placed parallel to the chamber) exhibited no additional tissue insult. MHD fluid flow, viewed by tracking microbeads with microscopy, occurred only when the magnet was present and stimulating electrodes were activated. Pulsating MHD flow with a frequency similar to the stimulating waveform was superimposed over thermal convection (from a hotplate) for Triton-KHGB, but fluid speed was up to twice as fast for ruhex-Triton-KHGB. A large transient ionic current, achieved when switching on the stimulating electrodes, generates MHD perturbations visible over varying peristaltic flow. The well-controlled flow methodology of redox-MHD is applicable to any tissue type, being useful in various drug uptake and toxicity studies, and can be combined equally with on- or off-device analysis modalities. Copyright © 2012 Wiley Periodicals, Inc.

Mass transport enhancement in redox flow batteries with corrugated fluidic networks

Science.gov (United States)

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.

Critical safety features of the vanadium redox flow battery

Science.gov (United States)

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

2017-05-01

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

Numerical studies of carbon paper-based vanadium redox flow batteries

International Nuclear Information System (INIS)

Won, Seongyeon; Oh, Kyeongmin; Ju, Hyunchul

2016-01-01

ABSTRACT: This study analyzed theoretically the effects of a carbon paper (CP)-based electrode on the performance of a vanadium redox flow battery (VRFB). Compared to conventional carbon felt-based electrode materials, the CP-based electrode showed superior characteristics in facilitating the redox reactions of VO"2"+/VO_2"+ and V"2"+/V"3"+ couples, such as better electrochemical activity and higher electronic conductivity. A three-dimensional, non-isothermal VRFB model developed in a previous study was applied to a range of single cell structures equipped with CP-based electrodes and flow channels in the current collectors. The model was then validated using the experimental data measured under the CP- and channel-based VRFB geometries. The model successfully captured the experimental trend that showed a higher discharging performance with increasing number of CP layers used for each electrode. The simulation results clearly showed that the activation overpotentials in the electrodes were reduced significantly using more CP layers, which dominated over the effects of increased mass transport limitation of vanadium ions due to the thicker electrode.

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

Science.gov (United States)

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.

A study of tiron in aqueous solutions for redox flow battery application

International Nuclear Information System (INIS)

Xu Yan; Wen Yuehua; Cheng Jie; Cao Gaoping; Yang Yusheng

2010-01-01

In this study, the electrochemical behavior of tiron in aqueous solutions and the influence of pH were investigated. A change of pH mainly produces the following results. In acidic solutions of pH below 4, the electrode reaction of tiron exhibits a simple process at a relatively high potential with a favorable quasi-reversibility. The tiron redox reaction exhibits fast electrode kinetics and a diffusion-controlled process. In solutions of pH above 4, the electrode reaction of tiron tends to be complicated. Thus, acidic aqueous solutions of pH below 4 are favorable for the tiron as active species of a redox flow battery (RFB). Constant-current electrolysis shows that a part of capacity is irreversible and the structure of tiron is changed for the first electrolysis, which may result from an ECE process for the tiron electro-oxidation. Thus, the tiron needs an activation process for the application of a RFB. Average coulombic and energy efficiencies of the tiron/Pb battery are 93 and 82%, respectively, showing that self-discharge is small during the short-term cycling. The preliminary exploration shows that the tiron is electrochemically promising for redox flow battery application.

A dynamic performance model for redox-flow batteries involving soluble species

International Nuclear Information System (INIS)

Shah, A.A.; Watt-Smith, M.J.; Walsh, F.C.

2008-01-01

A transient modelling framework for a vanadium redox-flow battery (RFB) is developed and experiments covering a range of vanadium concentration and electrolyte flow rate are conducted. The two-dimensional model is based on a comprehensive description of mass, charge and momentum transport and conservation, and is combined with a global kinetic model for reactions involving vanadium species. The model is validated against the experimental data and is used to study the effects of variations in concentration, electrolyte flow rate and electrode porosity. Extensions to the model and future work are suggested

Neue Elektrolyte zur Steigerung der Energiedichte einer nicht-wässrigen Vanadium-Acetylacetonat-Redox-Flow-Batterie

OpenAIRE

Herr, Tatjana

2015-01-01

Die Redox-Flow-Batterie ist eine vielversprechende Speicherungsmöglichkeit für stationäre Anwendungen. Bei dieser Batterie wird die Energie in einem flüssigen Elektrolyt gespeichert, wobei die Energiedichte von der Konzentration und dem Potentialfenster der gelösten redoxaktiven Substanz abhängt. Zur Steigerung der Energiedichte einer nicht-wässrigen Vanadium-Acetylacetonat-Redox-Flow-Batterie wurden organische Lösungsmittel, welche ein Potentialfenster bis zu 5 V aufweisen, und Lösungsmittel...

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

Science.gov (United States)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Redox-Flow-Batterie mit außenliegender Versorgungsleitung

OpenAIRE

Seipp, Thorsten; Dötsch, Christian; Berthold, Sascha

2011-01-01

A redox flow battery (1, 1') is presented and described, having at least one cell frame (4) surrounding a cell interior space (7) and having at least one supply line (2, 2') provided outside the cell frame (4) for supplying electrolyte to the cell interior space (7) and/or at least one disposal line (3, 3') provided outside the cell frame (4) for removing electrolyte from the cell interior space (4). In order to make greater degrees of freedom available in designing the cell so as to provide ...

Identifying and annotating human bifunctional RNAs reveals their versatile functions.

Science.gov (United States)

Chen, Geng; Yang, Juan; Chen, Jiwei; Song, Yunjie; Cao, Ruifang; Shi, Tieliu; Shi, Leming

2016-10-01

Bifunctional RNAs that possess both protein-coding and noncoding functional properties were less explored and poorly understood. Here we systematically explored the characteristics and functions of such human bifunctional RNAs by integrating tandem mass spectrometry and RNA-seq data. We first constructed a pipeline to identify and annotate bifunctional RNAs, leading to the characterization of 132 high-confidence bifunctional RNAs. Our analyses indicate that bifunctional RNAs may be involved in human embryonic development and can be functional in diverse tissues. Moreover, bifunctional RNAs could interact with multiple miRNAs and RNA-binding proteins to exert their corresponding roles. Bifunctional RNAs may also function as competing endogenous RNAs to regulate the expression of many genes by competing for common targeting miRNAs. Finally, somatic mutations of diverse carcinomas may generate harmful effect on corresponding bifunctional RNAs. Collectively, our study not only provides the pipeline for identifying and annotating bifunctional RNAs but also reveals their important gene-regulatory functions.

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

Science.gov (United States)

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.

Strategies for enhancing electrochemical activity of carbon-based electrodes for all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Flox, Cristina; Skoumal, Marcel; Rubio-Garcia, Javier; Andreu, Teresa; Morante, Juan Ramón

2013-01-01

Highlights: ► Improved reactions at the positive electrode in all-vanadium redox flow batteries. ► Graphene-derived and PAN-modified electrodes have been successfully prepared. ► Modification with bimetallic CuPt 3 nanocubes yielded the best catalytic behavior. ► N and O-containing groups enhances the vanadium flow battery performance. - Abstract: Two strategies for improving the electroactivity towards VO 2+ /VO 2 + redox pair, the limiting process in all-vanadium redox flow batteries (VFBs), were presented. CuPt 3 nanoparticles supported onto graphene substrate and nitrogen and oxygen polyacrylonitrile (PAN)-functionalized electrodes materials have been evaluated. The morphology, composition, electrochemical properties of all electrodes prepared was characterized with field emission-scanning electrode microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy and cell charge–discharge test. The presence of the CuPt 3 nanocubes and nitrogen and oxygen functionalities enhance the electrocatalytic activity of the electrodes materials accelerating the oxygen and electron transfer processes. The battery performance was also evaluated using PAN-functionalized electrodes exhibiting a high of energy efficiency of 84% (at current density 20 mA cm −2 ) up to 30th cycle, indicating a promising alternative for improving the VFB

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

Science.gov (United States)

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

2017-07-10

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

Renewable hydrogen generation from a dual-circuit redox flow battery

OpenAIRE

Amstutz, Veronique; Toghill, Kathryn Ellen; Powlesland, Francis; Vrubel, Heron; Comninellis, Christos; Hu, Xile; Girault, Hubert H.

2014-01-01

Redox flow batteries (RFBs) are particularly well suited for storing the intermittent excess supply of renewable electricity; so-called “junk” electricity. Conventional RFBs are charged and discharged electrochemically, with electricity stored as chemical energy in the electrolytes. In the RFB system reported here, the electrolytes are conventionally charged but are then chemically discharged over catalytic beds in separate external circuits. The catalytic reaction of particular interest gene...

Monitoring electrolyte concentrations in redox flow battery systems

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Electrodeposited nano-scale islands of ruthenium oxide as a bifunctional electrocatalyst for simultaneous catalytic oxidation of hydrazine and hydroxylamine

Energy Technology Data Exchange (ETDEWEB)

Zare, Hamid R., E-mail: hrzare@yazduni.ac.ir [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Nanotechnology Research Center, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Hashemi, S. Hossein; Benvidi, Ali [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of)

2010-06-04

For the first time, an electrodeposited nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles), as an excellent bifunctional electrocatalyst, was successfully used for hydrazine and hydroxylamine electrocatalytic oxidation. The results show that, at the present bifunctional modified electrode, two different redox couples of ruthenium oxides serve as electrocatalysts for simultaneous electrocatalytic oxidation of hydrazine and hydroxylamine. At the modified electrode surface, the peaks of differential pulse voltammetry (DPV) for hydrazine and hydroxylamine oxidation were clearly separated from each other when they co-exited in solution. Thus, it was possible to simultaneously determine hydrazine and hydroxylamine in the samples at a ruthenium oxide nanoparticles modified glassy carbon electrode (RuON-GCE). Linear calibration curves were obtained for 2.0-268.3 {mu}M and 268.3-417.3 {mu}M of hydrazine and for 4.0-33.8 {mu}M and 33.8-78.3 {mu}M of hydroxylamine at the modified electrode surface using an amperometric method. The amperometric method also exhibited the detection limits of 0.15 {mu}M and 0.45 {mu}M for hydrazine and hydroxylamine respectively. RuON-GCE was satisfactorily used for determination of spiked hydrazine in two water samples. Moreover, the studied bifunctional modified electrode exhibited high sensitivity, good repeatability, wide linear range and long-term stability.

Fundamental studies of uranium and neptunium redox flow batteries (II)

International Nuclear Information System (INIS)

Shiokawa, Y.; Yamamura, T.; Watanabe, N.

2002-01-01

The atomic power generation entails production of so-called minor actinides and accumulation of depleted uranium. The theoretical and experimental investigations are underway to transmute minor actinides for minimizing the long-term radiotoxicity and reducing the radioactive waste. The utilization, however, would be alternative means. The actinide redox couples, An(VI)/An(V) and An(IV)/An(III), have excellent properties as battery active materials. Here j the uranium and neptunium redox flow batteries for the electric power storage are discussed from the electrochemical properties of U, Np, Pu and Am [1,2]. One of the required properties for the batteries for electric power storage is high energy efficiency, which is defined by the ratio of the discharge energy to the charge energy. These energies are dependent on the rapidness of kinetics in the electrode reactions, namely the standard rate constants and also the internal resistance of the battery

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

A Quaternized Polysulfone Membrane for Zinc-Bromine Redox Flow Battery

Directory of Open Access Journals (Sweden)

Mingqiang Li

2014-01-01

Full Text Available A quaternized polysulfone (QNPSU composite membrane is fabricated for zinc-bromine redox flow battery. The structure of the membrane is examined by FT-IR spectra and SEM. The conductivity of the membrane is tested by electrochemical analyzer. After a zinc-bromine battery with this composite membrane is operated at different voltage while charging and at different current while discharging to examine the performance of the membrane, it is found that the discharge voltage was 0.9672 V and the power density was 6 mW/cm2 at a current of 0.1 A, which indicated that the novel composite membrane is a promising material for the flow battery.

Preparation and characterization of hybrid Nafion/silica and Nafion/silica/PTA membranes for redox flow batteries

Energy Technology Data Exchange (ETDEWEB)

Glibin, V.; Pupkevich, V.; Svirko, L.; Karamanev, D. [Western Ontario Univ., London, ON (Canada). Dept. of Biochemical and Chemical Engineering

2008-07-01

Redox flow batteries are both efficient and cost-effective. However, the long-term stability of most ion-exchange membranes is limited as a result of the high oxidation rates of ions with high redox potentials. A method of synthesizing multi-component Nafion-silica and Nafion-silica-PTA membranes was presented in this study, which also investigated the electrochemical and ion transport properties of the membranes. Membranes were cast from dimethylformamide (DMFA) solution. The iron ion diffusion kinetics of the Nafion-silica and Nafion-silica PTA membranes were studied by dialysis. Results of the investigation demonstrated that the introduction of silica and phosphotungstic acid (PTA) into the Nafion membrane composition resulted in a significant decrease of ion transfer through the membrane. The addition of PTA also increased membrane permeability to ferric ions. The low iron diffusion coefficient and high ionic conductivity of the Nafion-silica membrane makes it a promising material for use in redox flow batteries. 4 refs., 1 tab., 1 fig.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

Science.gov (United States)

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

Modelling the effects of oxygen evolution in the all-vanadium redox flow battery

International Nuclear Information System (INIS)

Al-Fetlawi, H.; Shah, A.A.; Walsh, F.C.

2010-01-01

The impact of oxygen evolution and bubble formation on the performance of an all-vanadium redox flow battery is investigated using a two-dimensional, non-isothermal model. The model is based on mass, charge, energy and momentum conservation, together with a kinetic model for the redox and gas-evolving reactions. The multi-phase mixture model is used to describe the transport of oxygen in the form of gas bubbles. Numerical simulations are compared to experimental data, demonstrating good agreement. Parametric studies are performed to investigate the effects of changes in the operating temperature, electrolyte flow rate and bubble diameter on the extent of oxygen evolution. Increasing the electrolyte flow rate is found to reduce the volume of the oxygen gas evolved in the positive electrode. A larger bubble diameter is demonstrated to increase the buoyancy force exerted on the bubbles, leading to a faster slip velocity and a lower gas volume fraction. Substantial changes are observed over the range of reported bubble diameters. Increasing the operating temperature was found to increase the gas volume as a result of the enhanced rate of O 2 evolution. The charge efficiency of the cell drops markedly as a consequence.

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

Science.gov (United States)

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.

Science.gov (United States)

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.

Optimization of a Vanadium Redox Flow Battery with Hydrogen generation

OpenAIRE

Wrang, Daniel

2016-01-01

We consider the modelling and optimal control of energy storage systems, in this study a Vanadium Redox Flow Battery. Such a battery can be introduced in the electrical grid to be charged when demand is low and discharged when demand is high, increasing the overall efficiency of the network while reducing costs and emission of greenhouse gases. The model of the battery proposed in this study is less complex than the majority of models on batteries and energy storage systems found in literatur...

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

A study of the Fe(III)/Fe(II)-triethanolamine complex redox couple for redox flow battery application

International Nuclear Information System (INIS)

Wen, Y.H.; Zhang, H.M.; Qian, P.; Zhou, H.T.; Zhao, P.; Yi, B.L.; Yang, Y.S.

2006-01-01

The electrochemical behavior of the Fe(III)/Fe(II)-triethanolamine(TEA) complex redox couple in alkaline medium and influence of the concentration of TEA were investigated. A change of the concentration of TEA mainly produces the following two results. (1) With an increase of the concentration of TEA, the solubility of the Fe(III)-TEA can be increased to 0.6 M, and the solubility of the Fe(II)-TEA is up to 0.4 M. (2) In high concentration of TEA with the ratio of TEA to NaOH ranging from 1 to 6, side reaction peaks on the cathodic main reaction of the Fe(III)-TEA complex at low scan rate can be minimized. The electrode process of Fe(III)-TEA/Fe(II)-TEA is electrochemically reversible with higher reaction rate constant than the uncomplexed species. Constant current charge-discharge shows that applying anodic active materials of relatively high concentrations facilitates the improvement of cell performance. The open-circuit voltage of the Fe-TEA/Br 2 cell with the Fe(III)-TEA of 0.4 M, after full charging, is nearly 2.0 V and is about 32% higher than that of the all-vanadium batteries, together with the energy efficiency of approximately 70%. The preliminary exploration shows that the Fe(III)-TEA/Fe(II)-TEA couple is electrochemically promising as negative redox couple for redox flow battery (RFB) application

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

Science.gov (United States)

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

Science.gov (United States)

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.

Composite Nafion 117-TMSP membrane for Fe-Cr redox flow battery applications

Energy Technology Data Exchange (ETDEWEB)

Haryadi, E-mail: haryadi@polban.ac.id [Department of Chemical Engineering, PoliteknikNegeri Bandung Indonesia (Indonesia); Gunawan, Y. B.; Harjogi, D. [Department of Electronic Engineering, PoliteknikNegeri Bandung Indonesia (Indonesia); Mursid, S. P. [Department of Energy Engineering, PoliteknikNegeri Bandung. Jl. GegerkalongHilir, Ds, Ciwaruga, Bandung, West Java Indonesia (Indonesia)

2016-04-19

The modification of Nafion 117 - TMSP (trimethoxysylilprophanthiol) composite membrane has been conducted by in-situ sol-gel method followed by characterization of structural and properties of material using spectroscopic techniques. The performance of composite membrane has then been examined in the single stack module of Fe-Cr Redox Flow Battery. It was found that the introduction of silica from TMSP through sol-gel process within the Nafion 117 membrane produced composite membrane that has slightly higher proton conductivity values as compared to the pristine of Nafion 117 membrane observed by electrochemical impedance spectroscopy. The degree of swelling of water in the composite membrane demonstrated greatly reduced than a pristine Nafion 117 signifying low water cross over. The SEM-EDX measurements indicated that there was no phase separation occurred suggesting that silica nanoparticles are distributed homogeneously within the composite membrane. The composite membrane used as separator in the system of Fe-Cr Redox Flow Battery revealed no cross mixing (crossover) occurred between anolyte and catholyte in the system as observed from the total voltage measurements that closed to the theoretical value. The battery efficiency generally increased as the volume of the electrolytes enlarged.

Composite Nafion 117-TMSP membrane for Fe-Cr redox flow battery applications

International Nuclear Information System (INIS)

Haryadi; Gunawan, Y. B.; Harjogi, D.; Mursid, S. P.

2016-01-01

The modification of Nafion 117 - TMSP (trimethoxysylilprophanthiol) composite membrane has been conducted by in-situ sol-gel method followed by characterization of structural and properties of material using spectroscopic techniques. The performance of composite membrane has then been examined in the single stack module of Fe-Cr Redox Flow Battery. It was found that the introduction of silica from TMSP through sol-gel process within the Nafion 117 membrane produced composite membrane that has slightly higher proton conductivity values as compared to the pristine of Nafion 117 membrane observed by electrochemical impedance spectroscopy. The degree of swelling of water in the composite membrane demonstrated greatly reduced than a pristine Nafion 117 signifying low water cross over. The SEM-EDX measurements indicated that there was no phase separation occurred suggesting that silica nanoparticles are distributed homogeneously within the composite membrane. The composite membrane used as separator in the system of Fe-Cr Redox Flow Battery revealed no cross mixing (crossover) occurred between anolyte and catholyte in the system as observed from the total voltage measurements that closed to the theoretical value. The battery efficiency generally increased as the volume of the electrolytes enlarged.

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

Science.gov (United States)

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.

Determining the Limiting Current Density of Vanadium Redox Flow Batteries

Directory of Open Access Journals (Sweden)

Jen-Yu Chen

2014-09-01

Full Text Available All-vanadium redox flow batteries (VRFBs are used as energy storage systems for intermittent renewable power sources. The performance of VRFBs depends on materials of key components and operating conditions, such as current density, electrolyte flow rate and electrolyte composition. Mass transfer overpotential is affected by the electrolyte flow rate and electrolyte composition, which is related to the limiting current density. In order to investigate the effect of operating conditions on mass transport overpotential, this study established a relationship between the limiting current density and operating conditions. First, electrolyte solutions with different states of charge were prepared and used for a single cell to obtain discharging polarization curves under various operating conditions. The experimental results were then analyzed and are discussed in this paper. Finally, this paper proposes a limiting current density as a function of operating conditions. The result helps predict the effect of operating condition on the cell performance in a mathematical model.

Non-isothermal modelling of the all-vanadium redox flow battery

International Nuclear Information System (INIS)

Al-Fetlawi, H.; Shah, A.A.; Walsh, F.C.

2009-01-01

An non-isothermal model for the all-vanadium redox flow battery (RFB) is presented. The two-dimensional model is based on a comprehensive description of mass, charge, energy and momentum transport and conservation, and is combined with a global kinetic model for reactions involving vanadium species. Heat is generated as a result of activation losses, electrochemical reaction and ohmic resistance. Numerical simulations demonstrate the effects of changes in the operating temperature on performance. It is shown that variations in the electrolyte flow rate and the magnitude of the applied current substantially alter the charge/discharge characteristics, the temperature rise and the distribution of temperature. The influence of heat losses on the charge/discharge behaviour and temperature distribution is investigated. Conditions for localised heating and membrane degradation are discussed.

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

Science.gov (United States)

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.

A three-dimensional model for negative half cell of the vanadium redox flow battery

International Nuclear Information System (INIS)

Ma Xiangkun; Zhang Huamin; Xing Feng

2011-01-01

A stationary, isothermal, three-dimensional model for negative half cell of the vanadium redox flow battery is developed, which is based on the comprehensive conservation laws, such as charge, mass and momentum, together with a kinetic model for reaction involving vanadium species. The model is validated against the results calculated by the available two-dimensional model. With the given geometry of the negative half cell, the distributions of velocity, concentration, overpotential and transfer current density in the sections that are perpendicular and parallel to the applied current are studied. It is shown that the distribution of the electrolyte velocity in the electrode has significant impact on the distribution of concentration, overpotential and transfer current density. The lower velocity in the electrode will cause the higher overpotential, further result in the side reaction and corrosion of key materials locally. The development of the design of the vanadium redox flow battery is discussed, and the further research is proposed.

Treatment of graphite felt by modified Hummers method for the positive electrode of vanadium redox flow battery

International Nuclear Information System (INIS)

Wu, Xiaoxin; Xu, Hongfeng; Shen, Yang; Xu, Pengcheng; Lu, Lu; Fu, Jie; Zhao, Hong

2014-01-01

A novel and highly effective treatment based on modified Hummers method was firstly used to improve the electrochemical activity of graphite felt as the positive electrode in all-vanadium redox flow battery (VRFB). The graphite felt was treated by the modified Hummers method and characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The electrochemical performance of the prepared electrode was evaluated through cyclic voltammetry and electrochemical impedance spectroscopy. Results show that graphite felt treated by modified Hummers method exhibits excellent electrocatalytic activity and reaction rate to vanadium redox couples. In our research, the hydrogen electrode and H 2 replaced the graphite felt and V 2+ /V 3+ couple in the negative side in the VRFB performance test. The coulombic, voltage, and energy efficiencies of the VRFB with the as-prepared electrodes at 50 mA cm −2 are 95.0%, 81.3%, and 77.2%, respectively. These values are much higher than those of the cell-assembled graphite felt electrodes that were conventionally and thermally treated. The graphite felt treated by the modified Hummers method carries more hydrophilic groups, such as–OH, on its defects, which is advantageous in facilitating the redox reaction of vanadium ions, thereby improving the operation efficiency of the vanadium redox flow battery

Examination of Amine-Functionalised Anion-Exchange Membranes for Possible Use in the All-Vanadium Redox Flow Battery

International Nuclear Information System (INIS)

Mallinson, Sarah L.; Varcoe, John R.; Slade, Robert C.T.

2014-01-01

The applicability of amine-functionalised anion-exchange membranes (AEMs) for use in the all-vanadium redox flow battery has been studied. A selection of radiation-grafted aminated membranes functionalised with dimethylamine, trimethylamine or diazabicyclo(2,2,2)octane were extensively tested. The success of each grafting process was confirmed by Raman and infrared spectroscopies, titrimetry and ionic conductivity measurements. The amine-functionalised membranes were found to have poor thermo-oxidative stability and high vanadium cation permeabilities. The results highlight the importance of balancing ionic conductivity with vanadium cation permeability and indicate that amine-based functional groups may not be suitably stable for the membranes to remain true AEMs when in use in the all-vanadium redox flow battery

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

Science.gov (United States)

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.

Development of a Novel Iodine-Vitamin C/Vanadium Redox Flow Battery

International Nuclear Information System (INIS)

Chen, Mei-Ling; Huang, Shu-Ling; Hsieh, Chin-Lung; Lee, Jan- Yen; Tsai, Tz-Jiun

2014-01-01

A novel (I + /I 2 )/vitamin C vs. V 4+ /V 5+ semi-vanadium redox flow battery (semi-VRFB) with iodine, vitamin C, and V 4+ /V 5+ redox couples, using multiple electrodes was investigated. The electrodes, Ni-P/carbon paper and Ni-P/TiO 2 /carbon paper, were modified by the electroless plating method and sol-gel process. The electrochemical characteristics and the performance of the semi-VRFB were verified by the cyclic voltammetry method and a charge-discharge test. This study shows modified electrodes can improve the reversibility and symmetry of the oxidation-reduction reaction of the semi-VRFB system, and effectively raise its storage ability. The coulomb efficiency of the semi-VRFB system is close to 96%, which is higher than the all-VRFB. The semi-VRFB system can reduce the amount of vanadium salt, therefore, it is not only a reduction in cost, but also has a great potential for the development of energy storage systems

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

Science.gov (United States)

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.

Review of material research and development for vanadium redox flow battery applications

International Nuclear Information System (INIS)

Parasuraman, Aishwarya; Lim, Tuti Mariana; Menictas, Chris; Skyllas-Kazacos, Maria

2013-01-01

The vanadium redox flow battery (VRB) is one of the most promising electrochemical energy storage systems deemed suitable for a wide range of renewable energy applications that are emerging rapidly to reduce the carbon footprint of electricity generation. Though the Generation 1 Vanadium redox flow battery (G1 VRB) has been successfully implemented in a number of field trials and demonstration projects around the world, it suffers from low energy density that limits its use to stationary applications. Extensive research is thus being carried out to improve its energy density and enhance its performance to enable mobile applications while simultaneously trying to minimize the cost by employing cost effective stack materials and effectively controlling the current operating procedures. The vast bulk of this research was conducted at the University of New South Wales (UNSW) in Sydney during the period 1985–2005, with a large number of other research groups contributing to novel membrane and electrode material development since then. This paper presents a historical overview of materials research and development for the VRB at UNSW, highlighting some of the significant findings that have contributed to improving the battery's performance over the years. Relevant work in this field by other research groups in recent times has also been reviewed and discussed

"Click" chemistry mildly stabilizes bifunctional gold nanoparticles for sensing and catalysis.

Science.gov (United States)

Li, Na; Zhao, Pengxiang; Liu, Na; Echeverria, María; Moya, Sergio; Salmon, Lionel; Ruiz, Jaime; Astruc, Didier

2014-07-01

A large family of bifunctional 1,2,3-triazole derivatives that contain both a polyethylene glycol (PEG) chain and another functional fragment (e.g., a polymer, dendron, alcohol, carboxylic acid, allyl, fluorescence dye, redox-robust metal complex, or a β-cyclodextrin unit) has been synthesized by facile "click" chemistry and mildly coordinated to nanogold particles, thus providing stable water-soluble gold nanoparticles (AuNPs) in the size range 3.0-11.2 nm with various properties and applications. In particular, the sensing properties of these AuNPs are illustrated through the detection of an analogue of a warfare agent (i.e., sulfur mustard) by means of a fluorescence "turn-on" assay, and the catalytic activity of the smallest triazole-AuNPs (core of 3.0 nm) is excellent for the reduction of 4-nitrophenol in water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance Modeling of a Vanadium Redox Flow Battery during Discharging

International Nuclear Information System (INIS)

Yang, W.W.; He, Y.L.; Li, Y.S.

2015-01-01

A two-dimensional quasi-steady-state model is presented to simulate coupled mass-species-charge transfer and electrochemical reactions in all vanadium redox flow battery. Emphasis is located on examining the influences of applied current density, initial vanadium concentration, initial acid concentration and electrolyte flow rate on overpotentials in both electrodes, ohmic loss in electrolyte phase as well as battery discharging voltage. It is indicated that overpotential in negative electrode is the dominant factor causing the loss of battery discharging voltage at relatively lower or higher state of charge, while ohmic loss in electrolyte phase is dominant when discharging at moderate state of charge. Increasing initial vanadium concentration, the battery discharging voltage is significantly increased due to the reduced overpotentials in both electrodes. With the increase in initial acid concentration, the battery discharging voltage is also obviously increased because of increased open circuit voltage and decreased ohmic loss in electrolyte phase. As the electrolyte flow rate increases, the total discharging time is extended due to the retarded concentration polarization and the battery discharging voltage is obviously increased at lower state of charge

Redox Flow Batteries, Hydrogen and Distributed Storage.

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

The development of an all copper hybrid redox flow battery using deep eutectic solvents

International Nuclear Information System (INIS)

Lloyd, David; Vainikka, Tuomas; Kontturi, Kyösti

2013-01-01

Highlights: • A novel redox flow battery based on a deep eutectic solvent is reported. • Favourable kinetics of the positive electrode reaction are shown. • The cell potential is 0.7 V. • Coulombic and energy efficiency are 95% and 62% respectively. • A separator based on jellifying the electrolyte using polyvinyl alcohol is reported. -- Abstract: The performance of a redox flow battery based on chlorocuprates dissolved in an ionic liquid analogue is reported at 50 °C. The kinetics of the positive electrode reaction at a graphite electrode are favourable with a heterogeneous rate constant, k 0 , of 9.5 × 10 −4 cm s −1 . Coulombic efficiency was typically 94% and independent of current density. The small cell potential of 0.75 V and slow mass transport result in energy efficiencies of only 52% and 62% at current densities of 10 and 7.5 mA/cm 2 respectively. The successful development of a separator by jellifying the electrolyte using polyvinyl alcohol is reported

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

Science.gov (United States)

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…

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

Science.gov (United States)

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

Science.gov (United States)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li2Sx 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.

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

Science.gov (United States)

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

2017-04-01

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

Solid-state electroanalytical characterization of the nonaqueous proton-conducting redox gel containing polyoxometallates

International Nuclear Information System (INIS)

Lewera, Adam; Zukowska, Grazyna; Miecznikowski, Krzysztof; Chojak, Malgorzata; Wieczorek, Wladyslaw; Kulesza, Pawel J.

2005-01-01

A novel polymetacrylate-based redox-conducting polymeric gel, into which Keggin-type polyoxometallate, phosphododecatungstic acid (H 3 PW 12 O 40 ), had been incorporated, was electrochemically characterized in the absence of external liquid supporting electrolyte using an ultramicrodisk-working electrode. The phosphotungstate component (15 wt.% of the gel block) was entrapped as the polar organic solvent solution within pores of the polymer matrix. H 3 PW 12 O 40 plays bifunctional role: it provides well-behaved redox centers and serves as strong acid (source of mobile protons). The solid-state voltammetric properties of the system are defined by the reversible one-electron transfers between phosphotungstate redox centers. The following parameters have been determined from the combination of potential step experiments performed in two limiting (radial and linear) diffusional regimes: the concentration of heteropolytungstate redox centers, 6 x 10 -2 mol dm -3 , and the apparent diffusion coefficient, 5 x 10 -7 cm 2 s -1 . The room temperature ionic (protonic) conductivity of the bulk gel was equal to 1.6 x 10 -3 S cm -1 . The charge propagation mechanism was found to be primarily controlled by physical diffusion of heteropolytungstate units within the gel pores rather than by electron hopping (self-exchange) between mixed-valence sites

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

Science.gov (United States)

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.

Vanadium Redox Flow Battery : Sizing of VRB in electrified heavy construction equipment

OpenAIRE

Zimmerman, Nathan

2014-01-01

In an effort to reduce global emissions by electrifying vehicles and machines with internal combustion engines has led to the development of batteries that are more powerful and efficient than the common lead acid battery.  One of the most popular batteries being used for such an installation is lithium ion, but due to its short effective usable lifetime, charging time, and costs has driven researcher to other technologies to replace it.  Vanadium redox flow batteries have come into the spotl...

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

Energy Technology Data Exchange (ETDEWEB)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li₂S_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.

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

Science.gov (United States)

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.

Microfluidic redox battery.

Science.gov (United States)

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.

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

Science.gov (United States)

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".

Single flexible nanofiber to simultaneously realize electricity-magnetism bifunctionality

International Nuclear Information System (INIS)

Yang, Ming; Sheng, Shujuan; Ma, Qianli; Lv, Nan; Yu, Wensheng; Wang, Jinxian; Dong, Xiangting; Liu, Guixia

2016-01-01

In order to develop new-typed multifunctional composite nanofibers, PANI/Fe 3 O 4 /PVP flexible bifunctional composite nanofibers with simultaneous electrical conduction and magnetism have been successfully fabricated via a facile electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of polyaniline (PANI) and Fe 3 O 4 nanoparticles (NPs). The bifunctional composite nanofibers simultaneously possess excellent electrical conductivity and magnetic properties. The electrical conductivity reaches up to the order of 10 -3 S·cm -1 . The electrical conductivity and saturation magnetization of the composite nanofibers can be respectively tuned by adding various amounts of PANI and Fe 3 O 4 NPs. The obtained electricity-magnetism bifunctional composite nanofibers are expected to possess many potential applications in areas such as electromagnetic interference shielding, special coating, microwave absorption, molecular electronics and future nanomechanics. More importantly, the design concept and construct technique are of universal significance to fabricate other bifunctional one-dimensional nanostructures. (author)

Carbon in bifunctional air electrodes in alkaline solution

International Nuclear Information System (INIS)

Tryk, D.; Aldred, W.; Yeager, E.

1983-01-01

Bifunctional O 2 electrodes can be used both to reduce and to generate O 2 in rechargeable metal-air batteries and fuel cells. The factors controlling the O 2 reduction and generation reactions in gas-diffusional bifunctional O 2 electrodes are discussed. The resistance of such electrodes, as established from voltammetry curves, has been found to increase markedly during anodic polarization and to be dependent upon the electrode fabrication technique. Carbon blacks with more graphitic structure than Shawinigan black have been found to be more resistant to electro-oxidation. The further extension of cycle life of bifunctional electrodes using carbon is critically dependent on finding more oxidation-resistant carbons that at the same time have other surface properties meeting the requirements for catalyzed gas-diffusion electrodes

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

Science.gov (United States)

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.

The developments and challenges of cerium half-cell in zinc–cerium redox flow battery for energy storage

International Nuclear Information System (INIS)

Xie, Zhipeng; Liu, Qingchao; Chang, Zhiwen; Zhang, Xinbo

2013-01-01

Zinc–cerium redox flow batteries (ZCBs) are emerging as a very promising new technology with the potential to store a large amount of energy economically and efficiently, thanking to its highest thermodynamic open-circuit cell voltage among all the currently studied aqueous redox flow batteries. However, there are numerous scientific and technical challenges that must be overcome if this alluring promise is to turn into reality, from designing the battery structure, to optimizing the electrolyte compositions and elucidating the complex chemical reactions that occur during charge and discharge. This review article is the first summary of the most significant developments and challenges of cerium half-cell and the current understanding of their chemistry. We are certain that this review will be of great interest to audience over a broad range, especially in fields of energy storage, electrochemistry, and chemical engineering

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.

Science.gov (United States)

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.

All-Vanadium Dual Circuit Redox Flow Battery for Renewable Hydrogen Generation and Desulfurisation

OpenAIRE

Peljo, Pekka Eero; Vrubel, Heron; Amstutz, Veronique; Pandard, Justine; Morgado, Joana; Santasalo-Aarnio, Annukka; Lloyd, David; Gumy, Frederic; Dennison, C R; Toghill, Kathryn; Girault, Hubert

2016-01-01

An all-vanadium dual circuit redox flow battery is an electrochemical energy storage system capable to function as a conventional battery, but also to produce hydrogen and perform desulfurization when surplus of electricity is available by chemical discharge of the battery electrolytes. The hydrogen reactor chemically discharging the negative electrolyte has been designed and scaled up to kW scale, while different options to discharge the positive electrolyte have been evaluated, including ox...

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

Science.gov (United States)

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.

Effect of L-glutamic acid on the positive electrolyte for all-vanadium redox flow battery

International Nuclear Information System (INIS)

Liang, Xinxing; Peng, Sui; Lei, Ying; Gao, Chao; Wang, Nanfang; Liu, Suqin; Fang, Dong

2013-01-01

Highlights: ► Amino acid is used as additive for all-vanadium redox flow battery. ► The additive can significantly improve performance of positive electrolyte. ► Mechanism for the improvement is investigated. -- Abstract: L-Glutamic acid is used as an additive for the positive electrolyte of all-vanadium redox flow battery (VRFB), and its effect on the thermal stability and electrochemical activity is investigated. It is found that the addition of L-glutamic can significantly alleviate the precipitation of V 2 O 5 from positive electrolyte. The conservation rate of V(V) ion can be as high as 58% after 2 M V(V) solution being kept in 40 °C for 89 h. Besides, L-glutamic can also improve the mass transport and electrochemical performance of anolyte. A high coulombic efficiency of over 95% and energy efficiency of 74% are obtained. XPS spectra illustrate that L-glutamic can react with the surface of carbon felt electrode and introduce more oxygen-containing and nitrogen-containing groups, which should be responsible for the improvement of electrochemical performance

Redox conditions effect on flow accelerated corrosion: Influence of hydrazine and oxygen

Energy Technology Data Exchange (ETDEWEB)

Bouvier, O. de [EDF, R and D Div., Moret sur Loing (France); Bouchacourt, M. [EDF, Engineering and Service Div., Villeurbanne (France); Fruzzetti, K. [EPRI, Science and Technology Div., Palo Alto, CA (United States)

2002-07-01

Flow accelerated corrosion (FAC) of carbon steels has been studied world-wide for more than twenty years and is now fairly well understood. The influence of several parameters like water chemistry (i.e. pH and oxygen content), temperature, hydrodynamic or mass transfer conditions (i.e. flow velocity, geometry, steam quality..) and steel composition on the corrosion kinetics has been demonstrated both theoretically and experimentally. However, the effect of a reducing environment and variable redox conditions have not yet been fully explored. It's well known that a reducing environment is effective in increasing the resistance of steam generator tubing to intergranular attack / stress corrosion cracking (IGA/SCC) and pitting. In that way, secondary water chemistry specifications have been modified from low hydrazine to high hydrazine chemistry in the steam-water circuit. Nevertheless, increasing hydrazine levels up to 200 {mu}g/kg could have a detrimental effect by potentially enhancing the FAC process. Moreover, in order to have a complete understanding of the possible impact of the water chemistry environment it is also important to consider the impact of redox conditions during shutdowns (cold and/or hot shutdowns) and start up periods when aerated water injections are made to maintain a constant water level in the Steam Generators from the auxiliary feedwater circuit. Therefore, a common EDF and EPRI R and D effort has been recently carried out to study the effects of hydrazine and oxygen on FAC. The results are presented as follows. (authors)

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

Science.gov (United States)

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.

Copper nanoparticle-deposited graphite felt electrodes for all vanadium redox flow batteries

International Nuclear Information System (INIS)

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

2016-01-01

Highlights: • Copper nanoparticle is proposed as electrocatalyst for VRFBs for the first time. • Propose a binder-free copper nanoparticle decorated electrode. • The energy efficiency is up to 80.1% at 300 mA cm"−"2, enhancing more than 17%. • High stability and capacity retention are achieved by battery with copper catalyst. - Abstract: A copper nanoparticle deposited graphite felt electrode for all vanadium redox flow batteries (VRFBs) is developed and tested. It is found that the copper catalyst enables a significant improvement in the electrochemical kinetics of the V"3"+/V"2"+ redox reaction. The battery’s utilization of the electrolyte and energy efficiency are found to be as high as 83.7% and 80.1%, at a current density of 300 mA cm"−"2, which are 53.1% and 17.8% higher than those of the battery without the catalyst. Moreover, the present battery shows a good stability during the cycle test. The results suggest that the inexpensive copper nanoparticle catalyst without tedious preparation process offers a great promise for VRFB application.

Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery

International Nuclear Information System (INIS)

Yamamura, Tomoo; Shiokawa, Yoshinobu; Yamana, Hajimu; Moriyama, Hirotake

2002-01-01

The redox flow battery using uranium as the negative and the positive active materials in polar aprotic solvents was proposed. In order to establish the guiding principle for the uranium compounds as the active materials, the investigation of uranium β-diketonate complexes was conducted on (i) the solubility of active materials, (ii) the electrode reaction of U(VI) and U(IV) β-diketonate complexes and (iii) the estimation of the open circuit voltage of the battery. The solubilities of higher than 0.8 mol dm -3 of U(VI) complexes and higher than 0.4 mol dm -3 of a U(IV) complex were obtained in the solvents. The electrode reactions of U(pta) 4 , UO 2 (dpm) 2 , UO 2 (fod) 2 and UO 2 (pta) 2 were first studied and the redox potentials of uranium β-diketonates were thermodynamically discussed. The open circuit voltage is estimated more than 1 V by using Hacac or Hdpm. The larger open circuit voltage is expected when a ligand with the larger basicity is used

Single flexible nanofiber to simultaneously realize electricity-magnetism bifunctionality

Energy Technology Data Exchange (ETDEWEB)

Yang, Ming; Sheng, Shujuan; Ma, Qianli; Lv, Nan; Yu, Wensheng; Wang, Jinxian; Dong, Xiangting; Liu, Guixia, E-mail: wenshengyu2009@sina.com, E-mail: dongxiangting888@163.com [Key Laboratory of Applied Chemistry and Nanotechnology at Universities of Jilin Province, Changchun University of Science and Technology, Changchun (China)

2016-03-15

In order to develop new-typed multifunctional composite nanofibers, PANI/Fe{sub 3}O{sub 4}/PVP flexible bifunctional composite nanofibers with simultaneous electrical conduction and magnetism have been successfully fabricated via a facile electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of polyaniline (PANI) and Fe{sub 3}O{sub 4} nanoparticles (NPs). The bifunctional composite nanofibers simultaneously possess excellent electrical conductivity and magnetic properties. The electrical conductivity reaches up to the order of 10{sup -3} S·cm{sup -1}. The electrical conductivity and saturation magnetization of the composite nanofibers can be respectively tuned by adding various amounts of PANI and Fe{sub 3}O{sub 4} NPs. The obtained electricity-magnetism bifunctional composite nanofibers are expected to possess many potential applications in areas such as electromagnetic interference shielding, special coating, microwave absorption, molecular electronics and future nanomechanics. More importantly, the design concept and construct technique are of universal significance to fabricate other bifunctional one-dimensional nanostructures. (author)

A non-aqueous all-copper redox flow battery with highly soluble active species

International Nuclear Information System (INIS)

Li, Yun; Sniekers, Jeroen; Malaquias, João; Li, Xianfeng; Schaltin, Stijn; Stappers, Linda; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F.J.

2017-01-01

A metal-based redox pair with acetonitrile as ligand [Cu(MeCN)_4][Tf_2N] is described for use in non-aqueous redox flow battery (RFB). The electrode kinetics of the anode and cathode are studied using cyclic voltammetry. The Cu"2"+/Cu"+ and Cu"+/Cu couples in this system yield a cell potential of 1.24 V. The diffusion coefficient for [Cu(MeCN)_4][Tf_2N] in acetonitrile is estimated to be 6.8 × 10"−"6 cm"2 s"−"1 at room temperature. The copper-acetonitrile complex has a very high solubility of 1.68 M in acetonitrile, the most widely used organic solvent for non-aqueous electrochemical applications. Hence, a maximum theoretical energy density around 28 Wh L"−"1 can be reached with the reported system. The RFB with this electrolyte shows a promising performance, with coulombic efficiencies of 87% and energy efficiencies of 44% (5 mA cm"−"2).

Crystallization of bi-functional ligand protein complexes.

Science.gov (United States)

Antoni, Claudia; Vera, Laura; Devel, Laurent; Catalani, Maria Pia; Czarny, Bertrand; Cassar-Lajeunesse, Evelyn; Nuti, Elisa; Rossello, Armando; Dive, Vincent; Stura, Enrico Adriano

2013-06-01

Homodimerization is important in signal transduction and can play a crucial role in many other biological systems. To obtaining structural information for the design of molecules able to control the signalization pathways, the proteins involved will have to be crystallized in complex with ligands that induce dimerization. Bi-functional drugs have been generated by linking two ligands together chemically and the relative crystallizability of complexes with mono-functional and bi-functional ligands has been evaluated. There are problems associated with crystallization with such ligands, but overall, the advantages appear to be greater than the drawbacks. The study involves two matrix metalloproteinases, MMP-12 and MMP-9. Using flexible and rigid linkers we show that it is possible to control the crystal packing and that by changing the ligand-enzyme stoichiometric ratio, one can toggle between having one bi-functional ligand binding to two enzymes and having the same ligand bound to each enzyme. The nature of linker and its point of attachment on the ligand can be varied to aid crystallization, and such variations can also provide valuable structural information about the interactions made by the linker with the protein. We report here the crystallization and structure determination of seven ligand-dimerized complexes. These results suggest that the use of bi-functional drugs can be extended beyond the realm of protein dimerization to include all drug design projects. Copyright © 2013 Elsevier Inc. All rights reserved.

Solid-state electroanalytical characterization of the nonaqueous proton-conducting redox gel containing polyoxometallates

Energy Technology Data Exchange (ETDEWEB)

Lewera, Adam [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Zukowska, Grazyna [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warsaw (Poland); Miecznikowski, Krzysztof [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Chojak, Malgorzata [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Wieczorek, Wladyslaw [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warsaw (Poland); Kulesza, Pawel J. [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland)]. E-mail: pkulesza@chem.uw.edu.pl

2005-04-22

A novel polymetacrylate-based redox-conducting polymeric gel, into which Keggin-type polyoxometallate, phosphododecatungstic acid (H{sub 3}PW{sub 12}O{sub 40}), had been incorporated, was electrochemically characterized in the absence of external liquid supporting electrolyte using an ultramicrodisk-working electrode. The phosphotungstate component (15 wt.% of the gel block) was entrapped as the polar organic solvent solution within pores of the polymer matrix. H{sub 3}PW{sub 12}O{sub 40} plays bifunctional role: it provides well-behaved redox centers and serves as strong acid (source of mobile protons). The solid-state voltammetric properties of the system are defined by the reversible one-electron transfers between phosphotungstate redox centers. The following parameters have been determined from the combination of potential step experiments performed in two limiting (radial and linear) diffusional regimes: the concentration of heteropolytungstate redox centers, 6 x 10{sup -2} mol dm{sup -3}, and the apparent diffusion coefficient, 5 x 10{sup -7} cm{sup 2} s{sup -1}. The room temperature ionic (protonic) conductivity of the bulk gel was equal to 1.6 x 10{sup -3} S cm{sup -1}. The charge propagation mechanism was found to be primarily controlled by physical diffusion of heteropolytungstate units within the gel pores rather than by electron hopping (self-exchange) between mixed-valence sites.

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

Science.gov (United States)

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.

Bifunctional chelates of Rh-105 and Au-199 as potential radiotherapeutic agents

International Nuclear Information System (INIS)

Troutner, D.E.; Schlemper, E.O.

1990-01-01

Since last year we have: continued the synthesis of pentadentate bifunctional chelating agents based on diethylene triamine; studied the chelation Rh-105, Au-198 (as model for Au-199) and Tc-99m with these agents as well as chelation of Pd-109, Cu-67, In-111, and Co-57 with some of them; synthesized a new class of potential bifunctional chelating agents based on phenylene diamine; investigated the behavior of Au-198 as a model for Au-199; begun synthesis of bifunctional chelating agents based on terpyridly and similar ligands; and continued attempts to produce tetradentate bifunctional chelates based on diaminopropane. Each of these will be addressed in this report

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

Energy Technology Data Exchange (ETDEWEB)

Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2018-01-31

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 where energy 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. Thus, there is an urgent call to develop efficient (high-energy density) and low-cost RFCs to meet the efflorescent energy storage demands. 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. In order to address the second challenge of reducing cost of the RFCs, we plan to use iron (Fe) metal as it regularly occupies multiple oxidation states and is the second most abundant metal in the earth’s crust that makes it an ideal metal for improved energy densities, higher potentials, and numbers of electrons per molecule while maintaining potential cost competitiveness. Density functional theory calculations considering solvation effects will be performed to yield accurate predictions of redox potentials.

Performance of a vanadium redox flow battery with tubular cell design

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Recent Development of Nanocomposite Membranes for Vanadium Redox Flow Batteries

Directory of Open Access Journals (Sweden)

Sang-Ho Cha

2015-01-01

Full Text Available The vanadium redox flow battery (VRB has received considerable attention due to its long cycle life, flexible design, fast response time, deep-discharge capability, and low pollution emissions in large-scale energy storage. The key component of VRB is an ion exchange membrane that prevents cross mixing of the positive and negative electrolytes by separating two electrolyte solutions, while allowing the conduction of ions. This review summarizes efforts in developing nanocomposite membranes with reduced vanadium ion permeability and improved proton conductivity in order to achieve high performance and long life of VRB systems. Moreover, functionalized nanocomposite membranes will be reviewed for the development of next-generation materials to further improve the performance of VRB, focusing on their properties and performance of VRB.

Dynamic modelling of hydrogen evolution effects in the all-vanadium redox flow battery

International Nuclear Information System (INIS)

Shah, A.A.; Al-Fetlawi, H.; Walsh, F.C.

2010-01-01

A model for hydrogen evolution in an all-vanadium redox flow battery is developed, coupling the dynamic conservation equations for charge, mass and momentum with a detailed description of the electrochemical reactions. Bubble formation at the negative electrode is included in the model, taking into account the attendant reduction in the liquid volume and the transfer of momentum between the gas and liquid phases, using a modified multiphase-mixture approach. Numerical simulations are compared to experimental data for different vanadium concentrations and mean linear electrolyte flow rates, demonstrating good agreement. Comparisons to simulations with negligible hydrogen evolution demonstrate the effect of gas evolution on the efficiency of the battery. The effects of reactant concentration, flow rate, applied current density and gas bubble diameter on hydrogen evolution are investigated. Significant variations in the gas volume fraction and the bubble velocity are predicted, depending on the operating conditions.

Model-based design and optimization of vanadium redox flow batteries

Energy Technology Data Exchange (ETDEWEB)

Koenig, Sebastian

2017-07-19

This work targets on increasing the efficiency of the Vanadium Redox Flow Battery (VRFB) using a model-based approach. First, a detailed instruction for setting up a VRFB model on a system level is given. Modelling of open-circuit-voltage, ohmic overpotential, concentration overpotential, Vanadium crossover, shunt currents as well as pump power demand is presented. All sub-models are illustrated using numerical examples. Using experimental data from three battery manufacturers, the voltage model validated. The identified deviations reveal deficiencies in the literature model. By correctly deriving the mass transfer coefficients and adapting the effective electrode area, these deficiencies are eliminated. The validated battery model is then deployed in an extensive design study. By varying the electrode area between 1000 and 4000 cm{sup 2} and varying the design of the electrolyte supply channel, twenty-four different cell designs are created using finite element analysis. These designs are subsequently simulated in 40-cell stacks deployed in systems with a single stack and systems with a three-stack string. Using the simulation results, the impact of different design parameters on different loss mechanisms is investigated. While operating the VRFB, the electrolyte flow rate is the most important operational parameter. A novel, model-based optimization strategy is presented and compared to established flow rate control strategies. Further, a voltage controller is introduced which delays the violation of cell voltage limits by controlling the flow rate as long as the pump capacity is not fully exploited.

Model-based design and optimization of vanadium redox flow batteries

International Nuclear Information System (INIS)

Koenig, Sebastian

2017-01-01

This work targets on increasing the efficiency of the Vanadium Redox Flow Battery (VRFB) using a model-based approach. First, a detailed instruction for setting up a VRFB model on a system level is given. Modelling of open-circuit-voltage, ohmic overpotential, concentration overpotential, Vanadium crossover, shunt currents as well as pump power demand is presented. All sub-models are illustrated using numerical examples. Using experimental data from three battery manufacturers, the voltage model validated. The identified deviations reveal deficiencies in the literature model. By correctly deriving the mass transfer coefficients and adapting the effective electrode area, these deficiencies are eliminated. The validated battery model is then deployed in an extensive design study. By varying the electrode area between 1000 and 4000 cm 2 and varying the design of the electrolyte supply channel, twenty-four different cell designs are created using finite element analysis. These designs are subsequently simulated in 40-cell stacks deployed in systems with a single stack and systems with a three-stack string. Using the simulation results, the impact of different design parameters on different loss mechanisms is investigated. While operating the VRFB, the electrolyte flow rate is the most important operational parameter. A novel, model-based optimization strategy is presented and compared to established flow rate control strategies. Further, a voltage controller is introduced which delays the violation of cell voltage limits by controlling the flow rate as long as the pump capacity is not fully exploited.

Utilizing a vanadium redox flow battery to avoid wind power deviation penalties in an electricity market

International Nuclear Information System (INIS)

Turker, Burak; Arroyo Klein, Sebastian; Komsiyska, Lidiya; Trujillo, Juan José; Bremen, Lueder von; Kühn, Martin; Busse, Matthias

2013-01-01

Highlights: • Vanadium redox flow battery utilized for wind power grid integration was studied. • Technical and financial analyses at single wind farm level were performed. • 2 MW/6 MW h VRFB is suitable for mitigating power deviations for a 10 MW wind farm. • Economic incentives might be required in the short-term until the VRFB prices drop. - Abstract: Utilizing a vanadium redox flow battery (VRFB) for better market integration of wind power at a single wind farm level was evaluated. A model which combines a VRFB unit and a medium sized (10 MW) wind farm was developed and the battery was utilized to compensate for the deviations resulting from the forecast errors in an electricity market bidding structure. VRFB software model which was introduced in our previous paper was integrated with real wind power data, power forecasts and market data based on the Spanish electricity market. Economy of the system was evaluated by financial assessments which were done by considering the VRFB costs and the amount of deviation penalty payments resulting from forecast inaccuracies

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

Energy Technology Data Exchange (ETDEWEB)

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

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 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 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.

Single flexible nanofiber to achieve simultaneous photoluminescence-electrical conductivity bifunctionality.

Science.gov (United States)

Sheng, Shujuan; Ma, Qianli; Dong, Xiangting; Lv, Nan; Wang, Jinxian; Yu, Wensheng; Liu, Guixia

2015-02-01

In order to develop new-type multifunctional composite nanofibers, Eu(BA)3 phen/PANI/PVP bifunctional composite nanofibers with simultaneous photoluminescence and electrical conductivity have been successfully fabricated via electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of Eu(BA)3 phen and polyaniline (PANI). X-Ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), fluorescence spectroscopy and a Hall effect measurement system are used to characterize the morphology and properties of the composite nanofibers. The results indicate that the bifunctional composite nanofibers simultaneously possess excellent photoluminescence and electrical conductivity. Fluorescence emission peaks of Eu(3+) ions are observed in the Eu(BA)3 phen/PANI/PVP photoluminescence-electrical conductivity bifunctional composite nanofibers. The electrical conductivity reaches up to the order of 10(-3)  S/cm. The luminescent intensity and electrical conductivity of the composite nanofibers can be tuned by adjusting the amounts of Eu(BA)3 phen and PANI. The obtained photoluminescence-electrical conductivity bifunctional composite nanofibers are expected to possess many potential applications in areas such as microwave absorption, molecular electronics, biomedicine and future nanomechanics. More importantly, the design concept and construction technique are of universal significance to fabricate other bifunctional one-dimensional naonomaterials. Copyright © 2014 John Wiley & Sons, Ltd.

Redox-assisted Li+-storage in lithium-ion batteries

International Nuclear Information System (INIS)

Huang Qizhao; Wang Qing

2016-01-01

Interfacial charge transfer is the key kinetic process dictating the operation of lithium-ion battery. Redox-mediated charge propagations of the electronic (e − and h + ) and ionic species (Li + ) at the electrode–electrolyte interface have recently gained increasing attention for better exploitation of battery materials. This article briefly summarises the energetic and kinetic aspects of lithium-ion batteries, and reviews the recent progress on various redox-assisted Li + storage approaches. From molecular wiring to polymer wiring and from redox targeting to redox flow lithium battery, the role of redox mediators and the way of the redox species functioning in lithium-ion batteries are discussed. (topical review)

Investigation on the electrode process of the Mn(II)/Mn(III) couple in redox flow battery

International Nuclear Information System (INIS)

Xue Fangqin; Wang Yongliang; Wang Wenhong; Wang Xindong

2008-01-01

The Mn(II)/Mn(III) couple has been recognized as a potential anode for redox flow batteries to take the place of the V(IV)/V(V) in all-vanadium redox battery (VRB) and the Br 2 /Br - in sodium polysulfide/bromine (PSB) because it has higher standard electrode potential. In this study, the electrochemical behavior of the Mn(II)/Mn(III) couple on carbon felt and spectral pure graphite were investigated by cyclic voltammetry, steady polarization curve, electrochemical impedance spectroscopy, transient potential-step experiment, X-ray diffraction and charge-discharge experiments. Results show that the Mn(III) disproportionation reaction phenomena is obvious on the carbon felt electrode while it is weak on the graphite electrode owing to its fewer active sites. The reaction mechanism on carbon felt was discussed in detail. The reversibility of Mn(II)/Mn(III) is best when the sulfuric acid concentration is 5 M on the graphite electrode. Performance of a RFB employing Mn(II)/Mn(III) couple as anolyte active species and V(III)/V(II) as catholyte ones was evaluated with constant-current charge-discharge tests. The average columbic efficiency is 69.4% and the voltage efficiency is 90.4% at a current density of 20 mA cm -2 . The whole energy efficiency is 62.7% close to that of the all-vanadium battery and the average discharge voltage is about 14% higher than that of an all-vanadium battery. The preliminary exploration shows that the Mn(II)/Mn(III) couple is electrochemically promising for redox flow battery

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

Science.gov (United States)

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.

High-Performance Vanadium Redox Flow Batteries with Graphite Felt Electrodes

Directory of Open Access Journals (Sweden)

Trevor J. Davies

2018-01-01

Full Text Available A key objective in the development of vanadium redox flow batteries (VRFBs is the improvement of cell power density. At present, most commercially available VRFBs use graphite felt electrodes under relatively low compression. This results in a large cell ohmic resistance and limits the maximum power density. To date, the best performing VRFBs have used carbon paper electrodes, with high active area compression pressures, similar to that used in fuel cells. This article investigates the use of felt electrodes at similar compression pressures. Single cells are assembled using compression pressures of 0.2–7.5 bar and tested in a VRFB system. The highest cell compression pressure, combined with a thin Nafion membrane, achieved a peak power density of 669 mW cm−2 at a flow rate of 3.2 mL min−1 per cm2 of active area, more than double the previous best performance from a felt-VRFB. The results suggest that felt electrodes can compete with paper electrodes in terms of performance when under similar compression pressures, which should help guide electrode development and cell optimization in this important energy storage technology.

Bifunctional Interface of Au and Cu for Improved CO2 Electroreduction.

Science.gov (United States)

Back, Seoin; Kim, Jun-Hyuk; Kim, Yong-Tae; Jung, Yousung

2016-09-07

Gold is known currently as the most active single-element electrocatalyst for CO2 electroreduction reaction to CO. In this work, we combine Au with a second metal element, Cu, to reduce the amount of precious metal content by increasing the surface-to-mass ratio and to achieve comparable activity to Au-based catalysts. In particular, we demonstrate that the introduction of a Au-Cu bifunctional "interface" is more beneficial than a simple and conventional homogeneous alloying of Au and Cu in stabilizing the key intermediate species, *COOH. The main advantages of the proposed metal-metal bifunctional interfacial catalyst over the bimetallic alloys include that (1) utilization of active materials is improved, and (2) intrinsic properties of metals are less affected in bifunctional catalysts than in alloys, which can then facilitate a rational bifunctional design. These results demonstrate for the first time the importance of metal-metal interfaces and morphology, rather than the simple mixing of the two metals homogeneously, for enhanced catalytic synergies.

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

Science.gov (United States)

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.

Numerical modelling of a bromide-polysulphide redox flow battery. Part 2: Evaluation of a utility-scale system

International Nuclear Information System (INIS)

Scamman, Daniel P.; Roberts, Edward P.L.; Reade, Gavin W.

2009-01-01

Numerical modelling of redox flow battery (RFB) systems allows the technical and commercial performance of different designs to be predicted without costly lab, pilot and full-scale testing. A numerical model of a redox flow battery was used in conjunction with a simple cost model incorporating capital and operating costs to predict the technical and commercial performance of a 120 MWh/15 MW utility-scale polysulphide-bromine (PSB) storage plant for arbitrage applications. Based on 2006 prices, the system was predicted to make a net loss of 0.45 p kWh -1 at an optimum current density of 500 A m -2 and an energy efficiency of 64%. The system was predicted to become economic for arbitrage (assuming no further costs were incurred) if the rate constants of both electrolytes could be increased to 10 -5 m s -1 , for example by using a suitable (low cost) electrocatalyst. The economic viability was found to be strongly sensitive to the costs of the electrochemical cells and the electrical energy price differential. (author)

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

Science.gov (United States)

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.

Neural Network Predictive Control for Vanadium Redox Flow Battery

Directory of Open Access Journals (Sweden)

Hai-Feng Shen

2013-01-01

Full Text Available The vanadium redox flow battery (VRB is a nonlinear system with unknown dynamics and disturbances. The flowrate of the electrolyte is an important control mechanism in the operation of a VRB system. Too low or too high flowrate is unfavorable for the safety and performance of VRB. This paper presents a neural network predictive control scheme to enhance the overall performance of the battery. A radial basis function (RBF network is employed to approximate the dynamics of the VRB system. The genetic algorithm (GA is used to obtain the optimum initial values of the RBF network parameters. The gradient descent algorithm is used to optimize the objective function of the predictive controller. Compared with the constant flowrate, the simulation results show that the flowrate optimized by neural network predictive controller can increase the power delivered by the battery during the discharge and decrease the power consumed during the charge.

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

Science.gov (United States)

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.

Fabrication of Freestanding Sheets of Multiwalled Carbon Nanotubes (Buckypapers) for Vanadium Redox Flow Batteries and Effects of Fabrication Variables on Electrochemical Performance

International Nuclear Information System (INIS)

Mustafa, Ibrahim; Lopez, Ivan; Younes, Hammad; Susantyoko, Rahmat Agung; Al-Rub, Rashid Abu; Almheiri, Saif

2017-01-01

Typically, multiwalled carbon nanotubes (MWCNTs) are drop-casted on the surface of the underlying carbon substrates; the outcome is a randomly distributed MWCNT layers leading to uncontrollable structure and unreproducible results. Additionally, we suspect that the electrochemical response is influenced by the primary carbon-based substrate. Herein, we propose the use of freestanding sheets of MWCNTs (buckypapers, BP electrodes) as electrode materials for vanadium redox flow batteries to directly probe the electrochemical activity of MWCNTs toward VO 2+ /VO 2 + and V 2+ /V 3+ redox couples; henceforth, eliminating the need for an underlying carbon substrate. The amount of surfactant and the sonication time used during the fabrication of BP electrodes affect their morphological characteristics and electrochemical performances. Although the electrical conductivity of BP electrodes decreases with increasing surfactant amount and increasing sonication time, the heterogeneous rate constants for both redox couples increase as these fabrication variables are increased, indicating that the performance-limiting process is not electrical conductivity but the number of active sites available for the electrochemical reaction. The standard heterogeneous rate constant of the BP electrode with the highest amount of surfactant is comparable to those of state-of-the-art electrodes. Our promising results call for more research on the potential use of BP electrodes in redox flow batteries.

Rebalancing Redox to Improve Biobutanol Production by Clostridium tyrobutyricum

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Chao Ma

2015-12-01

Full Text Available Biobutanol is a sustainable green biofuel that can substitute for gasoline. Carbon flux has been redistributed in Clostridium tyrobutyricum via metabolic cell engineering to produce biobutanol. However, the lack of reducing power hampered the further improvement of butanol production. The objective of this study was to improve butanol production by rebalancing redox. Firstly, a metabolically-engineered mutant CTC-fdh-adhE2 was constructed by introducing heterologous formate dehydrogenase (fdh and bifunctional aldehyde/alcohol dehydrogenase (adhE2 simultaneously into wild-type C. tyrobutyricum. The mutant evaluation indicated that the fdh-catalyzed NADH-producing pathway improved butanol titer by 2.15-fold in the serum bottle and 2.72-fold in the bioreactor. Secondly, the medium supplements that could shift metabolic flux to improve the production of butyrate or butanol were identified, including vanadate, acetamide, sodium formate, vitamin B12 and methyl viologen hydrate. Finally, the free-cell fermentation produced 12.34 g/L of butanol from glucose using the mutant CTC-fdh-adhE2, which was 3.88-fold higher than that produced by the control mutant CTC-adhE2. This study demonstrated that the redox engineering in C. tyrobutyricum could greatly increase butanol production.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Bifunctional organocatalysts for the asymmetric synthesis of axially chiral benzamides

Directory of Open Access Journals (Sweden)

Ryota Miyaji

2017-08-01

Full Text Available Bifunctional organocatalysts bearing amino and urea functional groups in a chiral molecular skeleton were applied to the enantioselective synthesis of axially chiral benzamides via aromatic electrophilic bromination. The results demonstrate the versatility of bifunctional organocatalysts for the enantioselective construction of axially chiral compounds. Moderate to good enantioselectivities were afforded with a range of benzamide substrates. Mechanistic investigations were also carried out.

Coulter dispersant as positive electrolyte additive for the vanadium redox flow battery

International Nuclear Information System (INIS)

Chang Fang; Hu Changwei; Liu Xiaojiang; Liu Lian; Zhang Jianwen

2012-01-01

Coulter dispersants were investigated as the additive into the positive electrolyte (more than 1.8 M vanadium ions) of vanadium redox flow battery (VRB). The electrolyte stability tests showed that, at 45, 50 and 60 °C, the addition of 0.050–0.10 w/w Coulter dispersant IIIA (mainly containing coconut oil amine adduct with 15 ethylene oxide groups) into the positive electrolyte of VRB could significantly delay the time of precipitate formation from 1.8–12.3 h to 30.3 h ∼ 19.3 days. Moreover, the trace amount of Coulter dispersant IIIA as the additive can enhance the electrolyte stability without changing the valence state of vanadium ions, reducing the reversibility of the redox reactions and incurring other side reactions at the electrode. Using the Coulter IIIA dispersant as the additive also improved the energy efficiency of the VRB. The UV–vis spectra confirmed that the trace amount of Coulter IIIA dispersant did not chemically react with V(V) to form new substances. The synergy of Coulombic repulsion and steric hindrance between the macromolecular cationic surfactant additive and the solution reduced the aggregation of vanadium ions into V 2 O 5 and increased the supersaturation of V 2 O 5 crystal in the solution.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Solution casting Nafion/polytetrafluoroethylene membrane for vanadium redox flow battery application

International Nuclear Information System (INIS)

Teng, Xiangguo; Sun, Cui; Dai, Jicui; Liu, Haiping; Su, Jing; Li, Faqiang

2013-01-01

Highlights: ► Nafion/polytetrafluoroethylene (PTFE) blend membranes were prepared by solution casting method. ► The blend membranes were tested for vanadium redox flow battery (VRB) application. ► The blend membranes show lower vanadium ion permeability than that of recast Nafion membrane. ► In VRB single cell test, the blend membrane shows superior performances than that of pure recast Nafion. -- Abstract: Solution casting method was adopted using Nafion and polytetrafluoroethylene (PTFE) solution to prepare Nafion/PTFE blend membranes for vanadium redox flow battery application. The physicochemical properties of the membranes were characterized by using water uptake, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermal analysis (TA). The electrochemical properties of the membranes were examined by using electrochemical impedance spectroscopy (EIS) and single cell test. Despite the high miscibility of PTFE with Nafion, the addition of hydrophobic PTFE reduces the water uptake, ion exchange capacity (IEC) and conductivity of blend membranes. But PTFE can increase the crystallinity, thermal stability of Nafion/PTFE membranes and reduce the vanadium permeability. The blend membrane with PTFE (30 wt%, N 0.7 P 0.3 ) was chosen and investigated for VRB single cell test. The energy efficiency of this VRB with N 0.7 P 0.3 membrane was 85.1% at current density of 50 mA cm −2 , which was superior to that of recast Nafion (r-Nafion) membrane (80.5%). Self-discharge test shows that the decay of open circuit potential of N 0.7 P 0.3 membrane is much lower than that of r-Nafion membrane. More than 50 cycles charge–discharge test proved that the N 0.7 P 0.3 membrane possesses high stability in long time running. Chemical stabilities of the chosen N 0.7 P 0.3 membrane are further proved by soaking the membrane for 3 weeks in highly oxidative V(V) solution. All results suggest that the addition of PTFE is a simple and effective way to

Experimental Testing Procedures and Dynamic Model Validation for Vanadium Redox Flow Battery Storage System

DEFF Research Database (Denmark)

Baccino, Francesco; Marinelli, Mattia; Nørgård, Per Bromand

2013-01-01

The paper aims at characterizing the electrochemical and thermal parameters of a 15 kW/320 kWh vanadium redox flow battery (VRB) installed in the SYSLAB test facility of the DTU Risø Campus and experimentally validating the proposed dynamic model realized in Matlab-Simulink. The adopted testing...... efficiency of the battery system. The test procedure has general validity and could also be used for other storage technologies. The storage model proposed and described is suitable for electrical studies and can represent a general model in terms of validity. Finally, the model simulation outputs...

Electrochemical redox processes involving soluble cerium species

International Nuclear Information System (INIS)

Arenas, L.F.; Ponce de León, C.; Walsh, F.C.

2016-01-01

Highlights: • The relevance of cerium in laboratory and industrial electrochemistry is considered. • The history of fundamental electrochemical studies and applications is considered. • The chemistry, redox thermodynamics and electrode kinetics of cerium are summarised. • The uses of cerium ions in synthesis, energy storage, analysis and environmental treatment are illustrated. • Research needs and development perspectives are discussed. - Abstract: Anodic oxidation of cerous ions and cathodic reduction of ceric ions, in aqueous acidic solutions, play an important role in electrochemical processes at laboratory and industrial scale. Ceric ions, which have been used for oxidation of organic wastes and off-gases in environmental treatment, are a well-established oxidant for indirect organic synthesis and specialised cleaning processes, including oxide film removal from tanks and process pipework in nuclear decontamination. They also provide a classical reagent for chemical analysis in the laboratory. The reversible oxidation of cerous ions is an important reaction in the positive compartment of various redox flow batteries during charge and discharge cycling. A knowledge of the thermodynamics and kinetics of the redox reaction is critical to an understanding of the role of cerium redox species in these applications. Suitable choices of electrode material (metal or ceramic; coated or uncoated), geometry/structure (2-or 3-dimensional) and electrolyte flow conditions (hence an acceptable mass transport rate) are critical to achieving effective electrocatalysis, a high performance and a long lifetime. This review considers the electrochemistry of soluble cerium species and their diverse uses in electrochemical technology, especially for redox flow batteries and mediated electrochemical oxidation.

[Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

International Nuclear Information System (INIS)

1991-01-01

Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III)

[Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

Energy Technology Data Exchange (ETDEWEB)

1991-12-31

Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

(Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents)

Energy Technology Data Exchange (ETDEWEB)

1991-01-01

Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

Electrocatalysis in the vanadium redox flow battery and coupling the redox flow battery with the fuel cell

OpenAIRE

Britz, Anette Beata

2015-01-01

In den Redox-Fluss-Batterien (RFB) bilden die Funktionskomponenten: Elektrode, Membran und Elektrolyt die limitierenden Faktoren für die Leistung der Batterie. Als Elektrodenmaterial werden kohlenstoffbasierte Materialien verwendet. Durch geeignete Modifizierung dieser Elektroden kann die Stromdichte sowie die Energieeffizienz verbessert werden. Die richtige Wahl der Membran kann einem Kapazitätsverlust während der Lade- und Entladezyklen entgegenwirken. In dieser Arbeit wurden die Funktio...

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

Directory of Open Access Journals (Sweden)

Géraldine Merle

2013-12-01

Full Text Available 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.

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

Science.gov (United States)

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

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

Energy Technology Data Exchange (ETDEWEB)

Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2018-01-29

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 energy 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-Br₂) 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-Br₂ 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.

Enzyme mediated synthesis of polypyrrole in the presence of chondroitin sulfate and redox mediators of natural origin

International Nuclear Information System (INIS)

Grijalva-Bustamante, G.A.; Evans-Villegas, A.G.; Castillo-Castro, T. del; Castillo-Ortega, M.M.; Cruz-Silva, R.; Huerta, F.; Morallón, E.

2016-01-01

Polypyrrole (PPy) was synthesized by enzyme mediated oxidation of pyrrole using naturally occurring compounds as redox mediators. The catalytic mechanism is an enzymatic cascade reaction in which hydrogen peroxide is the oxidizer and soybean peroxidase, in the presence of acetosyringone, syringaldehyde or vanillin, acts as a natural catalysts. The effect of the initial reaction composition on the polymerization yield and electrical conductivity of PPy was analyzed. Morphology of the PPy particles was studied by scanning electron microscopy and transmission electron microscopy whereas the chemical structure was studied by X-ray photoelectron and Fourier transformed infrared spectroscopic techniques. The redox mediators increased the polymerization yield without a significant modification of the electronic structure of PPy. The highest conductivity of PPy was reached when chondroitin sulfate was used simultaneously as dopant and template during pyrrole polymerization. Electroactive properties of PPy obtained from natural precursors were successfully used in the amperometric quantification of uric acid concentrations. PPy increases the amperometric sensitivity of carbon nanotube screen-printed electrodes toward uric acid detection. - Highlights: • A new method of pyrrole polymerization using naturally occurring redox mediators and doping agents was studied. • The catalytic efficiency of different redox mediators toward pyrrole oxidation was evaluated. • Two different naturally occurring polymers were studied as bifunctional steric stabilizer/doping agents. • Polypyrrole improves the amperometric response of carbon nanotube screen printed electrodes toward uric acid sensing.

Enzyme mediated synthesis of polypyrrole in the presence of chondroitin sulfate and redox mediators of natural origin

Energy Technology Data Exchange (ETDEWEB)

Grijalva-Bustamante, G.A. [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Evans-Villegas, A.G. [Departamento de Ciencias Químico Biológicas, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Castillo-Castro, T. del, E-mail: terecat@polimeros.uson.mx [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Castillo-Ortega, M.M. [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Cruz-Silva, R. [Research Center for Exotic Nanocarbons, Shinshu University, 4-17-1 Wakasato, 380-8553, Nagano (Japan); Huerta, F. [Departamento Ingeniería Textil y Papelera, Universitat Politecnica de Valencia, Plaza Ferrandiz y Carbonell, 1, E-03801 Alcoy (Spain); Morallón, E. [Departamento Química Física e Instituto Universitario de Materiales, Universidad de Alicante, Ap. 99, E-03080 Alicante (Spain)

2016-06-01

Polypyrrole (PPy) was synthesized by enzyme mediated oxidation of pyrrole using naturally occurring compounds as redox mediators. The catalytic mechanism is an enzymatic cascade reaction in which hydrogen peroxide is the oxidizer and soybean peroxidase, in the presence of acetosyringone, syringaldehyde or vanillin, acts as a natural catalysts. The effect of the initial reaction composition on the polymerization yield and electrical conductivity of PPy was analyzed. Morphology of the PPy particles was studied by scanning electron microscopy and transmission electron microscopy whereas the chemical structure was studied by X-ray photoelectron and Fourier transformed infrared spectroscopic techniques. The redox mediators increased the polymerization yield without a significant modification of the electronic structure of PPy. The highest conductivity of PPy was reached when chondroitin sulfate was used simultaneously as dopant and template during pyrrole polymerization. Electroactive properties of PPy obtained from natural precursors were successfully used in the amperometric quantification of uric acid concentrations. PPy increases the amperometric sensitivity of carbon nanotube screen-printed electrodes toward uric acid detection. - Highlights: • A new method of pyrrole polymerization using naturally occurring redox mediators and doping agents was studied. • The catalytic efficiency of different redox mediators toward pyrrole oxidation was evaluated. • Two different naturally occurring polymers were studied as bifunctional steric stabilizer/doping agents. • Polypyrrole improves the amperometric response of carbon nanotube screen printed electrodes toward uric acid sensing.

Factors affecting the performance of the Zn-Ce redox flow battery

International Nuclear Information System (INIS)

Nikiforidis, Georgios; Cartwright, Rory; Hodgson, David; Hall, David; Berlouis, Leonard

2014-01-01

The Hull Cell was used to investigate the impact of current density j on the morphology and uniformity of zinc electrodeposited from a 2.5 mol dm −3 Zn 2+ solution in 1.5 mol dm −3 methanesulfonic acid at 40 °C onto carbon-composite surfaces. The range of the applied deposition current density used was between 1 mA cm −2 and 100 mA cm −2 . Good, robust deposits were obtained when j ≥ 10 mA cm 2 whereas at j's lower than this, patchy films formed due to the competing hydrogen evolution reaction (HER) on the bare carbon-composite surface. An understanding of these effects and its application in the redox flow battery enabled both the coulombic and cell potential efficiencies to be maintained at relatively high values, 90% and 69% respectively, indicating a successful inhibition of the HER on the fully formed Zn layer. Flow velocity at the low Reynolds number in the cell (Re <200) had little impact on the electrochemical cell performance. Depletion of the cerium species became an issue for long charge times

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

Science.gov (United States)

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.

Nitrogen-Doped Graphene:Effects of nitrogen species on the properties of the vanadium redox flow battery

International Nuclear Information System (INIS)

Shi, Lang; Liu, Suqin; He, Zhen; Shen, Junxi

2014-01-01

Nitrogen-doped graphene nanosheets (NGS), prepared by a simple hydrothermal reaction of graphene oxide (GO) with urea as nitrogen source were studied as positive electrodes in vanadium redox flow battery (VRFB). The synthesized NGS with the nitrogen level as high as 10.12 atom% is proven to be a promising material for VRFB. The structures and electrochemical properties of the materials are investigated by scanning electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry and electrochemical impendence spectroscopy. The results demonstrate that not only the nitrogen doping level but the nitrogen type in the NGS are significant for its catalytic activity towards the [VO] 2+ /[VO 2 ] + redox couple reaction. In more detail, among four types of nitrogen species (pyridinic-N, pyrrolic-N, quaternary-N, oxidic-N) doped into the graphene lattice, quaternary-N play mainly roles for improving the catalytic activity toward the [VO] 2+ /[VO 2 ] + couple reaction

Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting.

Science.gov (United States)

Ling, Chongyi; Shi, Li; Ouyang, Yixin; Zeng, Xiao Cheng; Wang, Jinlan

2017-08-09

Nanosheet supported single-atom catalysts (SACs) can make full use of metal atoms and yet entail high selectivity and activity, and bifunctional catalysts can enable higher performance while lowering the cost than two separate unifunctional catalysts. Supported single-atom bifunctional catalysts are therefore of great economic interest and scientific importance. Here, on the basis of first-principles computations, we report a design of the first single-atom bifunctional eletrocatalyst, namely, isolated nickel atom supported on β 12 boron monolayer (Ni 1 /β 12 -BM), to achieve overall water splitting. This nanosheet supported SAC exhibits remarkable electrocatalytic performance with the computed overpotential for oxygen/hydrogen evolution reaction being just 0.40/0.06 V. The ab initio molecular dynamics simulation shows that the SAC can survive up to 800 K elevated temperature, while enacting a high energy barrier of 1.68 eV to prevent isolated Ni atoms from clustering. A viable experimental route for the synthesis of Ni 1 /β 12 -BM SAC is demonstrated from computer simulation. The desired nanosheet supported single-atom bifunctional catalysts not only show great potential for achieving overall water splitting but also offer cost-effective opportunities for advancing clean energy technology.

Tuning of redox regulatory mechanisms, reactive oxygen species and redox homeostasis under salinity stress

Directory of Open Access Journals (Sweden)

Hossain eSazzad

2016-05-01

Full Text Available Soil salinity is a crucial environmental constraint which limits biomass production at many sites on a global scale. Saline growth conditions cause osmotic and ionic imbalances, oxidative stress and perturb metabolism, e.g. the photosynthetic electron flow. The plant ability to tolerate salinity is determined by multiple biochemical and physiological mechanisms protecting cell functions, in particular by regulating proper water relations and maintaining ion homeostasis. Redox homeostasis is a fundamental cell property. Its regulation includes control of reactive oxygen species (ROS generation, sensing deviation from and readjustment of the cellular redox state. All these redox related functions have been recognized as decisive factors in salinity acclimation and adaptation. This review focuses on the core response of plants to overcome the challenges of salinity stress through regulation of ROS generation and detoxification systems and to maintain redox homeostasis. Emphasis is given to the role of NADH oxidase (RBOH, alternative oxidase (AOX, the plastid terminal oxidase (PTOX and the malate valve with the malate dehydrogenase isoforms under salt stress. Overwhelming evidence assigns an essential auxiliary function of ROS and redox homeostasis to salinity acclimation of plants.

In-situ investigation of hydrogen evolution behavior in vanadium redox flow batteries

International Nuclear Information System (INIS)

Wei, L.; Zhao, T.S.; Xu, Q.; Zhou, X.L.; Zhang, Z.H.

2017-01-01

Highlights: • An in-situ method to investigate hydrogen evolution in VRFBs is developed. • The rate of hydrogen evolution during battery operation is quantified. • The gas evolution behaviors in the charge process of VRFBs are observed. - Abstract: In this work, we conceived and fabricated a three-electrode electrochemical cell and transparent vanadium redox flow battery to in-situ investigate the hydrogen evolution reaction during battery operation. Experimental results show that operating temperature has a strong influence on the HER rate. In particular, compared with V"3"+ reduction reaction, HER is more sensitive to temperature variation. It is also found that, contrary to the conventional wisdom that side reactions occur at the late stage of the charge process, H_2 evolves at a relatively low SOC. About 0.26 and 1.94 mL H_2 were collected at an early (SOC lower than 20%) and end of the charge process, respectively, suggesting that attention to the hydrogen formation at the negative electrode in the early charge process should also be paid to during long-term battery operations. Moreover, the produced hydrogen gas at the negative side prefers to form macroscopically observable bubbles onto the electrode surface, covering the active sites for vanadium redox reactions, while oxygen evolution (including CO_2 production) at the positive side corrodes electrode surface and introduces certain oxygen-containing functional groups.

Development of Integrally Molded Bipolar Plates for All-Vanadium Redox Flow Batteries

Directory of Open Access Journals (Sweden)

Chih-Hsun Chang

2016-05-01

Full Text Available All-vanadium redox flow batteries (VRBs are potential energy storage systems for renewable power sources because of their flexible design, deep discharge capacity, quick response time, and long cycle life. To minimize the energy loss due to the shunt current, in a traditional design, a flow field is machined on two electrically insulated frames with a graphite plate in between. A traditional bipolar plate (BP of a VRB consists of many components, and thus, the assembly process is time consuming. In this study, an integrally molded BP is designed and fabricated to minimize the manufacturing cost. First, the effects of the mold design and injection parameters on frame formability were analyzed by simulation. Second, a new graphite plate design for integral molding was proposed, and finally, two integrally molded BPs were fabricated and compared. Results show that gate position significantly affects air traps and the maximum volume shrinkage occurs at the corners of a BP. The volume shrinkage can be reduced using a large graphite plate embedded within the frame.

Effects of additives on the stability of electrolytes for all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Zhang, Jianlu; Li, Liyu; Nie, Zimin; Chen, Baowei; Vijayakumar, M.; Kim, Soowhan; Wang, Wei; Schwenzer, Birgit; Liu, Jun; Yang, Zhenguo

2011-01-01

The stability of the electrolytes for all-vanadium redox flow battery was investigated with ex-situ heating/cooling treatment and in-situ flow-battery testing methods. The effects of inorganic and organic additives have been studied. The additives containing the ions of potassium, phosphate, and polyphosphate are not suitable stabilizing agents because of their reactions with V(V) ions, forming precipitates of KVSO6 or VOPO4. Of the chemicals studied, polyacrylic acid and its mixture with CH3SO3H are the most promising stabilizing candidates which can stabilize all the four vanadium ions (V2+, V3+, VO2+, and VO2+) in electrolyte solutions up to 1.8 M. However, further effort is needed to obtain a stable electrolyte solution with >1.8 M V5+ at temperatures higher than 40 C.

Composite separators and redox flow batteries based on porous separators

Science.gov (United States)

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.

Fat & fabulous: bifunctional lipids in the spotlight.

Science.gov (United States)

Haberkant, Per; Holthuis, Joost C M

2014-08-01

Understanding biological processes at the mechanistic level requires a systematic charting of the physical and functional links between all cellular components. While protein-protein and protein-nucleic acid networks have been subject to many global surveys, other critical cellular components such as membrane lipids have rarely been studied in large-scale interaction screens. Here, we review the development of photoactivatable and clickable lipid analogues-so-called bifunctional lipids-as novel chemical tools that enable a global profiling of lipid-protein interactions in biological membranes. Recent studies indicate that bifunctional lipids hold great promise in systematic efforts to dissect the elaborate crosstalk between proteins and lipids in live cells and organisms. This article is part of a Special Issue entitled Tools to study lipid functions. Copyright © 2014 Elsevier B.V. All rights reserved.

Mechanish of dTTP Inhibition of the Bifunctional dCTP Deaminase:dUTPase Encoded by Mycobacterium tuberculosis

DEFF Research Database (Denmark)

Helt, Signe Smedegaard; Thymark, Majbritt; Harris, Pernille

2008-01-01

Recombinant deoxycytidine triphosphate (dCTP) deaminase from Mycobacterium tuberculosis was produced in Escherichia coli and purified. The enzyme proved to be a bifunctional dCTP deaminase:deoxyuridine triphosphatase. As such, the M. tuberculosis enzyme is the second bifunctional enzyme to be cha......Recombinant deoxycytidine triphosphate (dCTP) deaminase from Mycobacterium tuberculosis was produced in Escherichia coli and purified. The enzyme proved to be a bifunctional dCTP deaminase:deoxyuridine triphosphatase. As such, the M. tuberculosis enzyme is the second bifunctional enzyme...

Integrated Photoelectrochemical Solar Energy Conversion and Organic Redox Flow Battery Devices

KAUST Repository

Li, Wenjie

2016-09-21

Building on regenerative photoelectrochemical solar cells and emerging electrochemical redox flow batteries (RFBs), more efficient, scalable, compact, and cost-effective hybrid energy conversion and storage devices could be realized. An integrated photoelectrochemical solar energy conversion and electrochemical storage device is developed by integrating regenerative silicon solar cells and 9,10-anthraquinone-2,7-disulfonic acid (AQDS)/1,2-benzoquinone-3,5-disulfonic acid (BQDS) RFBs. The device can be directly charged by solar light without external bias, and discharged like normal RFBs with an energy storage density of 1.15 Wh L−1 and a solar-to-output electricity efficiency (SOEE) of 1.7 % over many cycles. The concept exploits a previously undeveloped design connecting two major energy technologies and promises a general approach for storing solar energy electrochemically with high theoretical storage capacity and efficiency.

An enhancement to Vynnycky's model for the all-vanadium redox flow battery

International Nuclear Information System (INIS)

Chen, Ching Liang; Yeoh, Hak Koon; Chakrabarti, Mohammed Harun

2014-01-01

Highlights: • Improvements are made on an existing 1-D stationary VRFB model. • Effects of species concentration and electrolyte flow rate are captured. • Predictions on charge-discharge curves are improved over existing 1-D model. - Abstract: An enhanced one-dimensional (1-D) stationary model for the all-vanadium redox flow battery (VRFB) is developed based on an existing 1-D model proposed by Vynnycky [Energy, 36 (2011): 2242 – 2256]. The enhanced model incorporates species conservation equations along with an advection term to describe the concentration changes in the porous electrodes. In addition, a complete Nernst equation, which accounts for proton concentrations in the VRFB is also included to improve the cell voltage prediction without using any arbitrary fitting contact voltage. The enhanced 1-D model is validated against experimental data from the literature and the ability of the model to predict the cell performance is investigated. The cell voltage prediction shows significant improvement over Vynnycky's 1-D model and also compares surprisingly well with higher-dimensional models. This enhanced 1-D model is also capable of capturing the cell performance at different electrolyte flow rates, especially evidenced by the polarization curves. Using both the power based and round-trip efficiencies, the optimal electrolyte flow rate for the VRFB can be determined. This enhanced 1-D model is expected to serve as a useful design tool for the development and optimization of VRFB systems

Molecular Engineering with Organic Carbonyl Electrode Materials for Advanced Stationary and Redox Flow Rechargeable Batteries.

Science.gov (United States)

Zhao, Qing; Zhu, Zhiqiang; Chen, Jun

2017-12-01

Organic carbonyl electrode materials that have the advantages of high capacity, low cost and being environmentally friendly, are regarded as powerful candidates for next-generation stationary and redox flow rechargeable batteries (RFBs). However, low carbonyl utilization, poor electronic conductivity and undesired dissolution in electrolyte are urgent issues to be solved. Here, we summarize a molecular engineering approach for tuning the capacity, working potential, concentration of active species, kinetics, and stability of stationary and redox flow batteries, which well resolves the problems of organic carbonyl electrode materials. As an example, in stationary batteries, 9,10-anthraquinone (AQ) with two carbonyls delivers a capacity of 257 mAh g -1 (2.27 V vs Li + /Li), while increasing the number of carbonyls to four with the formation of 5,7,12,14-pentacenetetrone results in a higher capacity of 317 mAh g -1 (2.60 V vs Li + /Li). In RFBs, AQ, which is less soluble in aqueous electrolyte, reaches 1 M by grafting -SO 3 H with the formation of 9,10-anthraquinone-2,7-disulphonic acid, resulting in a power density exceeding 0.6 W cm -2 with long cycling life. Therefore, through regulating substituent groups, conjugated structures, Coulomb interactions, and the molecular weight, the electrochemical performance of carbonyl electrode materials can be rationally optimized. This review offers fundamental principles and insight into designing advanced carbonyl materials for the electrodes of next-generation rechargeable batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Main regularities of radiolytic transformations of bifunctional organic compounds

International Nuclear Information System (INIS)

Petryaev, E.P.; Shadyro, O.I.

1985-01-01

General regularities of the radiolysis of bifunctional organic compounds (α-diols, ethers of α-diols, amino alcohols, hydroxy aldehydes and hydroxy asids) in aqueous solutions from the early stages of the process to formation of finite products are traced. It is pointed out that the most characteristic course of radiation-chemical, transformation of bifunctional compounds in agueous solutions in the fragmentation process with monomolecular decomposition of primary radicals of initial substrances and simultaneous scission of two vicinal in respect to radical centre bonds via five-membered cyclic transient state. The data obtained are of importance for molecular radiobiology

Improvement of the Performance of Graphite Felt Electrodes for Vanadium-Redox-Flow-Batteries by Plasma Treatment

Directory of Open Access Journals (Sweden)

Eva-Maria Hammer

2014-02-01

Full Text Available In the frame of the present contribution oxidizing plasma pretreatment is used for the improvement of the electrocatalytic activity of graphite felt electrodes for Vanadium-Redox-Flow-Batteries (VRB. The influence of the working gas media on the catalytic activity and the surface morphology is demonstrated. The electrocatalytical properties of the graphite felt electrodes were examined by cyclic voltammetry and electrochemical impedance spectroscopy. The obtained results show that a significant improvement of the redox reaction kinetics can be achieved for all plasma modified samples using different working gasses (Ar, N2 and compressed air in an oxidizing environment. Nitrogen plasma treatment leads to the highest catalytical activities at the same operational conditions. Through a variation of the nitrogen plasma treatment duration a maximum performance at about 14 min cm-2 was observed, which is also represented by a minimum of 90 Ω in the charge transfer resistance obtained by EIS measurements. The morphology changes of the graphitized surface were followed using SEM.

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

Science.gov (United States)

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.

Studies on membrane for redox flow battery. 9. Crosslinking of the membrane by the electron radiation and durability of the membrane

International Nuclear Information System (INIS)

Ohya, Haruhiko; Minamihira, Kazunori; Hwang, Gab-Jin; Kawahara, Takashi; Aihara, Masahiko; Negishi, Youichi; Kang, An-Soo.

1995-01-01

Chlorosulfonated homogeneous and asymmetric cation exchange membranes were tested as separators for the all-vanadium redox flow battery. The membrane was prepared by chlorosulfonation of the polyethylene film in vapour phase. In the case of the polyethylene film of 20 μm thickness used for the homogeneous membrane, area resistivity of 0.5 Ω · cm 2 in 2M KCl aq. solution was reached at 120 min. chlorosulfonation time. In the case of heat laminated 20 μm thick PE film on a neutral porous polyolefin film of 200 μm thickness used for the asymmetric membrane, a minimum area resistivity of 1 Ω · cm 2 in 2M KCl was achieved at 120 min. chlorosulfonation time. The performance evaluation of the membranes as separators in the all-vanadium redox flow battery was also measured. The area resistivity of the membranes in the measuring-cell using charge-discharge current density 63.7 mA/cm 2 was 1.4 Ω · cm 2 and 2.2 Ω · cm 2 for charge and discharge respectively for the homogeneous membrane, and 3.6 Ω · cm 2 and 4.3 Ω · cm 2 for charge discharge cycles respectively for the asymmetric membrane. The chlorosulfonated homogeneous cation exchange membrane was cross-linked by the electron radiation to improve durability of the membrane. The crosslinked membrane which has the high degree of cross-linking, did not shown the mechanical breakage by swelling or shrinking in the acidic vanadium solution, but its area resistivity in the all-vanadium redox flow battery was increased. (author)

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

Science.gov (United States)

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.

Research and development of peripheral technology for photovoltaic power systems. Research and development of redox flow battery for photovoltaic power generation; Shuhen gijutsu no kenkyu kaihatsu. Taiyoko hatsuden`yo redox denchi no kenkyu kaihatsu

Energy Technology Data Exchange (ETDEWEB)

Tatsuta, M [New Energy and Industrial Technology Development Organization, Tokyo (Japan)

1994-12-01

This paper reports the study results on R and D of redox flow battery for photovoltaic power generation in fiscal 1994. (1) On the production method of electrolyte, silica reduction treatment was attempted to use ammonium metavanadate recovered from boiler as electrolyte of redox flow battery. Silica removal rates more than 90% were achieved by crystallizing V as polyvanadate while keeping molten silica. It was ascertained in minicell experiment that trivalent and quadrivalent V electrolytes produced from recovered V are applicable to continuous charge/discharge operation for one week. (2) On development of battery systems, the relation between battery characteristics and physicochemical properties of carbon fiber electrodes was studied to improve carbon fiber electrodes. The efficiency of 80% was achieved at current density of 160mA/cm{sup 2} by use of layered electrodes, resulting in considerable cost reduction. Performance evaluation operation of the 2kW battery prepared in the last fiscal year was also carried out. 4 figs.

A mathematical model for the iron/chromium redox battery

Science.gov (United States)

Fedkiw, P. S.; Watts, R. W.

1984-01-01

A mathematical model has been developed to describe the isothermal operation of a single anode-separator-cathode unit cell in a redox-flow battery and has been applied to the NASA iron/chromium system. The model, based on porous electrode theory, incorporates redox kinetics, mass transfer, and ohmic effects as well as the parasitic hydrogen reaction which occurs in the chromium electrode. A numerical parameter study was carried out to predict cell performance to aid in the rational design, scale-up, and operation of the flow battery. The calculations demonstrate: (1) an optimum electrode thickness and electrolyte flow rate exist; (2) the amount of hydrogen evolved and, hence, cycle faradaic efficiency, can be affected by cell geometry, flow rate, and charging procedure; (3) countercurrent flow results in enhanced cell performance over cocurrent flow; and (4) elevated temperature operation enhances cell performance.

Hydrogen evolution at the negative electrode of the all-vanadium redox flow batteries

Science.gov (United States)

Sun, Che-Nan; Delnick, Frank M.; Baggetto, Loïc; Veith, Gabriel M.; Zawodzinski, Thomas A.

2014-02-01

This work demonstrates a quantitative method to determine the hydrogen evolution rate occurring at the negative carbon electrode of the all vanadium redox flow battery (VRFB). Two carbon papers examined by buoyancy measurements yield distinct hydrogen formation rates (0.170 and 0.005 μmol min-1 g-1). The carbon papers have been characterized using electron microscopy, nitrogen gas adsorption, capacitance measurement by electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS). We find that the specific electrochemical surface area (ECSA) of the carbon material has a strong influence on the hydrogen generation rate. This is discussed in light of the use of high surface area material to obtain high reaction rates in the VRFB.

Mn3O4 anchored on carbon nanotubes as an electrode reaction catalyst of V(IV)/V(V) couple for vanadium redox flow batteries

International Nuclear Information System (INIS)

He, Zhangxing; Dai, Lei; Liu, Suqin; Wang, Ling; Li, Chuanchang

2015-01-01

Highlights: • Mn 3 O 4 /MWCNTs (multi-walled carbon nanotubes) composite fabricated by a simple solvothermal method was developed as electrochemical catalyst of V(IV)/V(V) redox couple for vanadium redox flow batteries for the first time. • The electrocatalytic kinetics of the redox reactions of three electrocatalysts (pure Mn 3 O 4 , pure MWCNTs, Mn 3 O 4 /MWCNTs) were compared, and were in the order of Mn 3 O 4 /MWCNTs > MWCNTs > Mn 3 O 4 . • The cell using Mn 3 O 4 /MWCNTs has lower electrochemical polarization, with larger discharge capacity and energy efficiency. The average energy efficiency of the cell using Mn 3 O 4 /MWCNTs is 84.65%, 3.73% higher than that of the pristine cell. - Abstract: Mn 3 O 4 /MWCNTs (multi-walled carbon nanotubes) composite fabricated by a simple solvothermal method was developed as electrochemical catalyst of V(IV)/V(V) redox couple for vanadium redox flow batteries. The electrochemical activity of V(IV)/V(V) redox couple can be enhanced by the electrochemical catalysts (Mn 3 O 4 , MWCNTs, Mn 3 O 4 /MWCNTs), and the electrocatalytic kinetics of the redox reactions were in the order of Mn 3 O 4 /MWCNTs > MWCNTs > Mn 3 O 4 . The cell using Mn 3 O 4 /MWCNTs composite as electrochemical catalyst was assembled and the charge-discharge performance was evaluated. Compared with the pristine cell, the cell using positive graphite felt modified by Mn 3 O 4 /MWCNTs had lower electrochemical polarization, larger discharge capacity and energy efficiency. The average energy efficiency of the cell using modified positive electrode for 50 cycles was 84.65%, 3.73% higher than that of the pristine cell. The superior electrocatalytic performance of Mn 3 O 4 /MWCNTs composite was mainly due to the effective mixed conducting network, facilitating the electron transport and ion diffusion in the electrode/electrolyte interface

Increasing the energy density of the non-aqueous vanadium redox flow battery with new electrolytes; Neue Elektrolyte zur Steigerung der Energiedichte einer nicht-waessrigen Vanadium-Acetylacetonat-Redox-Flow-Batterie

Energy Technology Data Exchange (ETDEWEB)

Herr, Tatjana

2015-07-01

Redox flow battery (RFB) is a promising energy storage technology which is similar to a polymer electrolyte membrane fuel cell. Currently, this electrochemical energy conversion device is used as a storage system for renewable energies or as uninterruptable power source. All-Vanadium-RFB (VRFB) and Zinc-Bromine-RFB are most well-known types of the aqueous RFB for these applications. But also the non-aqueous RFB is becoming more and more famous, because non-aqueous electrolytes offer wider operating temperature ranges, wider stable potential windows and a potentially higher energy density. However, current research studies show that the solubility of the most used redox active species is not sufficient. Therefore, present study aims to show concepts in order to solve this problem. Vanadium(III)acetylacetonate (V(acac){sub 3}) is used as active species, supported by tetrabutylammonium hexafluorophosphate. In acetonitrile it shows two quasi-reversible redox couples and a cell potential ∝2.2 V. The maximum solubility is ∝0.6 M. In this work other solvents and solvent mixtures were examined with the objective of increasing the solubility of V(acac){sub 3}. In 1,3-dioxolane the solubility was e.g. 0.8 M, dimethyl sulfoxide showed good battery performance with the highest energy efficiency ∝44 %. Acetylacetone is able to regenerate V(acac){sub 3} from the side product that is formed by reaction with water. The new electrolyte solution consisting of acetonitrile, 1,3-dioxolane and dimethyl sulfoxide nearly doubled the solubility of V(acac){sub 3}. In galvanostatic charge-discharge tests, single cell V(acac){sub 3} RFB exhibited energy efficiency between 25-50 % depending an test conditions. Also, the influence of water and oxygen addition an electrolyte was investigated. Finally, experiments with different ambient temperatures show that V(acac){sub 3} RFB is able to operate at temperatures such as 0 C and -25 C.

Synthesis, characterization and catalytic activity of acid-base bifunctional materials through protection of amino groups

Energy Technology Data Exchange (ETDEWEB)

Shao, Yanqiu [College of Chemistry, Jilin University, Changchun 130023 (China); College of Chemistry, Mudanjiang Normal University, Mudanjiang 157012 (China); Liu, Heng; Yu, Xiaofang [College of Chemistry, Jilin University, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130023 (China); Kan, Qiubin, E-mail: qkan@mail.jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130023 (China)

2012-03-15

Graphical abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. Highlights: Black-Right-Pointing-Pointer The acid-base bifunctional material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized through protection of amino groups. Black-Right-Pointing-Pointer The obtained bifunctional material was tested for aldol condensation. Black-Right-Pointing-Pointer The SO{sub 3}H-SBA-15-NH{sub 2} catalyst containing amine and sulfonic acid groups exhibited excellent acid-basic properties. -- Abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. X-ray diffraction (XRD), N{sub 2} adsorption-desorption, transmission electron micrographs (TEM), back titration, {sup 13}C magic-angle spinning (MAS) NMR and {sup 29}Si magic-angle spinning (MAS) NMR were employed to characterize the synthesized materials. The obtained bifunctional material was tested for aldol condensation reaction between acetone and 4-nitrobenzaldehyde. Compared with monofunctional catalysts of SO{sub 3}H-SBA-15 and SBA-15-NH{sub 2}, the bifunctional sample of SO{sub 3}H-SBA-15-NH{sub 2} containing amine and sulfonic acid groups exhibited excellent acid-basic properties, which make it possess high activity for the aldol condensation.

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

Science.gov (United States)

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.

Integrated Photoelectrochemical Solar Energy Conversion and Organic Redox Flow Battery Devices.

Science.gov (United States)

Li, Wenjie; Fu, Hui-Chun; Li, Linsen; Cabán-Acevedo, Miguel; He, Jr-Hau; Jin, Song

2016-10-10

Building on regenerative photoelectrochemical solar cells and emerging electrochemical redox flow batteries (RFBs), more efficient, scalable, compact, and cost-effective hybrid energy conversion and storage devices could be realized. An integrated photoelectrochemical solar energy conversion and electrochemical storage device is developed by integrating regenerative silicon solar cells and 9,10-anthraquinone-2,7-disulfonic acid (AQDS)/1,2-benzoquinone-3,5-disulfonic acid (BQDS) RFBs. The device can be directly charged by solar light without external bias, and discharged like normal RFBs with an energy storage density of 1.15 Wh L -1 and a solar-to-output electricity efficiency (SOEE) of 1.7 % over many cycles. The concept exploits a previously undeveloped design connecting two major energy technologies and promises a general approach for storing solar energy electrochemically with high theoretical storage capacity and efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A high-performance carbon nanoparticle-decorated graphite felt electrode for vanadium redox flow batteries

International Nuclear Information System (INIS)

Wei, L.; Zhao, T.S.; Zhao, G.; An, L.; Zeng, L.

2016-01-01

Highlights: • Propose a carbon nanoparticle-decorated graphite felt electrode for VRFBs. • The energy efficiency is up to 84.8% at 100 mA cm"−"2. • The new electrode allows the peak power density to reach 508 mW cm"−"2. - Abstract: Increasing the performance of vanadium redox flow batteries (VRFBs), especially the energy efficiency and power density, is critically important to reduce the system cost to a level for widespread commercialization. Unlike conventional VRFBs with flow-through structure, in this work we create a VRFB featuring a flow-field structure with a carbon nanoparticle-decorated graphite felt electrode for the battery. This novel structure, exhibiting a significantly reduced ohmic loss through reducing electrode thickness, an increased surface area and improved electrocatalytic activity by coating carbon nanoparticles, allows the energy efficiency up to 84.8% at a current density of as high as 100 mA cm"−"2 and the peak power density to reach a value of 508 mW cm"−"2. In addition, it is demonstrated that the battery with this proposed structure exhibits a substantially improved rate capability and capacity retention as opposed to conventional flow-through structured battery with thick graphite felt electrodes.

Dynamic electro-thermal modeling of all-vanadium redox flow battery with forced cooling strategies

International Nuclear Information System (INIS)

Wei, Zhongbao; Zhao, Jiyun; Xiong, Binyu

2014-01-01

Highlights: • A dynamic electro-thermal model is proposed for VRB with forced cooling. • The Foster network is adopted to model the battery cooling process. • Both the electrolyte temperature and terminal voltage can be accurately predicted. • The flow rate of electrolyte and coolant significantly impact battery performance. - Abstract: The present study focuses on the dynamic electro-thermal modeling for the all-vanadium redox flow battery (VRB) with forced cooling strategies. The Foster network is adopted to dynamically model the heat dissipation of VRB with heat exchangers. The parameters of Foster network are extracted by fitting the step response of it to the results of linearized CFD model. Then a complete electro-thermal model is proposed by coupling the heat generation model, Foster network and electrical model. Results show that the established model has nearly the same accuracy with the nonlinear CFD model in electrolyte temperature prediction but drastically improves the computational efficiency. The modeled terminal voltage is also benchmarked with the experimental data under different current densities. The electrolyte temperature is found to be significantly influenced by the flow rate of coolant. As compared, although the electrolyte flow rate has unremarkable impact on electrolyte temperature, its effect on system pressure drop and battery efficiency is significant. Increasing the electrolyte flow rate improves the coulombic efficiency, voltage efficiency and energy efficiency simultaneously but at the expense of higher pump power demanded. An optimal flow rate exists for each operating condition to maximize the system efficiency

Cobalt(II) complexes with azole-pyridine type ligands for non-aqueous redox-flow batteries: Tunable electrochemistry via structural modification

Science.gov (United States)

Armstrong, Craig G.; Toghill, Kathryn E.

2017-05-01

A single species redox flow battery employing a new class of cobalt(II) complexes with 'tunable' tridentate azole-pyridine type ligands is reported. Four structures were synthesised and their electrochemical, physical and battery characteristics were investigated as a function of successive substitution of the ligand terminal pyridyl donors. The Co(II/I) and Co(III/II) couples are stable and quasi-reversible on gold and glassy carbon electrodes, however redox potentials are tunable allowing the cobalt potential difference to be preferentially increased from 1.07 to 1.91 V via pyridine substitution with weaker σ-donating/π-accepting 3,5-dimethylpyrazole groups. The charge-discharge properties of the system were evaluated using an H-type glass cell and graphite rod electrodes. The complexes delivered high Coulombic efficiencies of 89.7-99.8% and very good voltaic efficiencies of 70.3-81.0%. Consequently, energy efficiencies are high at 63.1-80.8%, marking an improvement on other similar non-aqueous systems. Modification of the ligands also improved solubility from 0.18 M to 0.50 M via pyridyl substitution with 3,5-dimethylpyrazole, though the low solubility of the complexes limits the overall energy capacity to between 2.58 and 12.80 W h L-1. Preliminary flow cell studies in a prototype flow cell are also demonstrated.

Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

Energy Technology Data Exchange (ETDEWEB)

Mai, Zhensheng; Bi, Cheng; Dai, Hua [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100039 (China); Zhang, Huamin; Li, Xianfeng [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China)

2011-01-01

Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-23

The microstructure of the perfluorinated sulfonic acid proton exchange membranes such as Nafion significantly affects their transport properties and performance in a vanadium redox flow battery (VRB). In this work, Nafion membranes with various equivalent weights (EW) ranging from 1000 to 1500 are prepared and the structure-property-performance relationship is investigated. Nuclear magnetic resonance (NMR) and small-angle X-ray scattering (SAXS) studies revealed their composition and morphology variances, which lead to major differences in key transport properties related to proton conduction and vanadium ion permeation. Their performances are further characterized as VRB membranes. Based on those understanding, a new perfluorosulfonic acid 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 50mA∙cm-2) was achieved along with a stable cyclical capacity over prolonged cycling.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

2017-06-01

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

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

Science.gov (United States)

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.

Hybrid energy storage systems utilizing redox active organic compounds

Science.gov (United States)

Wang, Wei; Xu, Wu; Li, Liyu; Yang, Zhenguo

2015-09-08

Redox flow batteries (RFB) have attracted considerable interest due to their ability to store large amounts of power and energy. Non-aqueous energy storage systems that utilize at least some aspects of RFB systems are attractive because they can offer an expansion of the operating potential window, which can improve on the system energy and power densities. One example of such systems has a separator separating first and second electrodes. The first electrode includes a first current collector and volume containing a first active material. The second electrode includes a second current collector and volume containing a second active material. During operation, the first source provides a flow of first active material to the first volume. The first active material includes a redox active organic compound dissolved in a non-aqueous, liquid electrolyte and the second active material includes a redox active metal.

Synthesis of flexible electrodes based on electrospun carbon nanofibers with Mn_3O_4 nanoparticles for vanadium redox flow battery application

International Nuclear Information System (INIS)

Di Blasi, A.; Busaccaa, C.; Di Blasia, O.; Briguglioa, N.; Squadritoa, G.; Antonuccia, V.

2017-01-01

Highlights: • Mn_3O_4/CNF electrode is investigated for vanadium redox flow battery application. • The high reversibility is ascribed to the several type of redox couples on the spinel structure. • Cell electrochemical parameters confirm the high reversibility for Mn_3O_4/CNF electrodes. - Abstract: Flexible carbon nanofiber (CNF)-based electrodes and CNF with a 20% of manganese oxide incorporated (Mn_3O_4/CNF) are prepared by using the electrospinning method for vanadium redox flow battery (VRFB) application. A blend consisting of manganese acetate (Mn(OAc)_2) and polyacrilonitrile (PAN) is electrospun and successively subjected to different thermal treatments in which the growth of Mn_3O_4 particles and CNFs occurred together guaranteeing an appropriate electron conductivity for electrodes thus synthesized. Cyclic voltammetry (CV) measurements show an interesting electrocatalytic activity toward the [VO]"2"+/[VO_2]"+ as well as the V"2"+/V"3"+ redox reactions for the Mn_3O_4/CNF electrospun sample. Charge-discharge tests, carried out at 80 mA cm"−"2, show a state of charge (SOC) and a depth of discharge (DoD) of 81% and 73%, respectively, for the cells assembled with Mn_3O_4/CNF electrodes. These data are indicative of a high vanadium active species utilization thanks to the better electrocatalytic activity at high current densities. Furthermore, the cell with Mn_3O_4/CNF shows EE values of about 81% (88% of VE and 92% of CE) vs. 70% (75% of VE and 93% of CE) with respect to a commercial carbon felt (CF) electrode used for comparison. These results are attributable to the higher oxygen species content as well as the improved electron conductivity due to the synergetic effect of the more graphitic carbon and to the structural defects within the Mn_3O_4 spinel structure.

Energy efficiency of neptunium redox battery in comparison with vanadium battery

International Nuclear Information System (INIS)

Yamamura, T.; Watanabe, N.; Shiokawa, Y.

2006-01-01

A neptunium ion possesses two isostructural and reversible redox couples (Np 3+ /Np 4+ and NpO 2 + /NpO 2 2+ ) and is therefore suitable as an active material for a redox-flow battery. Since the plastic formed carbon (PFC) is known to show the largest k values for Np(IV)/Np(III) and Np(V)/Np(VI) reactions among various carbon electrodes, a cell was constructed by using the PFC, with the circulation induced by bubbling gas through the electrolyte. In discharge experiments with a neptunium and a vanadium battery using the cell, the former showed a lower voltage loss which suggests a smaller reaction overvoltage. Because of the high radioactivity of the neptunium, it was difficult to obtain sufficient circulation required for the redox-flow battery, therefore a model for evaluating the energy efficiency of the redox-flow battery was developed. By using the known k values for neptunium and vanadium electrode reactions at PFC electrodes, the energy efficiency of the neptunium battery was calculated to be 99.1% at 70 mA cm -2 , which exceeds that of the vanadium battery by ca. 16%

Synthesis of deuterium-labeled analogs of the lipid hydroperoxide-derived bifunctional electrophile 4-oxo-2(E)-nonenal

OpenAIRE

Arora, Jasbir S.; Oe, Tomoyuki; Blair, Ian A.

2011-01-01

Lipid hydroperoxides undergo homolytic decomposition into the bifunctional 4-hydroxy-2(E)-nonenal and 4-oxo-2(E)-nonenal (ONE). These bifunctional electrophiles are highly reactive and can readily modify intracellular molecules including glutathione (GSH), deoxyribonucleic acid (DNA) and proteins. Lipid hydroperoxide-derived bifunctional electrophiles are thought to contribute to the pathogenesis of a number of diseases. ONE is an α,β-unsaturated aldehyde that can react in multiple ways and w...

Performance of a vanadium redox flow battery with a VANADion membrane

International Nuclear Information System (INIS)

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

2016-01-01

Highlights: • Performance of the VANADion membrane in flow batteries is evaluated. • The battery with present membrane shows good rate capability. • The battery with present membrane offers good capacity retention. • The high performance and low cost make the membrane promising in VRFBs. - Abstract: Conventional vanadium redox flow batteries (VRFBs) using Nafion 115 suffered from issues associated with high ohmic resistance and high capital cost. In this work, we report a commercial membrane (VANADion), consisting of a porous layer and a dense Nafion layer, as a promising alternative to Nafion 115. In the dual-layer structure, the porous layer (∼210 μm) can offer a high ionic conductivity and the dense Nafion layer (∼20 μm) can depress the convective flow of electrolyte through the membrane. By comparing with the conventional Nafion 115 in a VRFB, it is found that the change from the conventional Nafion 115 to the composite one results in an increase in the energy efficiency from 71.3% to 76.2% and an increase in the electrolyte utilization from 54.1% to 68.4% at a current density of as high as 240 mA cm"−"2. In addition, although two batteries show the comparable cycling performance at current densities ranging from 80 mA cm"−"2 to 240 mA cm"−"2, the composite membrane is estimated to be significantly cheaper than the conventional Nafion 115 due to the fact that the porous layer is rather cost-effective and the dense Nafion layer is rather thin. The impressive combination of desirable performance and low cost makes this composite membrane highly promising in the VRFB applications.

Effects of operating temperature on the performance of vanadium redox flow batteries

International Nuclear Information System (INIS)

Zhang, C.; Zhao, T.S.; Xu, Q.; An, L.; Zhao, G.

2015-01-01

Highlights: • The effect of the operating temperature on the VRFB’s performance is studied. • The voltage efficiency and peak power density increases with temperature. • High temperatures aggravate the coulombic efficiency drop and the capacity decay. • The outcomes suggest that thermal management of operating VRFBs is essential. - Abstract: For an operating flow battery system, how the battery’s performance varies with ambient temperatures is of practical interest. To gain an understanding of the general thermal behavior of vanadium redox flow batteries (VRFBs), we devised and tested a laboratory-scale single VRFB by varying the operating temperature. The voltage efficiency of the VRFB is found to increase from 86.5% to 90.5% at 40 mA/cm 2 when the operating temperature is increased from 15 °C to 55 °C. The peak discharge power density is also observed to increase from 259.5 mW/cm 2 to 349.8 mW/cm 2 at the same temperature increment. The temperature increase, however, leads to a slight decrease in the coulombic efficiency from 96.2% to 93.7% at the same temperature increments. In addition, the capacity degradation rate is found to be higher at higher temperatures

Bifunctional chelating agent for the design and development of site specific radiopharmaceuticals and biomolecule conjugation strategy

Science.gov (United States)

Katti, Kattesh V.; Prabhu, Kandikere R.; Gali, Hariprasad; Pillarsetty, Nagavara Kishore; Volkert, Wynn A.

2003-10-21

There is provided a method of labeling a biomolecule with a transition metal or radiometal in a site specific manner to produce a diagnostic or therapeutic pharmaceutical compound by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radio metal or a transition metal, and covalently linking the resulting metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. Also provided is a method of synthesizing the --PR.sub.2 containing biomolecules by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radiometal or a transition metal, and covalently linking the resulting radio metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. There is provided a therapeutic or diagnostic agent comprising a --PR.sub.2 containing biomolecule.

The electrochemical catalytic activity of single-walled carbon nanotubes towards VO2+/VO2+ and V3+/V2+ redox pairs for an all vanadium redox flow battery

International Nuclear Information System (INIS)

Li Wenyue; Liu Jianguo; Yan Chuanwei

2012-01-01

Highlights: ► SWCNT shows excellent electrochemical catalytic activity towards VO 2 + /VO 2+ and V 3+ /V 2+ redox couples. ► The anodic reactions are more sensitive to the surface oxygen atom content change compared with the cathodic reactions. ► The enhanced battery performance clearly demonstrated that the SWCNT is suitable to be used as an electrode catalyst for VRFB. - Abstract: Single-walled carbon nanotube (SWCNT) was used as an electrode catalyst for an all vanadium redox flow battery (VRFB). The electrochemical property of SWCNT towards VO 2 + /VO 2+ and V 3+ /V 2+ was carefully characterized by cyclic voltammetric (CV) and electrochemical impedance spectroscopy (EIS) measurements. The peak current values for these redox pairs were significantly higher on the modified glassy carbon electrode compared with those obtained on the bare electrode, suggesting the excellent electrochemical activity of the SWCNT. Moreover, it was proved that the anodic process was more dependent on the surface oxygen of the SWCNT than the cathodic process through changing its surface oxygen content. Detailed EIS analysis of different modified electrodes revealed that the charge and mass transfer processes were accelerated at the modified electrode–electrolyte interface, which could be ascribed to the large specific surface area, the surface defects and the oxygen functional groups of the SWCNT. The enhanced battery performance effectively demonstrated that the SWCNT was suitable to serve as an electrode catalyst for the VRFB.

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

Science.gov (United States)

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.

Redox zone II. Coupled modeling of groundwater flow, solute transport, chemical reactions and microbial processes in the Aespoe island

International Nuclear Information System (INIS)

Samper, Javier; Molinero, Jorge; Changbing Yang; Guoxiang Zhang

2003-12-01

The Redox Zone Experiment was carried out at the Aespoe HRL in order to study the redox behaviour and the hydrochemistry of an isolated vertical fracture zone disturbed by the excavation of an access tunnel. Overall results and interpretation of the Redox Zone Project were reported by Banwart et al. Later, Banwart presented a summary of the hydrochemistry of the Redox Zone Experiment. Coupled groundwater flow and reactive transport models of this experiment were carried out by Molinero who proposed a revised conceptual model for the hydrogeology of the Redox Zone Experiment which could explain simultaneously measured drawdown and salinity data. The numerical model was found useful to understand the natural system. Several conclusions were drawn about the redox conditions of recharge waters, cation exchange capacity of the fracture zone and the role of mineral phases such as pyrite, calcite, hematite and goethite. This model could reproduce the measured trends of dissolved species, except for bicarbonate and sulphate which are affected by microbially-mediated processes. In order to explore the role of microbial processes, a coupled numerical model has been constructed which accounts for water flow, reactive transport and microbial processes. The results of this model is presented in this report. This model accounts for groundwater flow and reactive transport in a manner similar to that of Molinero and extends the preliminary microbial model of Zhang by accounting for microbially-driven organic matter fermentation and organic matter oxidation. This updated microbial model considers simultaneously the fermentation of particulate organic matter by yeast and the oxidation of dissolved organic matter, a product of fermentation. Dissolved organic matter is produced by yeast and serves also as a substrate for iron-reducing bacteria. Model results reproduce the observed increase in bicarbonate and sulfaphe concentration, thus adding additional evidence for the possibility

Redox zone II. Coupled modeling of groundwater flow, solute transport, chemical reactions and microbial processes in the Aespoe island

Energy Technology Data Exchange (ETDEWEB)

Samper, Javier; Molinero, Jorge; Changbing Yang; Guoxiang Zhang [Univ. Da Coruna (Spain)

2003-12-01

The Redox Zone Experiment was carried out at the Aespoe HRL in order to study the redox behaviour and the hydrochemistry of an isolated vertical fracture zone disturbed by the excavation of an access tunnel. Overall results and interpretation of the Redox Zone Project were reported by Banwart et al. Later, Banwart presented a summary of the hydrochemistry of the Redox Zone Experiment. Coupled groundwater flow and reactive transport models of this experiment were carried out by Molinero who proposed a revised conceptual model for the hydrogeology of the Redox Zone Experiment which could explain simultaneously measured drawdown and salinity data. The numerical model was found useful to understand the natural system. Several conclusions were drawn about the redox conditions of recharge waters, cation exchange capacity of the fracture zone and the role of mineral phases such as pyrite, calcite, hematite and goethite. This model could reproduce the measured trends of dissolved species, except for bicarbonate and sulphate which are affected by microbially-mediated processes. In order to explore the role of microbial processes, a coupled numerical model has been constructed which accounts for water flow, reactive transport and microbial processes. The results of this model is presented in this report. This model accounts for groundwater flow and reactive transport in a manner similar to that of Molinero and extends the preliminary microbial model of Zhang by accounting for microbially-driven organic matter fermentation and organic matter oxidation. This updated microbial model considers simultaneously the fermentation of particulate organic matter by yeast and the oxidation of dissolved organic matter, a product of fermentation. Dissolved organic matter is produced by yeast and serves also as a substrate for iron-reducing bacteria. Model results reproduce the observed increase in bicarbonate and sulfaphe concentration, thus adding additional evidence for the possibility

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

Energy Technology Data Exchange (ETDEWEB)

Yu, Xiaofang [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Zou, Yongcun [State Key Laboratory of Inoranic Synthesis and Preparative Chemistryg, College of Chemistry, Jilin University, Changchun 130012 (China); Wu, Shujie; Liu, Heng [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Kan, Qiubin, E-mail: qkan@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China)

2011-06-15

Graphical abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst. The obtained sample of SO{sub 3}H-MCM-41-NH{sub 2} containing amine and sulfonic acids exhibits excellent catalytic activity in aldol condensation reaction. Research highlights: {yields} Synthesize acid-base bifunctional mesoporous materials SO{sub 3}H-MCM-41-NH{sub 2}. {yields} Oxidation and then thermolysis to generate acidic site and basic site. {yields} Exhibit good catalytic performance in aldol condensation reaction between acetone and various aldehydes. -- Abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO{sub 3}H-MCM-41-NH{sub 2}. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state {sup 13}C CP/MAS NMR and solid-state {sup 29}Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO{sub 3}H-MCM-41-NH{sub 2}) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.

Phosphorus mobilization in rewetted peat and sand at variable flow rate and redox regimes

DEFF Research Database (Denmark)

Kjærgaard, Charlotte; Heiberg, Lisa; Jensen, Henning S.

2012-01-01

the upward percolation of groundwater with variable O2 content and flow rate, we investigated the hydro-biogeochemical Fe and P dynamics in intact cores of a carbon rich peat and carbon poor sand. Percolation of deionized water with high, low or no O2 supply at 10 °C caused markedly different in situ redox...... rates from 7.6 to 11 mg P m−2 day−1. Organic or particulate P contributed to 40–45% of total P losses from the peat. In contrast, the high O2 supply during high flow rate kept the peat oxic and lowered TP release rates to 6.7 mg P m−2 day−1. The carbon poor sand demonstrated that this soil type...... regimes in the two soils during 21 or 67 days of continuous percolation at either 1 or 4 mm h−1. Anoxic conditions occurred in the peat soil at both low oxygen supply and anoxic infiltration, causing reductive Fe(III) dissolution with high Fe(II) and P effluent concentrations and total P (TP) release...

Feasibility of a Supporting-Salt-Free Nonaqueous Redox Flow Battery Utilizing Ionic Active Materials.

Science.gov (United States)

Milshtein, Jarrod D; Fisher, Sydney L; Breault, Tanya M; Thompson, Levi T; Brushett, Fikile R

2017-05-09

Nonaqueous redox flow batteries (NAqRFBs) are promising devices for grid-scale energy storage, but high projected prices could limit commercial prospects. One route to reduced prices is to minimize or eliminate the expensive supporting salts typically employed in NAqRFBs. Herein, the feasibility of a flow cell operating in the absence of supporting salt by utilizing ionic active species is demonstrated. These ionic species have high conductivities in acetonitrile (12-19 mS cm -1 ) and cycle at 20 mA cm -2 with energy efficiencies (>75 %) comparable to those of state-of-the-art NAqRFBs employing high concentrations of supporting salt. A chemistry-agnostic techno-economic analysis highlights the possible cost savings of minimizing salt content in a NAqRFB. This work offers the first demonstration of a NAqRFB operating without supporting salt. The associated design principles can guide the development of future active species and could make NAqRFBs competitive with their aqueous counterparts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox-capacitor to connect electrochemistry to redox-biology.

Science.gov (United States)

Kim, Eunkyoung; Leverage, W Taylor; Liu, Yi; White, Ian M; Bentley, William E; Payne, Gregory F

2014-01-07

It is well-established that redox-reactions are integral to biology for energy harvesting (oxidative phosphorylation), immune defense (oxidative burst) and drug metabolism (phase I reactions), yet there is emerging evidence that redox may play broader roles in biology (e.g., redox signaling). A critical challenge is the need for tools that can probe biologically-relevant redox interactions simply, rapidly and without the need for a comprehensive suite of analytical methods. We propose that electrochemistry may provide such a tool. In this tutorial review, we describe recent studies with a redox-capacitor film that can serve as a bio-electrode interface that can accept, store and donate electrons from mediators commonly used in electrochemistry and also in biology. Specifically, we (i) describe the fabrication of this redox-capacitor from catechols and the polysaccharide chitosan, (ii) discuss the mechanistic basis for electron exchange, (iii) illustrate the properties of this redox-capacitor and its capabilities for promoting redox-communication between biology and electrodes, and (iv) suggest the potential for enlisting signal processing strategies to "extract" redox information. We believe these initial studies indicate broad possibilities for enlisting electrochemistry and signal processing to acquire "systems level" redox information from biology.

Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

Science.gov (United States)

Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

2015-12-01

The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites. Here we show for a bifunctional catalyst—comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder—that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

Investigation of Ir-modified carbon felt as the positive electrode of an all-vanadium redox flow battery

International Nuclear Information System (INIS)

Wang, W.H.; Wang, X.D.

2007-01-01

Porous graphite felts have been used as electrode materials for all-vanadium redox flow batteries due to their wide operating potential range, stability as both an anode and a cathode, and availability in high surface area. In this paper, the carbon felt was modified by pyrolysis of Ir reduced from H 2 IrCl 6 . ac impedance and steady-state polarization measurements showed that the Ir-modified materials have improved activity and lowered overpotential of the desired V(IV)/V(V) redox process. Ir-modification of carbon felt enhanced the electro-conductivity of electrode materials. The Ir-material, when coated on the graphite felt electrode surface, lowered the cell internal resistance. A test cell was assembled with the Ir-modified carbon felt as the activation layer of the positive electrode, the unmodified raw felt as the activation layer of the negative electrode. At an operating current density of 20 mA cm -2 , a voltage efficiency of 87.5% was achieved. The resistance of the cell using Ir-modified felt decreased 25% compared to the cell using non-modified felt

AGC of a multi-area power system under deregulated environment using redox flow batteries and interline power flow controller

Directory of Open Access Journals (Sweden)

Tulasichandra Sekhar Gorripotu

2015-12-01

Full Text Available In this paper, Proportional Integral Derivative with Filter (PIDF is proposed for Automatic Generation Control (AGC of a multi-area power system in deregulated environment. Initially, a two area four units thermal system without any physical constraints is considered and the gains of the PIDF controller are optimized employing Differential Evolution (DE algorithm using ITAE criterion. The superiority of proposed DE optimized PIDF controller over Fuzzy Logic controller is demonstrated. Then, to further improve the system performance, an Interline Power Flow Controller (IPFC is placed in the tie-line and Redox Flow Batteries (RFB is considered in the first area and the controller parameters are tuned. Additionally, to get an accurate insight of the AGC problem, important physical constraints such as Time Delay (TD and Generation Rate Constraints (GRC are considered and the controller parameters are retuned. The performance of proposed controller is evaluated under different operating conditions that take place in a deregulated power market. Further, the proposed approach is extended to a two area six units hydro thermal system. Finally, sensitivity analysis is performed by varying the system parameters and operating load conditions from their nominal values.

Performance enhancement in vanadium redox flow battery using platinum-based electrocatalyst synthesized by polyol process

International Nuclear Information System (INIS)

Jeong, Sanghyun; Kim, Sunhoe; Kwon, Yongchai

2013-01-01

Sluggish reaction rate of [VO] 2+ /[VO 2 ] + redox couple is an obstacle to be addressed in vanadium redox flow battery (VRFB). To improve the slow reaction rate, Pt/C catalyst synthesized by polyol method is suggested. Its catalytic activity, reaction reversibility and charge–discharge performance are evaluated by half cell and single cell tests, while its crystal structure, particle size and particle distribution are measured by XRD and TEM. The XRD and TEM measurements show the polyol Pt/C catalyst has larger electrochemically active surface (EAS) area and smaller particle size than commercial Pt/C catalyst. When catalytic activities of all the catalysts are estimated, the Pt-included catalysts demonstrate high peak current ratio, small peak potential difference and high electron transfer rate constant, confirming that their catalytic activity and reaction reversibility are excellent. In charge–discharge performance tests, the catalysts indicate high efficiencies as well as low overpotential and internal resistance. Excellent performances of the Pt-included catalysts are attributed to positively charged Pts that serve as active sites for activating [VO] 2+ /[VO 2 ] + reaction. Indeed, adoption of the Pt-included catalysts, especially, use of the polyol Pt/C consisting of uniform and small particles helps improve performance of VRFB

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography

DEFF Research Database (Denmark)

Baier, Sina; Damsgaard, Christian Danvad; Klumpp, Michael

2017-01-01

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesi...

Redox environment in stem and differentiated cells: A quantitative approach

Directory of Open Access Journals (Sweden)

O.G. Lyublinskaya

2017-08-01

Full Text Available Stem cells are believed to maintain a specific intracellular redox status through a combination of enhanced removal capacity and limited production of ROS. In the present study, we challenge this assumption by developing a quantitative approach for the analysis of the pro- and antioxidant ability of human embryonic stem cells in comparison with their differentiated descendants, as well as adult stem and non-stem cells. Our measurements showed that embryonic stem cells are characterized by low ROS level, low rate of extracellular hydrogen peroxide removal and low threshold for peroxide-induced cytotoxicity. However, biochemical normalization of these parameters to cell volume/protein leads to matching of normalized values in stem and differentiated cells and shows that tested in the present study cells (human embryonic stem cells and their fibroblast-like progenies, adult mesenchymal stem cells, lymphocytes, HeLa maintain similar intracellular redox status. Based on these observations, we propose to use ROS concentration averaged over the cell volume instead of ROS level as a measure of intracellular redox balance. We show that attempts to use ROS level for comparative analysis of redox status of morphologically different cells could lead to false conclusions. Methods for the assessment of ROS concentration based on flow cytometry analysis with the use of H2DCFDA dye and HyPer, genetically encoded probe for hydrogen peroxide, are discussed. Keywords: Embryonic stem cells, Differentiated cells, ROS, Redox status, H2DCFDA, HyPer, Flow cytometry, Quantitative redox biology

Electrochemical investigation of thermically treated graphene oxides as electrode materials for vanadium redox flow battery

International Nuclear Information System (INIS)

Di Blasi, O.; Briguglio, N.; Busacca, C.; Ferraro, M.; Antonucci, V.; Di Blasi, A.

2015-01-01

Highlights: • Graphene oxide is synthesized at high temperatures in a reducing environment. • Treated graphene oxide-based electrodes are prepared by the wet impregnation method. • Electrochemical performance is evaluated as a function of the physico-chemical properties. - Abstract: Thermically treated graphene oxides (TT-GOs) are synthesized at different temperatures, 100 °C, 150 °C, 200 °C and 300 °C in a reducing environment (20% H 2 /He) and investigated as electrode materials for vanadium redox flow battery (VRFB) applications. The treated graphene oxide-based electrodes are prepared by the wet impregnation method using carbon felt (CF) as support. The main aim is to achieve a suitable distribution of the dispersed graphene oxides on the CF surface in order to investigate the electrocatalytic activity for the VO 2+ /VO 2 + and V 2+ /V 3+ redox reactions in the perspective of a feasible large area electrodes scale-up for battery configuration of practical interest. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are carried out in a three electrode half-cell to characterize the electrochemical properties of the TT-GO-based electrodes. Physico-chemical characterizations are carried out to corroborate the electrochemical results. The TT-GO sample treated at 100 °C (TT-GO-100) shows the highest electrocatalytic activity in terms of peak to peak separation (ΔE = 0.03 V) and current density intensity (∼0.24 A cm −2 at 30 mV/s) both toward the VO 2+ /VO 2 + and V 2+ /V 3+ redox reactions. This result is correlated to the presence of hydroxyl (−OH) and carboxyl (−COOH) species that act as active sites. A valid candidate is individuated as effective anode and cathode electrode in the perspective of electrodes scale-up for battery configuration of practical interest

Design and Evaluation of a Boron Dipyrrin Electrophore for Redox Flow Batteries.

Science.gov (United States)

Heiland, Niklas; Cidarér, Clemens; Rohr, Camilla; Piescheck, Mathias; Ahrens, Johannes; Bröring, Martin; Schröder, Uwe

2017-08-29

A boron dipyrrin (BODIPY) dye was designed as a molecular single-component electrophore for redox flow batteries. All positions of the BODIPY core were assessed on the basis of literature data, in particular cyclic voltammetry and density functional calculations, and a minimum required substitution pattern was designed to provide solubility, aggregation, radical cation and anion stabilities, a large potential window, and synthetic accessibility. In-depth electrochemical and physical studies of this electrophore revealed suitable cathodic behavior and stability of the radical anion but rapid anodic decomposition of the radical cation. The three products that formed under the conditions of controlled oxidative electrolysis were isolated, and their structures were determined by spectroscopy and comparison with a synthetic model compound. From these structures, a benzylic radical reactivity, initiated by one-electron oxidation, was concluded to play the major role in this unexpected decomposition. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An electrochemical study on the positive electrode side of the zinc–cerium hybrid redox flow battery

International Nuclear Information System (INIS)

Nikiforidis, Georgios; Berlouis, Léonard; Hall, David; Hodgson, David

2014-01-01

Highlights: •Elevated temperatures favoured the Ce 3+/4+ reaction on the Pt, Pt–Ir and carbon substrates. •j o increased with temperature over the range 25 °C to 60 °C for all substrates. •Non-porous carbon substrates showed higher reversibility on the Ce 3+/4+ reaction. •Surface degradation of the carbon electrodes occurred due to the high positive potentials. •The Pt–Ir coatings gave the largest j o at 60 °C and appear best suited for use as the positive electrode in the Zn–Ce RFB. -- Abstract: In this study, the electrochemical behaviour of the Ce 3+/4+ redox couple in methanesulfonic acid medium on various electrode substrates was investigated as a function of temperature. Carbon composite electrodes as well as platinum and platinum iridium coated electrodes were studied for their suitability in carrying out the Ce 3+/4+ redox reaction. Cyclic voltammetry in 0.8 mol dm −3 cerium and 4.5 mol dm −3 methanesulfonic acid solution showed that elevated temperatures favoured the Ce 3+ /Ce 4+ reaction on the various platinum and platinum–iridium coated substrates as well as on carbon composite surfaces. The latter electrodes showed better kinetics than the metal coatings but deteriorated badly under the high positive potentials required for the cerium reaction. The exchange current density (j o ), obtained through Tafel extrapolation, polarisation resistance and electrochemical impedance spectroscopy measurements, increased with temperature over the range 25 °C to 60 °C. The Pt–Ir coatings gave the largest j o at 60 °C and appear best suited for use as the positive electrode in the Zn–Ce redox flow battery

Bifunctional xylanases and their potential use in biotechnology

Digital Repository Service at National Institute of Oceanography (India)

Khandeparker, R.; Numan, M.Th.

. J Chromatography 919:389–394 33. Hong SY, Lee JS, Cho KM, Math RK, Kim YH, Hong SJ, Cho YU, Kim H, Yun HD (2006) Assembling a novel bifunctional cel- lulase–xylanase from Thermotoga maritima by end-to-end fusion. Biotechnol Lett 28:1857–1862 34...

The aminoindanol core as a key scaffold in bifunctional organocatalysts

Directory of Open Access Journals (Sweden)

Isaac G. Sonsona

2016-03-01

Full Text Available The 1,2-aminoindanol scaffold has been found to be very efficient, enhancing the enantioselectivity when present in organocatalysts. This may be explained by its ability to induce a bifunctional activation of the substrates involved in the reaction. Thus, it is easy to find hydrogen-bonding organocatalysts ((thioureas, squaramides, quinolinium thioamide, etc. in the literature containing this favored structural core. They have been successfully employed in reactions such as Friedel–Crafts alkylation, Michael addition, Diels–Alder and aza-Henry reactions. However, the 1,2-aminoindanol core incorporated into proline derivatives has been scarcely explored. Herein, the most representative and illustrative examples are compiled and this review will be mainly focused on the cases where the aminoindanol moiety confers bifunctionality to the organocatalysts.

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

Science.gov (United States)

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.

Towards an all-copper redox flow battery based on a copper-containing ionic liquid.

Science.gov (United States)

Schaltin, Stijn; Li, Yun; Brooks, Neil R; Sniekers, Jeroen; Vankelecom, Ivo F J; Binnemans, Koen; Fransaer, Jan

2016-01-07

The first redox flow battery (RFB), based on the all-copper liquid metal salt [Cu(MeCN)4][Tf2N], is presented. Liquid metal salts (LMS) are a new type of ionic liquid that functions both as solvent and electrolyte. Non-aqueous electrolytes have advantages over water-based solutions, such as a larger electrochemical window and large thermal stability. The proof-of-concept is given that LMSs can be used as the electrolyte in RFBs. The main advantage of [Cu(MeCN)4][Tf2N] is the high copper concentration, and thus high charge and energy densities of 300 kC l(-1) and 75 W h l(-1) respectively, since the copper(i) ions form an integral part of the electrolyte. A Coulombic efficiency up to 85% could be reached.

Boosting Bifunctional Oxygen Electrocatalysis with 3D Graphene Aerogel-Supported Ni/MnO Particles.

Science.gov (United States)

Fu, Gengtao; Yan, Xiaoxiao; Chen, Yifan; Xu, Lin; Sun, Dongmei; Lee, Jong-Min; Tang, Yawen

2018-02-01

Electrocatalysts for oxygen-reduction and oxygen-evolution reactions (ORR and OER) are crucial for metal-air batteries, where more costly Pt- and Ir/Ru-based materials are the benchmark catalysts for ORR and OER, respectively. Herein, for the first time Ni is combined with MnO species, and a 3D porous graphene aerogel-supported Ni/MnO (Ni-MnO/rGO aerogel) bifunctional catalyst is prepared via a facile and scalable hydrogel route. The synthetic strategy depends on the formation of a graphene oxide (GO) crosslinked poly(vinyl alcohol) hydrogel that allows for the efficient capture of highly active Ni/MnO particles after pyrolysis. Remarkably, the resulting Ni-MnO/rGO aerogels exhibit superior bifunctional catalytic performance for both ORR and OER in an alkaline electrolyte, which can compete with the previously reported bifunctional electrocatalysts. The MnO mainly contributes to the high activity for the ORR, while metallic Ni is responsible for the excellent OER activity. Moreover, such bifunctional catalyst can endow the homemade Zn-air battery with better power density, specific capacity, and cycling stability than mixed Pt/C + RuO 2 catalysts, demonstrating its potential feasibility in practical application of rechargeable metal-air batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

International Nuclear Information System (INIS)

Li, Hu; Govind, Khokarale Santosh; Kotni, Ramakrishna; Shunmugavel, Saravanamurugan; Riisager, Anders; Yang, Song

2014-01-01

Graphical abstract: Catalytic conversion of carbohydrates into HMF and EMF in ethanol/DMSO with acid–base bifunctional hybrid nanospheres prepared from self-assembly of corresponding basic amino acids and HPA. - Highlights: • Acid–base bifunctional nanospheres were efficient for production of EMF from sugars. • Synthesis of EMF in a high yield of 76.6% was realized from fructose. • Fructose based biopolymers could also be converted into EMF with good yields. • Ethyl glucopyranoside was produced in good yields from glucose in ethanol. - Abstract: A series of acid–base bifunctional hybrid nanospheres prepared from the self-assembly of basic amino acids and phosphotungstic acid (HPA) with different molar ratios were employed as efficient and recyclable catalysts for synthesis of liquid biofuel 5-ethoxymethylfurfural (EMF) from various carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl glucopyranoside in good yields could be obtained from glucose in ethanol. Moreover, the nanocatalyst functionalized with acid and basic sites was able to be reused several times with no significant loss in catalytic activity

Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

Science.gov (United States)

Abrams , Robert H.; Loague, Keith; Kent, Douglas B.

1998-01-01

The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

Carbon felt and carbon fiber - A techno-economic assessment of felt electrodes for redox flow battery applications

Science.gov (United States)

Minke, Christine; Kunz, Ulrich; Turek, Thomas

2017-02-01

Carbon felt electrodes belong to the key components of redox flow batteries. The purpose of this techno-economic assessment is to uncover the production costs of PAN- and rayon-based carbon felt electrodes. Raw material costs, energy demand and the impact of processability of fiber and felt are considered. This innovative, interdisciplinary approach combines deep insights into technical, ecologic and economic aspects of carbon felt and carbon fiber production. Main results of the calculation model are mass balances, cumulative energy demands (CED) and the production costs of conventional and biogenic carbon felts supplemented by market assessments considering textile and carbon fibers.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

An aqueous all-organic redox-flow battery employing a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl-containing polymer as catholyte and dimethyl viologen dichloride as anolyte

Science.gov (United States)

Hagemann, Tino; Winsberg, Jan; Grube, Mandy; Nischang, Ivo; Janoschka, Tobias; Martin, Norbert; Hager, Martin D.; Schubert, Ulrich S.

2018-02-01

Herein we present a new redox-flow battery (RFB) that employs a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) containing copolymer (P1) as catholyte and the viologen derivative N,N‧-dimethyl-4,4‧-bipyridinium dichloride (MV) as anolyte in an aqueous sodium chloride solution. This is the first time that a combination of an organic polymer and a low-molar-mass organic redox-active material is presented. The electrochemical behavior of the utilized charge-storage materials were investigated by cyclic voltammetry (CV) and feature reversible redox-reactions at E½ = 0.7 V (TEMPO/TEMPO+) and E½ = -0.6 V vs. AgCl/Ag (MV++/MV+•), which lead to a promising cell voltage of 1.3 V in the subsequent battery application. Studies were performed to determine the most suitable anion-exchange membrane (AEM), the ideal conducting salt concentration and the optimal flow rate. The resulting battery reveals a stable charge/discharge performance over 100 consecutive cycles with coulombic efficiencies of up to 95%, a high energy efficiency of 85% and an overall energy density of the electrolyte system of 3.8 W h L-1.

Two functionally distinct NADP+-dependent ferredoxin oxidoreductases maintain the primary redox balance of Pyrococcus furiosus.

Science.gov (United States)

Nguyen, Diep M N; Schut, Gerrit J; Zadvornyy, Oleg A; Tokmina-Lukaszewska, Monika; Poudel, Saroj; Lipscomb, Gina L; Adams, Leslie A; Dinsmore, Jessica T; Nixon, William J; Boyd, Eric S; Bothner, Brian; Peters, John W; Adams, Michael W W

2017-09-01

Electron bifurcation has recently gained acceptance as the third mechanism of energy conservation in which energy is conserved through the coupling of exergonic and endergonic reactions. A structure-based mechanism of bifurcation has been elucidated recently for the flavin-based enzyme NADH-dependent ferredoxin NADP + oxidoreductase I (NfnI) from the hyperthermophillic archaeon Pyrococcus furiosus. NfnI is thought to be involved in maintaining the cellular redox balance, producing NADPH for biosynthesis by recycling the two other primary redox carriers, NADH and ferredoxin. The P. furiosus genome encodes an NfnI paralog termed NfnII, and the two are differentially expressed, depending on the growth conditions. In this study, we show that deletion of the genes encoding either NfnI or NfnII affects the cellular concentrations of NAD(P)H and particularly NADPH. This results in a moderate to severe growth phenotype in deletion mutants, demonstrating a key role for each enzyme in maintaining redox homeostasis. Despite their similarity in primary sequence and cofactor content, crystallographic, kinetic, and mass spectrometry analyses reveal that there are fundamental structural differences between the two enzymes, and NfnII does not catalyze the NfnI bifurcating reaction. Instead, it exhibits non-bifurcating ferredoxin NADP oxidoreductase-type activity. NfnII is therefore proposed to be a bifunctional enzyme and also to catalyze a bifurcating reaction, although its third substrate, in addition to ferredoxin and NADP(H), is as yet unknown. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Annulated Dialkoxybenzenes as Catholyte Materials for Non-aqueous Redox Flow Batteries: Achieving High Chemical Stability through Bicyclic Substitution

International Nuclear Information System (INIS)

Zhang, Jingjing; Yang, Zheng; Shkrob, Ilya A.; Assary, Rajeev S.

2017-01-01

1,4-Dimethoxybenzene derivatives are materials of choice for use as catholytes in nonaqueous redox flow batteries, as they exhibit high open-circuit potentials and excellent electrochemical reversibility. However, chemical stability of these materials in their oxidized form needs to be improved. Disubstitution in the arene ring is used to suppress parasitic reactions of their radical cations, but this does not fully prevent ring-addition reactions. By incorporating bicyclic substitutions and ether chains into the dialkoxybenzenes, a novel catholyte molecule, 9,10-bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5, 8-dimethanenoanthracene (BODMA), is obtained and exhibits greater solubility and superior chemical stability in the charged state. As a result, a hybrid flow cell containing BODMA is operated for 150 charge–discharge cycles with minimal loss of capacity.

Flat flow profiles achieved with microfluidics generated by redox-magnetohydrodynamics.

Science.gov (United States)

Sahore, V; Fritsch, I

2013-12-17

Horizontal flow profiles having uniform velocities (3-13% RSD) at fixed heights across 0.5, 2.0, and 5.6 mm widths, with magnitudes of ≤124 μm/s, can be sustained along a ∼25.0 mm path using redox-magnetohydrodynamics (MHD) microfluidic pumping in a small volume (14.3 mm wide × 27.0 mm long × 620 μm high) on a chip. Uniform velocity profiles are important in moving volume elements without shape distortion for assays and separations for lab-on-a-chip applications. Fluid movement resulting from the MHD force (FB = j × B) was monitored with video microscopy by tracking 10 μm, polystyrene latex beads mixed into the solution. The ionic current density, j, was generated in 0.095 M K3Fe(CN)6, 0.095 M K4Fe(CN)6, and 0.095 M KCl by applying a constant current across a 0.5, 2.0, or 5.6 mm gap between an anode-cathode pair of electrodes, consisting of one to four shorted parallel, coplanar gold microbands [each 25.0 mm × 98 μm × ∼100 nm (thickness), and separated by 102 μm] fabricated on an insulated silicon substrate. By shorting the increasing numbers of microbands together, increasing currents (118, 180, 246, and 307 μA) could be applied without electrode damage, and the impact of ionic current density gradients on velocity profiles over the anodes and cathodes could also be investigated. The magnetic field, B, was produced with a 0.36 T NdFeB permanent magnet beneath the chip. Data analysis was performed using particle image velocimetry software. A vertical flow profile was also obtained in the middle of the 5.6 mm gap.

The effects of surface modification on carbon felt electrodes for use in vanadium redox flow batteries

International Nuclear Information System (INIS)

Kim, Ki Jae; Kim, Young-Jun; Kim, Jae-Hun; Park, Min-Sik

2011-01-01

Highlights: ► We observed the physical and chemical changes on the surface of carbon felts after various surface modifications. ► The surface area and chemistry of functional groups formed on the surface of carbon felt are critical to determine the kinetics of the redox reactions of vanadium ions. ► By incorporation of the surface modifications into the electrode preparation, the electrochemical activity of carbon felts could be notably enhanced. - Abstract: The surface of carbon felt electrodes has been modified for improving energy efficiency of vanadium redox flow batteries. For comparative purposes, the effects of various surface modifications such as mild oxidation, plasma treatment, and gamma-ray irradiation on the electrochemical properties of carbon felt electrodes were investigated at optimized conditions. The cell energy efficiency was improved from 68 to 75% after the mild oxidation of the carbon felt at 500 °C for 5 h. This efficiency improvement could be attributed to the increased surface area of the carbon felt electrode and the formation of functional groups on its surface as a result of the modification. On the basis of various structural and electrochemical characterizations, a relationship between the surface nature and electrochemical activity of the carbon felt electrodes is discussed.

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

Science.gov (United States)

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.

All-Iron Redox Flow Battery Tailored for Off-Grid Portable Applications.

Science.gov (United States)

Tucker, Michael C; Phillips, Adam; Weber, Adam Z

2015-12-07

An all-iron redox flow battery is proposed and developed for end users without access to an electricity grid. The concept is a low-cost battery which the user assembles, discharges, and then disposes of the active materials. The design goals are: (1) minimize upfront cost, (2) maximize discharge energy, and (3) utilize non-toxic and environmentally benign materials. These are different goals than typically considered for electrochemical battery technology, which provides the opportunity for a novel solution. The selected materials are: low-carbon-steel negative electrode, paper separator, porous-carbon-paper positive electrode, and electrolyte solution containing 0.5 m Fe2 (SO4 )3 active material and 1.2 m NaCl supporting electrolyte. With these materials, an average power density around 20 mW cm(-2) and a maximum energy density of 11.5 Wh L(-1) are achieved. A simple cost model indicates the consumable materials cost US$6.45 per kWh(-1) , or only US$0.034 per mobile phone charge. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox potentials and kinetics of the Ce 3+/Ce 4+ redox reaction and solubility of cerium sulfates in sulfuric acid solutions

Science.gov (United States)

Paulenova, A.; Creager, S. E.; Navratil, J. D.; Wei, Y.

Experimental work was performed with the aim of evaluating the Ce 4+/Ce 3+ redox couple in sulfuric acid electrolyte for use in redox flow battery (RFB) technology. The solubility of cerium sulfates in 0.1-4.0 M sulfuric acid at 20-60 °C was studied. A synergistic effect of both sulfuric acid concentration and temperature on the solubility of cerous sulfate was observed. The solubility of cerous sulfate significantly decreased with rising concentration of sulfuric acid and rising temperature, while the solubility of ceric sulfate goes through a significant maximum at 40 °C. Redox potentials and the kinetics of the cerous/ceric redox reaction were also studied under the same temperature-concentration conditions. The redox potentials were measured using the combined redox electrode (Pt-Ag/AgCl) in equimolar Ce 4+/Ce 3+ solutions (i.e.[Ce 3+]=[Ce 4+]) in sulfuric acid electrolyte. The Ce 3+/Ce 4+ redox potentials significantly decrease (i.e. shift to more negative values) with rising sulfuric acid concentration; a small maximum is observed at 40 °C. Cyclic voltammetric experiments confirmed slow electrochemical kinetics of the Ce 3+/Ce 4+ redox reaction on carbon glassy electrodes (CGEs) in sulfuric acid solutions. The observed dependencies of solubilities, the redox potentials and the kinetics of Ce 3+/Ce 4+ redox reaction on sulfuric acid concentration are thought to be the result of inequivalent complexation of the two redox species by sulfate anions: the ceric ion is much more strongly bound to sulfate than is the cerous ion. The best temperature-concentration conditions for the RFB electrolytes appear to be 40 °C and 1 M sulfuric acid, where the relatively good solubility of both cerium species, the maximum of redox potentials, and the more or less satisfying stability of CGE s were found. Even so, the relatively low solubility of cerium salts in sulfuric acid media and slow redox kinetics of the Ce 3+/Ce 4+ redox reaction at carbon indicate that the Ce 3+/Ce

Environmentally Benign Bifunctional Solid Acid and Base Catalysts

NARCIS (Netherlands)

Elmekawy, A.; Shiju, N.R.; Rothenberg, G.; Brown, D.R.

2014-01-01

Solid bifunctional acid-​base catalysts were prepd. in two ways on an amorphous silica support: (1) by grafting mercaptopropyl units (followed by oxidn. to propylsulfonic acid) and aminopropyl groups to the silica surface (NH2-​SiO2-​SO3H)​, and (2) by grafting only aminopropyl groups and then

The Redox Code.

Science.gov (United States)

Jones, Dean P; Sies, Helmut

2015-09-20

The redox code is a set of principles that defines the positioning of the nicotinamide adenine dinucleotide (NAD, NADP) and thiol/disulfide and other redox systems as well as the thiol redox proteome in space and time in biological systems. The code is richly elaborated in an oxygen-dependent life, where activation/deactivation cycles involving O₂ and H₂O₂ contribute to spatiotemporal organization for differentiation, development, and adaptation to the environment. Disruption of this organizational structure during oxidative stress represents a fundamental mechanism in system failure and disease. Methodology in assessing components of the redox code under physiological conditions has progressed, permitting insight into spatiotemporal organization and allowing for identification of redox partners in redox proteomics and redox metabolomics. Complexity of redox networks and redox regulation is being revealed step by step, yet much still needs to be learned. Detailed knowledge of the molecular patterns generated from the principles of the redox code under defined physiological or pathological conditions in cells and organs will contribute to understanding the redox component in health and disease. Ultimately, there will be a scientific basis to a modern redox medicine.

Ocular Toxicity Profile of ST-162 and ST-168 as Novel Bifunctional MEK/PI3K Inhibitors.

Science.gov (United States)

Smith, Andrew; Pawar, Mercy; Van Dort, Marcian E; Galbán, Stefanie; Welton, Amanda R; Thurber, Greg M; Ross, Brian D; Besirli, Cagri G

2018-04-30

ST-162 and ST-168 are small-molecule bifunctional inhibitors of MEK and PI3K signaling pathways that are being developed as novel antitumor agents. Previous small-molecule and biologic MEK inhibitors demonstrated ocular toxicity events that were dose limiting in clinical studies. We evaluated in vitro and in vivo ocular toxicity profiles of ST-162 and ST-168. Photoreceptor cell line 661W and adult retinal pigment epithelium cell line ARPE-19 were treated with increasing concentrations of bifunctional inhibitors. Western blots, cell viability, and caspase activity assays were performed to evaluate MEK and PI3K inhibition and dose-dependent in vitro toxicity, and compared with monotherapy. In vivo toxicity profile was assessed by intravitreal injection of ST-162 and ST-168 in Dutch-Belted rabbits, followed by ocular examination and histological analysis of enucleated eyes. Retinal cell lines treated with ST-162 or ST-168 exhibited dose-dependent inhibition of MEK and PI3K signaling. Compared with inhibition by monotherapies and their combinations, bifunctional inhibitors demonstrated reduced cell death and caspase activity. In vivo, both bifunctional inhibitors exhibited a more favorable toxicity profile when compared with MEK inhibitor PD0325901. Novel MEK and PI3K bifunctional inhibitors ST-162 and ST-168 demonstrate favorable in vitro and in vivo ocular toxicity profiles, supporting their further development as potential therapeutic agents targeting multiple aggressive tumors.

Continuous Flow-Resonance Raman Spectroscopy of an Intermediate Redox State of Cytochrome-C

DEFF Research Database (Denmark)

Forster, M.; Hester, R. E.; Cartling, B.

1982-01-01

An intermediate redox state of cytochrome c at alkaline pH, generated upon rapid reduction by sodium dithionite, has been observed by resonance Raman (RR) spectroscopy in combination with the continuous flow technique. The RR spectrum of the intermediate state is reported for excitation both...... in the (alpha, beta) and the Soret optical absorption band. The spectra of the intermediate state are more like those of the stable reduced form than those of the stable oxidized form. For excitation of 514.5 nm, the most prominent indication of an intermediate state is the wave-number shift of one RR band from...... 1,562 cm-1 in the stable oxidized state through 1,535 cm-1 in the intermediate state to 1,544 cm-1 in the stable reduced state. For excitation at 413.1 nm, a band, present at 1,542 cm-1 in the stable reduced state but not present in the stable oxidized state, is absent in the intermediate state. We...

Numerical and experimental studies of stack shunt current for vanadium redox flow battery

International Nuclear Information System (INIS)

Yin, Cong; Guo, Shaoyun; Fang, Honglin; Liu, Jiayi; Li, Yang; Tang, Hao

2015-01-01

Highlights: • A coupled three-dimensional model of VRB cell stack is developed. • Shunt current of the stack is studied with the model and experiment. • Increased electrolyte resistance in channel and manifold lowers the shunt current. • Shunt current loss increases with stack cell number nonlinearly. - Abstract: The stack shunt current of VRB (vanadium redox flow battery) was investigated with experiments and 3D (three-dimensional) simulations. In the proposed model, cell voltages and electrolyte conductivities were calculated based on electrochemical reaction distributions and SOC (state of charge) values, respectively, while coulombic loss was estimated according to shunt current and vanadium ionic crossover through membrane. Shunt current distributions and coulombic efficiency are analyzed in terms of electrolyte conductivities and stack cell numbers. The distributions of cell voltages and shunt currents calculated with proposed model are validated with single cell and short stack tests. The model can be used to optimize VRB stack manifold and channel designs to improve VRB system efficiency

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Redox fronts

International Nuclear Information System (INIS)

Chapman, N.; McKinley, I.; Shea, M.; Smellie, J.

1993-01-01

This article describes the investigations of redox fronts performed at the Osamu Utsumi mine. Results obtained by modelling groups on the rate of movement of the redox fronts and on the chemical reactions involved are discussed. Some of the most important rockwater interactions which occur at redox fronts can be modelled reasonably well but the complex redox chemistry of elements like sulphur is poorly simulated. The observed enrichment of many trace elements close to the redox fronts could be of significance for high-level waste repositories, but cannot be quantified by existing models. (author) 6 figs., 1 tab

Spectroelectrochemical insights into structural and redox properties of immobilized endonuclease III and its catalytically inactive mutant

Science.gov (United States)

Moe, Elin; Rollo, Filipe; Silveira, Célia M.; Sezer, Murat; Hildebrandt, Peter; Todorovic, Smilja

2018-01-01

Endonuclease III is a Fe-S containing bifunctional DNA glycosylase which is involved in the repair of oxidation damaged DNA. Here we employ surface enhanced IR spectroelectrochemistry and electrochemistry to study the enzyme from the highly radiation- and desiccation-resistant bacterium Deinococcus radiodurans (DrEndoIII2). The experiments are designed to shed more light onto specific parameters that are currently proposed to govern damage search and recognition by endonucleases III. We demonstrate that electrostatic interactions required for the redox activation of DrEndoIII2 may result in high electric fields that alter its structural and thermodynamic properties. Analysis of inactive DrEndoIII2 (K132A/D150A double mutant) interacting with undamaged DNA, and the active enzyme interacting with damaged DNA also indicate that the electron transfer is modulated by subtle differences in the protein-DNA complex.

Endothelial Mechanotransduction, Redox Signaling and the Regulation of Vascular Inflammatory Pathways

Directory of Open Access Journals (Sweden)

Shampa Chatterjee

2018-06-01

Full Text Available The endothelium that lines the interior of blood vessels is directly exposed to blood flow. The shear stress arising from blood flow is “sensed” by the endothelium and is “transduced” into biochemical signals that eventually control vascular tone and homeostasis. Sensing and transduction of physical forces occur via signaling processes whereby the forces associated with blood flow are “sensed” by a mechanotransduction machinery comprising of several endothelial cell elements. Endothelial “sensing” involves converting the physical cues into cellular signaling events such as altered membrane potential and activation of kinases, which are “transmission” signals that cause oxidant production. Oxidants produced are the “transducers” of the mechanical signals? What is the function of these oxidants/redox signals? Extensive data from various studies indicate that redox signals initiate inflammation signaling pathways which in turn can compromise vascular health. Thus, inflammation, a major response to infection or endotoxins, can also be initiated by the endothelium in response to various flow patterns ranging from aberrant flow to alteration of flow such as cessation or sudden increase in blood flow. Indeed, our work has shown that endothelial mechanotransduction signaling pathways participate in generation of redox signals that affect the oxidant and inflammation status of cells. Our goal in this review article is to summarize the endothelial mechanotransduction pathways that are activated with stop of blood flow and with aberrant flow patterns; in doing so we focus on the complex link between mechanical forces and inflammation on the endothelium. Since this “inflammation susceptible” phenotype is emerging as a trigger for pathologies ranging from atherosclerosis to rejection post-organ transplant, an understanding of the endothelial machinery that triggers these processes is very crucial and timely.

Vanadium redox flow batteries to reach greenhouse gas emissions targets in an off-grid configuration

International Nuclear Information System (INIS)

Arbabzadeh, Maryam; Johnson, Jeremiah X.; De Kleine, Robert; Keoleian, Gregory A.

2015-01-01

Highlights: • We assess energy storage role in reaching emissions targets in an off-grid model. • The energy storage technology is vanadium redox flow battery (VRFB). • We evaluate life cycle GHG emissions and total cost of delivered electricity. • Generation mixes are optimized to meet emissions targets at the minimum cost. • For this model, integrating VRFB is economical to reach very low emissions targets. - Abstract: Energy storage may serve as a solution to the integration challenges of high penetrations of wind, helping to reduce curtailment, provide system balancing services, and reduce emissions. This study determines the minimum cost configuration of vanadium redox flow batteries (VRFB), wind turbines, and natural gas reciprocating engines in an off-grid model. A life cycle assessment (LCA) model is developed to determine the system configuration needed to achieve a variety of CO 2 -eq emissions targets. The relationship between total system costs and life cycle emissions are used to optimize the generation mixes to achieve emissions targets at the least cost and determine when VRFBs are preferable over wind curtailment. Different greenhouse gas (GHG) emissions targets are defined for the off-grid system and the minimum cost resource configuration is determined to meet those targets. This approach determines when the use of VRFBs is more cost effective than wind curtailment in reaching GHG emissions targets. The research demonstrates that while incorporating energy storage consistently reduces life cycle carbon emissions, it is not cost effective to reduce curtailment except under very low emission targets (190 g of CO2-eq/kW h and less for the examined system). This suggests that “overbuilding” wind is a more viable option to reduce life cycle emissions for all but the most ambitious carbon mitigation targets. The findings show that adding VRFB as energy storage could be economically preferable only when wind curtailment exceeds 66% for the

Bifunctional electrodes for unitised regenerative fuel cells

International Nuclear Information System (INIS)

Altmann, Sebastian; Kaz, Till; Friedrich, Kaspar Andreas

2011-01-01

Research highlights: → Different oxygen electrode configurations for the operation in a unitised reversible fuel cell were tested. → Polarisation curves and EIS measurements were recorded. → The mixture of catalysts performs best for the present stage of electrode development. → Potential improvements for the different compositions are discussed. - Abstract: The effects of different configurations and compositions of platinum and iridium oxide electrodes for the oxygen reaction of unitised regenerative fuel cells (URFC) are reported. Bifunctional oxygen electrodes are important for URFC development because favourable properties for the fuel cell and the electrolysis modes must be combined into a single electrode. The bifunctional electrodes were studied under different combinations of catalyst mixtures, multilayer arrangements and segmented configurations with single catalyst areas. Distinct electrochemical behaviour was observed for both modes and can be explained on the basis of impedance spectroscopy. The mixture of both catalysts performs best for the present stage of electrode development. Also, the multilayer electrodes yielded good results with the potential for optimisation. The influence of ionic and electronic resistances on the relative performance is demonstrated. However, penalties due to cross currents in the heterogeneous electrodes were identified and explained by comparing the performance curves with electrodes composed of a single catalyst. Potential improvements for the different compositions are discussed.

Assessment of the use of vanadium redox flow batteries for energy storage and fast charging of electric vehicles in gas stations

International Nuclear Information System (INIS)

Cunha, Álvaro; Brito, F.P.; Martins, Jorge; Rodrigues, Nuno; Monteiro, Vitor; Afonso, João L.; Ferreira, Paula

2016-01-01

A network of conveniently located fast charging stations is one of the possibilities to facilitate the adoption of Electric Vehicles (EVs). This paper assesses the use of fast charging stations for EVs in conjunction with VRFBs (Vanadium Redox Flow Batteries). These batteries are charged during low electricity demand periods and then supply electricity for the fast charging of EVs during day, thus implementing a power peak shaving process. Flow batteries have unique characteristics which make them especially attractive when compared with conventional batteries, such as their ability to decouple rated power from rated capacity, as well as their greater design flexibility and nearly unlimited life. Moreover, their liquid nature allows their installation inside deactivated underground gas tanks located at gas stations, enabling a smooth transition of gas stations' business model towards the emerging electric mobility paradigm. A project of a VRFB system to fast charge EVs taking advantage of existing gas stations infrastructures is presented. An energy and cost analysis of this concept is performed, which shows that, for the conditions tested, the project is technologically and economically viable, although being highly sensitive to the investment costs and to the electricity market conditions. - Highlights: • Assessment of Vanadium Redox Flow Battery use for EV fast charge in gas stations. • This novel system proposal allows power peak shaving and use of deactivated gas tanks. • Philosophy allows seamless business transition towards the Electric Mobility paradigm. • Project is technologically and economically viable, although with long payback times. • Future Cost cuts due to technology maturation will consolidate project attractiveness.

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

Science.gov (United States)

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.

Information processing through a bio-based redox capacitor: signatures for redox-cycling.

Science.gov (United States)

Liu, Yi; Kim, Eunkyoung; White, Ian M; Bentley, William E; Payne, Gregory F

2014-08-01

Redox-cycling compounds can significantly impact biological systems and can be responsible for activities that range from pathogen virulence and contaminant toxicities, to therapeutic drug mechanisms. Current methods to identify redox-cycling activities rely on the generation of reactive oxygen species (ROS), and employ enzymatic or chemical methods to detect ROS. Here, we couple the speed and sensitivity of electrochemistry with the molecular-electronic properties of a bio-based redox-capacitor to generate signatures of redox-cycling. The redox capacitor film is electrochemically-fabricated at the electrode surface and is composed of a polysaccharide hydrogel with grafted catechol moieties. This capacitor film is redox-active but non-conducting and can engage diffusible compounds in either oxidative or reductive redox-cycling. Using standard electrochemical mediators ferrocene dimethanol (Fc) and Ru(NH3)6Cl3 (Ru(3+)) as model redox-cyclers, we observed signal amplifications and rectifications that serve as signatures of redox-cycling. Three bio-relevant compounds were then probed for these signatures: (i) ascorbate, a redox-active compound that does not redox-cycle; (ii) pyocyanin, a virulence factor well-known for its reductive redox-cycling; and (iii) acetaminophen, an analgesic that oxidatively redox-cycles but also undergoes conjugation reactions. These studies demonstrate that the redox-capacitor can enlist the capabilities of electrochemistry to generate rapid and sensitive signatures of biologically-relevant chemical activities (i.e., redox-cycling). Published by Elsevier B.V.

Sorption of Pu(IV) from nitric acid by bifunctional anion-exchange resins

International Nuclear Information System (INIS)

Bartsch, R.A.; Zhang, Z.Y.; Elshani, S.; Zhao, W.; Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.; Chamberlin, R.M.

1999-01-01

Anion exchange is attractive for separating plutonium because the Pu(IV) nitrate complex is very strongly sorbed and few other metal ions form competing anionic nitrate complexes. The major disadvantage of this process has been the unusually slow rate at which the Pu(IV) nitrate complex is sorbed by the resin. The paper summarizes the concept of bifunctional anion-exchange resins, proposed mechanism for Pu(IV) sorption, synthesis of the alkylating agent, calculation of K d values from Pu(IV) sorption results, and conclusions from the study of Pu(IV) sorption from 7M nitric acid by macroporous anion-exchange resins including level of crosslinking, level of alkylation, length of spacer, and bifunctional vs. monofunctional anion-exchange resins

Bifunctional fluorescent probes for detection of amyloid aggregates and reactive oxygen species.

Science.gov (United States)

Needham, Lisa-Maria; Weber, Judith; Fyfe, James W B; Kabia, Omaru M; Do, Dung T; Klimont, Ewa; Zhang, Yu; Rodrigues, Margarida; Dobson, Christopher M; Ghandi, Sonia; Bohndiek, Sarah E; Snaddon, Thomas N; Lee, Steven F

2018-02-01

Protein aggregation into amyloid deposits and oxidative stress are key features of many neurodegenerative disorders including Parkinson's and Alzheimer's disease. We report here the creation of four highly sensitive bifunctional fluorescent probes, capable of H 2 O 2 and/or amyloid aggregate detection. These bifunctional sensors use a benzothiazole core for amyloid localization and boronic ester oxidation to specifically detect H 2 O 2 . We characterized the optical properties of these probes using both bulk fluorescence measurements and single-aggregate fluorescence imaging, and quantify changes in their fluorescence properties upon addition of amyloid aggregates of α-synuclein and pathophysiological H 2 O 2 concentrations. Our results indicate these new probes will be useful to detect and monitor neurodegenerative disease.

Bifunctional fluorescent probes for detection of amyloid aggregates and reactive oxygen species

Science.gov (United States)

Needham, Lisa-Maria; Weber, Judith; Fyfe, James W. B.; Kabia, Omaru M.; Do, Dung T.; Klimont, Ewa; Zhang, Yu; Rodrigues, Margarida; Dobson, Christopher M.; Ghandi, Sonia; Bohndiek, Sarah E.; Snaddon, Thomas N.; Lee, Steven F.

2018-02-01

Protein aggregation into amyloid deposits and oxidative stress are key features of many neurodegenerative disorders including Parkinson's and Alzheimer's disease. We report here the creation of four highly sensitive bifunctional fluorescent probes, capable of H2O2 and/or amyloid aggregate detection. These bifunctional sensors use a benzothiazole core for amyloid localization and boronic ester oxidation to specifically detect H2O2. We characterized the optical properties of these probes using both bulk fluorescence measurements and single-aggregate fluorescence imaging, and quantify changes in their fluorescence properties upon addition of amyloid aggregates of α-synuclein and pathophysiological H2O2 concentrations. Our results indicate these new probes will be useful to detect and monitor neurodegenerative disease.

Astaxanthin diferulate as a bifunctional antioxidant

DEFF Research Database (Denmark)

Papa, T.B.R.; Pinho, V.D.; Nascimento, E.P. do

2015-01-01

Abstract Astaxanthin when esterified with ferulic acid is better singlet oxygen quencher with k2 = (1.58 ± 0.1) 10(10) L mol(- 1)s(- 1) in ethanol at 25°C compared with astaxanthin with k2 = (1.12 ± 0.01) 10(9) L mol(- 1)s(- 1). The ferulate moiety in the astaxanthin diester is a better radical....... The mutual enhancement of antioxidant activity for the newly synthetized astaxanthin diferulate becoming a bifunctional antioxidant is rationalized according to a two-dimensional classification plot for electron donation and electron acceptance capability....

Ce(III)/Ce(IV) in methanesulfonic acid as the positive half cell of a redox flow battery

International Nuclear Information System (INIS)

Leung, P.K.; Ponce de Leon, C.; Low, C.T.J.; Walsh, F.C.

2011-01-01

The characteristics of the Ce(III)/Ce(IV) redox couple in methanesulfonic acid were studied at a platinum disk electrode (0.125 cm 2 ) over a wide range of electrolyte compositions and temperatures: cerium (III) methanesulfonate (0.1-1.2 mol dm -3 ), methanesulfonic acid (0.1-5.0 mol dm -3 ) and electrolyte temperatures (295-333 K). The cyclic voltammetry experiments indicated that the diffusion coefficient of Ce(III) ions was 0.5 x 10 -6 cm 2 s -1 and that the electrochemical kinetics for the oxidation of Ce(III) and the reduction of Ce(IV) was slow. The reversibility of the redox reaction depended on the electrolyte composition and improved at higher electrolyte temperatures. At higher methanesulfonic acid concentrations, the degree of oxygen evolution decreased by up to 50% when the acid concentration increased from 2 to 5 mol dm -3 . The oxidation of Ce(III) and reduction of Ce(IV) were also investigated during a constant current batch electrolysis in a parallel plate zinc-cerium flow cell with a 3-dimensional platinised titanium mesh electrode. The current efficiencies over 4.5 h of the process Ce(III) to Ce(IV) and 3.3 h electrolysis of the reverse reaction Ce(IV) to Ce(III) were 94.0 and 97.6%, respectively. With a 2-dimensional, planar platinised titanium electrode (9 cm 2 area), the redox reaction of the Ce(III)/Ce(IV) system was under mass-transport control, while the reaction on the 3-dimensional mesh electrode was initially under charge-transfer control but became mass-transport controlled after 2.5-3 h of electrolysis. The effect of the side reactions (hydrogen and oxygen evolution) on the current efficiencies and the conversion of Ce(III) and Ce(IV) are discussed.

Untersuchungen an a-C:H:Me beschichteten Substraten zur Eignung als alternatives Bipolarplattenmaterial für wässrige Vanadium Redox-Flow Batterien

OpenAIRE

Richards, Justin

2015-01-01

Für den Auf- und Ausbau der erneuerbaren Energien sind zentrale und dezentrale Zwischenspeicherlösungen unabdingbar. Eine potentielle Technologie ist die All-Vanadium Redox-Flow Batterie. Ein essentieller Schritt für den kommerziellen Durchbruch dieser Batterie-Technologie vom Prototypenstatus zur Serienfertigung ist die Entwicklung eines kostengünstigen, elektrisch hochleitfähigen und elektrochemisch stabilen beschichteten metallischen Materials für die inneren Stromableiter (Bipolarplatten)...

Redox behaviors of iron by absorption spectroscopy and redox potential measurement

International Nuclear Information System (INIS)

Oh, Jae Yong

2010-02-01

This work is performed to study the redox (reduction/oxidation) behaviors of iron in aqueous system by a combination of absorption spectroscopy and redox potential measurements. There are many doubts on redox potential measurements generally showing low accuracies and high uncertainties. In the present study, redox potentials are measured by utilizing various redox electrodes such as Pt, Au, Ag, and glassy carbon (GC) electrodes. Measured redox potentials are compared with calculated redox potentials based on the chemical oxidation speciation of iron and thermodynamic data by absorption spectroscopy, which provides one of the sensitive and selective spectroscopic methods for the chemical speciation of Fe(II/III). From the comparison analyses, redox potential values measured by the Ag redox electrode are fairly consistent with those calculated by the chemical aqueous speciation of iron in the whole system. In summary, the uncertainties of measured redox potentials are closely related with the total Fe concentration and affected by the formation of mixed potentials due to Fe(III) precipitates in the pH range of 6 ∼ 9 beyond the solubility of Fe(III), whilst being independent of the initially prepared concentration ratios between Fe(II) and Fe(III)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

Plant redox proteomics

DEFF Research Database (Denmark)

Navrot, Nicolas; Finnie, Christine; Svensson, Birte

2011-01-01

PTMs in regulating enzymatic activities and controlling biological processes in plants. Notably, proteins controlling the cellular redox state, e.g. thioredoxin and glutaredoxin, appear to play dual roles to maintain oxidative stress resistance and regulate signal transduction pathways via redox PTMs......In common with other aerobic organisms, plants are exposed to reactive oxygen species resulting in formation of post-translational modifications related to protein oxidoreduction (redox PTMs) that may inflict oxidative protein damage. Accumulating evidence also underscores the importance of redox....... To get a comprehensive overview of these types of redox-regulated pathways there is therefore an emerging interest to monitor changes in redox PTMs on a proteome scale. Compared to some other PTMs, e.g. protein phosphorylation, redox PTMs have received less attention in plant proteome analysis, possibly...

Untersuchung alternativer Elektrolyte und Membranen für die Vanadium-Redox-Flow-Batterie sowie die Kopplung der Batterie mit der photoelektrochemischen Wasserspaltung

OpenAIRE

Schley (geb. Baumgarten), Julia

2017-01-01

Für die Leistung einer Vanadium-Redox-Flow-Batterie (VRFB) sind die Funktionskomponenten Elektrode, Separator und Elektrolyt von entscheidender Bedeutung. In der konventionellen VRFB wird als Elektrolyt meist ein Vanadiumsulfatsalz, das in Schwefelsäure gelöst ist, verwendet. Da dieses aber nur eine begrenzte Löslichkeit aufweist, ist die Energiedichte der Batterie ebenfalls begrenzt. In der vorliegenden Arbeit wurde deshalb ein HCl-Elektrolytsystem untersucht, das eine erhöhte Löslichkeit fü...

A hydrogen-ferric ion rebalance cell operating at low hydrogen concentrations for capacity restoration of iron-chromium redox flow batteries

Science.gov (United States)

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

2017-06-01

To eliminate the adverse impacts of hydrogen evolution on the capacity of iron-chromium redox flow batteries (ICRFBs) during the long-term operation and ensure the safe operation of the battery, a rebalance cell that reduces the excessive Fe(III) ions at the positive electrolyte by using the hydrogen evolved from the negative electrolyte is designed, fabricated and tested. The effects of the flow field, hydrogen concentration and H2/N2 mixture gas flow rate on the performance of the hydrogen-ferric ion rebalance cell have been investigated. Results show that: i) an interdigitated flow field based rebalance cell delivers higher limiting current densities than serpentine flow field based one does; ii) the hydrogen utilization can approach 100% at low hydrogen concentrations (≤5%); iii) the apparent exchange current density of hydrogen oxidation reaction in the rebalance cell is proportional to the square root of the hydrogen concentration at the hydrogen concentration from 1.3% to 50%; iv) a continuous rebalance process is demonstrated at the current density of 60 mA cm-2 and hydrogen concentration of 2.5%. Moreover, the cost analysis shows that the rebalance cell is just approximately 1% of an ICRFB system cost.

Determination of dissolution rates of spent fuel in carbonate solutions under different redox conditions with a flow-through experiment

International Nuclear Information System (INIS)

Roellin, S.; Spahiu, K.; Eklund, U.-B.

2001-01-01

Dissolution rates of spent UO 2 fuel have been investigated using flow-through experiments under oxidizing, anoxic and reducing conditions. For oxidizing conditions, approximately congruent dissolution rates were obtained in the pH range 3-9.3 for U, Np, Ba, Tc, Cs, Sr and Rb. For these elements, steady-state conditions were obtained in the flow rate range 0.02-0.3 ml min -1 . The dissolution rates were about 3 mg d -1 m -2 for pH>6. For pH 2 (g) saturated solutions dropped by up to four orders of magnitude as compared to oxidizing conditions. Because of the very low concentrations, only U, Pu, Am, Mo, Tc and Cs could be measured. For anoxic conditions, both the redox potential and dissolution rates increased approaching the same values as under oxidizing conditions

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

Science.gov (United States)

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.

Physically-based impedance modeling of the negative electrode in All-Vanadium Redox Flow Batteries: insight into mass transport issues

International Nuclear Information System (INIS)

Zago, M.; Casalegno, A.

2017-01-01

Highlights: •Performance losses induced by migration though the porous electrode are negligible. •Convection at carbon fiber results in a linear branch at low frequency in Nyquist plot. •When the reaction is concentrated, diffusion losses though the electrode diminishes. •Diffusion process in the pores becomes more limiting at high current. •Charge transfer resistance decreases with increasing current. -- Abstract: Mass transport of the electrolyte over the porous electrode is one of the most critical issues hindering Vanadium Redox Flow Battery commercialization, leading to increased overpotential at high current and limiting system power density. In this work, a 1D physically based impedance model of Vanadium Redox Flow Battery negative electrode is developed, taking into account electrochemical reactions, convection at carbon fiber, diffusion in the pores and migration and diffusion through electrode thickness. The model is validated with respect to experimental data measured in a symmetric cell hardware, which allows to keep the State of Charge constant during the measurement. The physically based approach permits to elucidate the origin of different impedance features and quantify the corresponding losses. Charge transfer resistance decreases with increasing current and is generally lower compared to the ones related to mass transport phenomena. Migration losses through the porous electrode are negligible, while convection at carbon fiber is relevant and in Nyquist plot results in a linear branch at low frequency. In presence of significant convection losses the reaction tends to concentrate close to the channel: this leads to a reduction of diffusion losses through the electrode, while diffusion process in the pores becomes more limiting.

Bifunctional bridging linker-assisted synthesis and characterization of TiO{sub 2}/Au nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Žunič, Vojka, E-mail: vojka.zunic@ijs.si, E-mail: vojka13@gmail.com; Kurtjak, Mario; Suvorov, Danilo [Jožef Stefan Institute, Advanced Materials Department (Slovenia)

2016-11-15

Using a simple organic bifunctional bridging linker, titanium dioxide (TiO{sub 2}) nanoparticles were coupled with the Au nanoparticles to form TiO{sub 2}/Au nanocomposites with a variety of Au loadings. This organic bifunctional linker, meso-2,3-dimercaptosuccinic acid, contains two types of functional groups: (i) the carboxyl group, which enables binding to the TiO{sub 2}, and (ii) the thiol group, which enables binding to the Au. In addition, the organic bifunctional linker acts as a stabilizing agent to prevent the agglomeration and growth of the Au particles, resulting in the formation of highly dispersed Au nanoparticles. To form the TiO{sub 2}/Au nanocomposites in a simple way, we deliberately applied a synthetic method that simultaneously ensures: (i) the capping of the Au nanoparticles and (ii) the binding of different amounts of Au to the TiO{sub 2}. The TiO{sub 2}/Au nanocomposites formed with this method show enhanced UV and Vis photocatalytic activities when compared to the pure TiO{sub 2} nanopowders.Graphical Abstract.

Vanadium Electrolyte Studies for the Vanadium Redox Battery-A Review.

Science.gov (United States)

Skyllas-Kazacos, Maria; Cao, Liuyue; Kazacos, Michael; Kausar, Nadeem; Mousa, Asem

2016-07-07

The electrolyte is one of the most important components of the vanadium redox flow battery and its properties will affect cell performance and behavior in addition to the overall battery cost. Vanadium exists in several oxidation states with significantly different half-cell potentials that can produce practical cell voltages. It is thus possible to use the same element in both half-cells and thereby eliminate problems of cross-contamination inherent in all other flow battery chemistries. Electrolyte properties vary with supporting electrolyte composition, state-of-charge, and temperature and this will impact on the characteristics, behavior, and performance of the vanadium battery in practical applications. This Review provides a broad overview of the physical properties and characteristics of the vanadium battery electrolyte under different conditions, together with a description of some of the processing methods that have been developed to produce vanadium electrolytes for vanadium redox flow battery applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Properties of Current Collector in the All-vanadium Redox Flow Battery

International Nuclear Information System (INIS)

Hwang, Gan-Jin; Oh, Yong-Hwan; Ryu, Cheol-Hwi; Choi, Ho-Sang

2014-01-01

Two commercial carbon plates were evaluated as a current collector (bipolar plate) in the all vanadium redox-flow battery (V-RFB). The performance properties of V-RFB were test in the current density of 60 mA/cm 2 . The electromotive forces (OCV at SOC 100%) of V-RFB using A and B current collector were 1.47 V and 1.54 V. The cell resistance of V-RFB using A current collector was 4.44-5.00 Ω·cm 2 and 3.28-3.75 Ω·cm 2 for charge and discharge, respectively. The cell resistance of V-RFB using B current collector was 4.19-4.42Ω·cm 2 and 4.71-5.49Ω·cm 2 for charge and discharge, respectively. The performance of V-RFB using each current collector was evaluated. The performance of V-RFB using A current collector was 93.1%, 76.8% and 71.4% for average current efficiency, average voltage efficiency and average energy efficiency, respectively. The performance of V-RFB using B current collector was 96.4%, 73.6% and 71.0% for average current efficiency, average voltage efficiency and average energy efficiency, respectively

Highly enhanced electrochemical activity of Ni foam electrodes decorated with nitrogen-doped carbon nanotubes for non-aqueous redox flow batteries

Science.gov (United States)

Lee, Jungkuk; Park, Min-Sik; Kim, Ki Jae

2017-02-01

Nitrogen-doped carbon nanotubes (NCNTs) are directly grown on the surface of a three-dimensional (3D) Ni foam substrate by floating catalytic chemical vapor deposition (FCCVD). The electrochemical properties of the 3D NCNT-Ni foam are thoroughly examined as a potential electrode for non-aqueous redox flow batteries (RFBs). During synthesis, nitrogen atoms can be successfully doped onto the carbon nanotube (CNT) lattices by forming an abundance of nitrogen-based functional groups. The 3D NCNT-Ni foam electrode exhibits excellent electrochemical activities toward the redox reactions of [Fe (bpy)3]2+/3+ (in anolyte) and [Co(bpy)3]+/2+ (in catholyte), which are mainly attributed to the hierarchical 3D structure of the NCNT-Ni foam electrode and the catalytic effect of nitrogen atoms doped onto the CNTs; this leads to faster mass transfer and charge transfer during operation. As a result, the RFB cell assembled with 3D NCNT-Ni foam electrodes exhibits a high energy efficiency of 80.4% in the first cycle; this performance is maintained up to the 50th cycle without efficiency loss.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Effects of SOC-dependent electrolyte viscosity on performance of vanadium redox flow batteries

International Nuclear Information System (INIS)

Xu, Q.; Zhao, T.S.; Zhang, C.

2014-01-01

Highlights: • The correlations of electrolyte viscosity and SOC are obtained. • Effect of SOC-dependent electrolyte viscosity is considered in this model. • This model enables a more realistic simulation of variable distributions. • It provides accurate estimations of pumping work and system efficiency. - Abstract: The viscosity of the electrolyte in vanadium redox flow batteries (VRFBs) varies during charge and discharge as the concentrations of acid and vanadium ions in the electrolyte continuously change with the state of charge (SOC). In previous VRFB models, however, the electrolyte has been treated as a constant-viscosity solution. In this work, a mass-transport and electrochemical model taking account of the effect of SOC-dependent electrolyte viscosity is developed. The comparison between the present model and the model with the constant-viscosity simplification indicates that the consideration of the SOC-dependent electrolyte viscosity enables (i) a more realistic simulation of the distributions of overpotential and current density in the electrodes, and (ii) more accurate estimations of pumping work and the system efficiency of VRFBs

Zinc deposition and dissolution in methanesulfonic acid onto a carbon composite electrode as the negative electrode reactions in a hybrid redox flow battery

International Nuclear Information System (INIS)

Leung, P.K.; Ponce-de-Leon, C.; Low, C.T.J.; Walsh, F.C.

2011-01-01

Highlights: → Use methanesulfonic acid to avoid dendrite formation during a long (>4 h) zinc electrodeposition. → Electrochemical characterization of Zn(II) deposition and its morphology using methanesulfonic acid solutions. → Use of additives to improve the efficiency of zinc deposition and dissolution as the half cell reaction of a redox flow battery. - Abstract: Electrodeposition and dissolution of zinc in methanesulfonic acid were studied as the negative electrode reactions in a hybrid redox flow battery. Cyclic voltammetry at a rotating disk electrode was used to characterize the electrochemistry and the effect of process conditions on the deposition and dissolution rate of zinc in aqueous methanesulfonic acid. At a sufficiently high current density, the deposition process became a mass transport controlled reaction. The diffusion coefficient of Zn 2+ ions was 7.5 x 10 -6 cm 2 s -1 . The performance of the zinc negative electrode in a parallel plate flow cell was also studied as a function of Zn 2+ ion concentration, methanesulfonic acid concentration, current density, electrolyte flow rate, operating temperature and the addition of electrolytic additives, including potassium sodium tartarate, tetrabutylammonium hydroxide, and indium oxide. The current-, voltage- and energy efficiencies of the zinc-half cell reaction and the morphologies of the zinc deposits are also discussed. The energy efficiency improved from 62% in the absence of additives to 73% upon the addition of 2 x 10 -3 mol dm -3 of indium oxide as a hydrogen suppressant. In aqueous methanesulfonic acid with or without additives, there was no significant dendrite formation after zinc electrodeposition for 4 h at 50 mA cm -2 .

Synthesis and properties of novel sulfonated poly(arylene ether sulfone) ionomers for vanadium redox flow battery

Energy Technology Data Exchange (ETDEWEB)

Chen, Dongyang; Wang, Shuanjin; Xiao, Min; Meng, Yuezhong [The Key Laboratory of Low-carbon Chemistry and Energy Conservation of Guangdong Province, Institute of Optoelectronic and Functional Composite Materials, Sun Yat-Sen University, Guangzhou 510275 (China)

2010-12-15

Novel sulfonated poly(arylene ether sulfone)s with electron-withdrawing sulfone groups in each repeat unit were synthesized via step polymerization followed by post-sulfonation using chlorosulfonic acid. The sulfonation degree can be readily controlled by adjusting the feed ratio of the repeat unit of polymers to chlorosulfonic acid. The synthesized polymers are soluble in common aprotic solvents such as dimethyl sulfoxide, N,N'-dimethylacetamide and dimethylformamide, and can be cast into transparent membranes from their solutions. The ion exchange capacity, water uptake, swelling ratio, sulfonation degree, mechanical property, oxidative property, thermal property and proton conductivity were investigated in detail using different methodologies. As an objective to apply these polymers as separators for vanadium redox flow battery, the VO{sup 2+} permeability and cell performance for the single cell were examined and assessed. (author)

Synthesis and properties of novel sulfonated poly(arylene ether sulfone) ionomers for vanadium redox flow battery

Energy Technology Data Exchange (ETDEWEB)

Chen Dongyang [Key Laboratory of Low-carbon Chemistry and Energy Conservation of Guangdong Province, Institute of Optoelectronic and Functional Composite Materials, Sun Yat-Sen University, Guangzhou 510275 (China); Wang Shuanjin, E-mail: wangshj@mail.sysu.edu.c [Key Laboratory of Low-carbon Chemistry and Energy Conservation of Guangdong Province, Institute of Optoelectronic and Functional Composite Materials, Sun Yat-Sen University, Guangzhou 510275 (China); Xiao Min [Key Laboratory of Low-carbon Chemistry and Energy Conservation of Guangdong Province, Institute of Optoelectronic and Functional Composite Materials, Sun Yat-Sen University, Guangzhou 510275 (China); Meng Yuezhong, E-mail: mengyzh@mail.sysu.edu.c [Key Laboratory of Low-carbon Chemistry and Energy Conservation of Guangdong Province, Institute of Optoelectronic and Functional Composite Materials, Sun Yat-Sen University, Guangzhou 510275 (China)

2010-12-15

Novel sulfonated poly(arylene ether sulfone)s with electron-withdrawing sulfone groups in each repeat unit were synthesized via step polymerization followed by post-sulfonation using chlorosulfonic acid. The sulfonation degree can be readily controlled by adjusting the feed ratio of the repeat unit of polymers to chlorosulfonic acid. The synthesized polymers are soluble in common aprotic solvents such as dimethyl sulfoxide, N,N'-dimethylacetamide and dimethylformamide, and can be cast into transparent membranes from their solutions. The ion exchange capacity, water uptake, swelling ratio, sulfonation degree, mechanical property, oxidative property, thermal property and proton conductivity were investigated in detail using different methodologies. As an objective to apply these polymers as separators for vanadium redox flow battery, the VO{sup 2+} permeability and cell performance for the single cell were examined and assessed.

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

Science.gov (United States)

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.

Bifunctional catalysts for the direct production of liquid fuels from syngas

NARCIS (Netherlands)

Sartipi, S.

2014-01-01

Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve

Iminodiacetic acid as bifunctional linker for dimerization of cyclic RGD peptides

International Nuclear Information System (INIS)

Xu, Dong; Zhao, Zuo-Quan; Chen, Shu-Ting; Yang, Yong; Fang, Wei; Liu, Shuang

2017-01-01

Introduction: In this study, I2P-RGD 2 was used as the example to illustrate a novel approach for dimerization of cyclic RGD peptides. The main objective of this study was to explore the impact of bifunctional linkers (glutamic acid vs. iminodiacetic acid) on tumor-targeting capability and excretion kinetics of the 99m Tc-labeled dimeric cyclic RGD peptides. Methods: HYNIC-I2P-RGD 2 was prepared by reacting I2P-RGD 2 with HYNIC-OSu in the presence of diisopropylethylamine, and was evaluated for its α v β 3 binding affinity against 125 I-echistatin bound to U87MG glioma cells. 99m Tc-I2P-RGD 2 was prepared with high specific activity (~185 GBq/μmol). The athymic nude mice bearing U87MG glioma xenografts were used to evaluate its biodistribution properties and image quality in comparison with those of 99m Tc-3P-RGD 2 . Results: The IC 50 value for HYNIC-I2P-RGD 2 was determined to be 39 ± 6 nM, which was very close to that (IC 50 = 33 ± 5 nM) of HYNIC-3P-RGD 2 . Replacing glutamic acid with iminodiacetic acid had little impact on α v β 3 binding affinity of cyclic RGD peptides. 99m Tc-I2P-RGD 2 and 99m Tc-3P-RGD 2 shared similar tumor uptake values over the 2 h period, and its α v β 3 -specificity was demonstrated by a blocking experiment. The uptake of 99m Tc-I2P-RGD 2 was significantly lower than 99m Tc-3P-RGD 2 in the liver and kidneys. The U87MG glioma tumors were visualized by SPECT with excellent contrast using both 99m Tc-I2P-RGD 2 and 99m Tc-3P-RGD 2 . Conclusion: Iminodiacetic acid is an excellent bifunctional linker for dimerization of cyclic RGD peptides. Bifunctional linkers have significant impact on the excretion kinetics of 99m Tc radiotracers. Because of its lower liver uptake and better tumor/liver ratios, 99m Tc-I2P-RGD 2 may have advantages over 99m Tc-3P-RGD 2 for diagnosis of tumors in chest region. -- Graphical abstract: This report presents novel approach for dimerization of cyclic RGD peptides using iminodiacetic acid as a

Investigation on a-C:H:Me coated substrates as an alternative bipolar plate material in all-vanadium redox-flow batteries; Untersuchungen an a-C:H:Me beschichteten Substraten zur Eignung als alternatives Bipolarplattenmaterial fuer waessrige Vanadium Redox-Flow Batterien

Energy Technology Data Exchange (ETDEWEB)

Richards, Justin Frederick

2015-07-01

A crucial aspect of advancing in renewable energies is the development of affordable decentralized storage systems for the local or regional distribution grid. A technology with great potential is the all-vanadium redox-flow battery (VRFB) with the distinct feature of individual scalable power and capacity. The present work focusses on one of the essential parts in the redox-flow cell; the bipolar plates. By the application of metallic substrates instead of state-of-the-arte graphite composite plates, the design of the cell isn't limited anymore to the mechanical properties or fabrication process of the material. Although metals possess high ductility, which eases the production of such plates, they are prone to corrosion in the high acidic environment of the battery electrolyte. Therefore in this study amorphous carbon coatings (a-C:H) are investigated for corrosion protection. To attain the need of high electrical conductivity the carbon matrices is doped with a metallic element. Preferably refractory metals such as titanium, vanadium, chromium and tungsten were investigated as possible dopants. The electrochemical tests of the samples revealed less degradation the higher the coating thickness was. This can be found on all metallic substrates (material number: 1.4301, 3.7165 and 3.3535). Regarding the hydrogen overpotential, which is an essential value for the suppression of side reactions on the anode, the dominating factor was found to be the sort of doping material as well as the composition of the metallic adhesive layer between coating and substrate. Pores in the coating originate from defects in the substrates as well as from contaminations during the coating process. To understand the degradation mechanism an in-situ-corrosion cell was developed. By the means of these results, delamination could be found to be the predominant factor concerning degradation mechanisms at cathodic potentials. The degradation is initialized at the defects or at the edges

Redox front penetration in the fractured Toki Granite, central Japan: An analogue for redox reactions and redox buffering in fractured crystalline host rocks for repositories of long-lived radioactive waste

International Nuclear Information System (INIS)

Yamamoto, Koshi; Yoshida, Hidekazu; Akagawa, Fuminori; Nishimoto, Shoji; Metcalfe, Richard

2013-01-01

Highlights: • Deep redox front developed in orogenic granitic rock have been studied. • The process was controlled by the buffering capacity of minerals. • This is an analogue of redox front penetration into HLW repositories in Japan. - Abstract: Redox buffering is one important factor to be considered when assessing the barrier function of potential host rocks for a deep geological repository for long-lived radioactive waste. If such a repository is to be sited in fractured crystalline host rock it must be demonstrated that waste will be emplaced deeper than the maximum depth to which oxidizing waters can penetrate from the earth’s surface via fractures, during the assessment timeframe (typically 1 Ma). An analogue for penetration of such oxidizing water occurs in the Cretaceous Toki Granite of central Japan. Here, a deep redox front is developed along water-conducting fractures at a depth of 210 m below the ground surface. Detailed petrographical studies and geochemical analyses were carried out on drill core specimens of this redox front. The aim was to determine the buffering processes and behavior of major and minor elements, including rare earth elements (REEs), during redox front development. The results are compared with analytical data from an oxidized zone found along shallow fractures (up to 20 m from the surface) in the same granitic rock, in order to understand differences in elemental migration according to the depth below the ground surface of redox-front formation. Geochemical analyses by XRF and ICP-MS of the oxidized zone at 210 m depth reveal clear changes in Fe(III)/Fe(II) ratios and Ca depletion across the front, while Fe concentrations vary little. In contrast, the redox front identified along shallow fractures shows strong enrichments of Fe, Mn and trace elements in the oxidized zone compared with the fresh rock matrix. The difference can be ascribed to the changing Eh and pH of groundwater as it flows downwards in the granite, due to

3-D pore-scale resolved model for coupled species/charge/fluid transport in a vanadium redox flow battery

International Nuclear Information System (INIS)

Qiu Gang; Joshi, Abhijit S.; Dennison, C.R.; Knehr, K.W.; Kumbur, E.C.; Sun Ying

2012-01-01

The vanadium redox flow battery (VRFB) has emerged as a viable grid-scale energy storage technology that offers cost-effective energy storage solutions for renewable energy applications. In this paper, a novel methodology is introduced for modeling of the transport mechanisms of electrolyte flow, species and charge in the VRFB at the pore scale of the electrodes; that is, at the level where individual carbon fiber geometry and electrolyte flow are directly resolved. The detailed geometry of the electrode is obtained using X-ray computed tomography (XCT) and calibrated against experimentally determined pore-scale characteristics (e.g., pore and fiber diameter, porosity, and surface area). The processed XCT data is then used as geometry input for modeling of the electrochemical processes in the VRFB. The flow of electrolyte through the pore space is modeled using the lattice Boltzmann method (LBM) while the finite volume method (FVM) is used to solve the coupled species and charge transport and predict the performance of the VRFB under various conditions. An electrochemical model using the Butler–Volmer equations is used to provide species and charge coupling at the surfaces of the carbon fibers. Results are obtained for the cell potential distribution, as well as local concentration, overpotential and current density profiles under galvanostatic discharge conditions. The cell performance is investigated as a function of the electrolyte flow rate and external drawing current. The model developed here provides a useful tool for building the structure–property–performance relationship of VRFB electrodes.

Metabolic Control of Redox and Redox Control of Metabolism in Plants

Science.gov (United States)

Fernie, Alisdair R.

2014-01-01

Abstract Significance: Reduction-oxidation (Redox) status operates as a major integrator of subcellular and extracellular metabolism and is simultaneously itself regulated by metabolic processes. Redox status not only dominates cellular metabolism due to the prominence of NAD(H) and NADP(H) couples in myriad metabolic reactions but also acts as an effective signal that informs the cell of the prevailing environmental conditions. After relay of this information, the cell is able to appropriately respond via a range of mechanisms, including directly affecting cellular functioning and reprogramming nuclear gene expression. Recent Advances: The facile accession of Arabidopsis knockout mutants alongside the adoption of broad-scale post-genomic approaches, which are able to provide transcriptomic-, proteomic-, and metabolomic-level information alongside traditional biochemical and emerging cell biological techniques, has dramatically advanced our understanding of redox status control. This review summarizes redox status control of metabolism and the metabolic control of redox status at both cellular and subcellular levels. Critical Issues: It is becoming apparent that plastid, mitochondria, and peroxisome functions influence a wide range of processes outside of the organelles themselves. While knowledge of the network of metabolic pathways and their intraorganellar redox status regulation has increased in the last years, little is known about the interorganellar redox signals coordinating these networks. A current challenge is, therefore, synthesizing our knowledge and planning experiments that tackle redox status regulation at both inter- and intracellular levels. Future Directions: Emerging tools are enabling ever-increasing spatiotemporal resolution of metabolism and imaging of redox status components. Broader application of these tools will likely greatly enhance our understanding of the interplay of redox status and metabolism as well as elucidating and

Biomedical Applications of Gold Nanoparticles Functionalized Using Hetero-Bifunctional Poly(ethylene glycol) Spacer

National Research Council Canada - National Science Library

Fu, Wei; Shenoy, Dinesh; Li, Jane; Crasto, Curtis; Jones, Graham; Dimarzio, Charles; Sridhar, Srinivas; Amiji, Mansoor

2005-01-01

To increase the targeting potential, circulation time, and the flexibility of surface-attached biomedically-relevant ligands on gold nanoparticles, hetero-bifunctional poly(ethylene glycol) (PEG, MW 1,500...

D-bifunctional protein deficiency associated with drug resistant infantile spasms

NARCIS (Netherlands)

Buoni, Sabrina; Zannolli, Raffaella; Waterham, Hans; Wanders, Ronald; Fois, Alberto

2007-01-01

Peroxisomal disorders appear with a frequency of about 1:5000 in newborns. Peroxisomal D-bifunctional protein (D-BP), encoded by the HSD17B4 gene (gene ID: 3294; locus tag: HGNC:5213, chromosome 5q2; official symbol: HSD17B4; name: hydroxysteroid (17-beta) dehydrogenase; gene type: protein coding)

Assessing the impact of electrolyte conductivity and viscosity on the reactor cost and pressure drop of redox-active polymer flow batteries

Science.gov (United States)

Iyer, Vinay A.; Schuh, Jonathon K.; Montoto, Elena C.; Pavan Nemani, V.; Qian, Shaoyi; Nagarjuna, Gavvalapalli; Rodríguez-López, Joaquín; Ewoldt, Randy H.; Smith, Kyle C.

2017-09-01

Redox-active small molecules, used traditionally in redox flow batteries (RFBs), are susceptible to crossover and require expensive ion exchange membranes (IEMs) to achieve long lifetimes. Redox-active polymer (RAP) solutions show promise as candidate electrolytes to mitigate crossover through size-exclusion, enabling the use of porous separators instead of IEMs. Here, poly(vinylbenzyl ethyl viologen) is studied as a surrogate RAP for RFBs. For oxidized RAPs, ionic conductivity varies weakly between 1.6 and 2.1 S m-1 for RAP concentrations of 0.13-1.27 mol kg-1 (monomeric repeat unit per kg solvent) and 0.32 mol kg-1 LiBF4 with a minor increase upon reduction. In contrast, viscosity varies between 1.8 and 184.0 mPa s over the same concentration range with weakly shear-thinning rheology independent of oxidation state. Techno-economic analysis is used to quantify reactor cost as a function of electrolyte transport properties for RAP concentrations of 0.13-1.27 mol kg-1, assuming a hypothetical 3V cell and facile kinetics. Among these concentrations, reactor cost is minimized over a current density range of 600-1000 A m-2 with minimum reactor cost between 11-17 per kWh, and pumping pressures below 10 kPa. The predicted low reactor cost of RAP RFBs is enabled by sustained ionic mobility in spite of the high viscosity of concentrated RAP solutions.

Potentiometric chip-based multipumping flow system for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples.

Science.gov (United States)

Chango, Gabriela; Palacio, Edwin; Cerdà, Víctor

2018-08-15

A simple potentiometric chip-based multipumping flow system (MPFS) has been developed for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples. The proposed system was developed by using a poly(methyl methacrylate) chip microfluidic-conductor using the advantages of flow techniques with potentiometric detection. For this purpose, an automatic system has been designed and built by optimizing the variables involved in the process, such as: pH, ionic strength, stirring and sample volume. This system was applied successfully to water samples getting a versatile system with an analysis frequency of 12 samples per hour. Good correlation between chloride and fluoride concentration measured with ISE and ionic chromatography technique suggests satisfactory reliability of the system. Copyright © 2018 Elsevier B.V. All rights reserved.

Amplified and in situ detection of redox-active metabolite using a biobased redox capacitor.

Science.gov (United States)

Kim, Eunkyoung; Gordonov, Tanya; Bentley, William E; Payne, Gregory F

2013-02-19

Redox cycling provides a mechanism to amplify electrochemical signals for analyte detection. Previous studies have shown that diverse mediators/shuttles can engage in redox-cycling reactions with a biobased redox capacitor that is fabricated by grafting redox-active catechols onto a chitosan film. Here, we report that redox cycling with this catechol-chitosan redox capacitor can amplify electrochemical signals for detecting a redox-active bacterial metabolite. Specifically, we studied the redox-active bacterial metabolite pyocyanin that is reported to be a virulence factor and signaling molecule for the opportunistic pathogen P. aeruginosa. We demonstrate that redox cycling can amplify outputs from various electrochemical methods (cyclic voltammetry, chronocoulometry, and differential pulse voltammetry) and can lower the detection limit of pyocyanin to 50 nM. Further, the compatibility of this biobased redox capacitor allows the in situ monitoring of the production of redox-active metabolites (e.g., pyocyanin) during the course of P. aeruginosa cultivation. We anticipate that the amplified output of redox-active virulence factors should permit an earlier detection of life-threatening infections by the opportunistic pathogen P. aeruginosa while the "bio-compatibility" of this measurement approach should facilitate in situ study of the spatiotemporal dynamics of bacterial redox signaling.

Crosslinked anion exchange membranes prepared from poly(phenylene oxide) (PPO) for non-aqueous redox flow batteries

Science.gov (United States)

Li, Yun; Sniekers, Jeroen; Malaquias, João C.; Van Goethem, Cedric; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F. J.

2018-02-01

A stable and eco-friendly anion-exchange membrane (AEM) was prepared and applied in a non-aqueous all-copper redox flow battery (RFB). The AEM was prepared via a simple procedure, leading to a cross-linked structure containing quaternary ammonium groups without involvement of harmful trimethylamine. A network was thus constructed which ensured both ion transport and solvent resistance. The ion exchange capacity (IEC) of the membrane was tuned from 0.49 to 1.03 meq g-1 by varying the content of the 4, 4‧-bipyridine crosslinking agent. The membrane showed a good anion conductivity and retention of copper ions. As a proof of principle, a RFB single cell with this crosslinked membrane yielded a coulombic efficiency of 89%, a voltage efficiency of 61% and an energy efficiency of 54% at 7.5 mA cm-2.

Sulfonated Poly(Ether Ether Ketone)/Functionalized Carbon Nanotube Composite Membrane for Vanadium Redox Flow Battery Applications

International Nuclear Information System (INIS)

Jia, Chuankun; Cheng, Yuanhang; Ling, Xiao; Wei, Guanjie; Liu, Jianguo; Yan, Chuanwei

2015-01-01

A novel sulfonated poly(ether ether ketone) (SPEEK) membrane embedded with the short-carboxylic multi-walled carbon nanotube (we name it as SPEEK/SCCT membrane) for vanadium redox flow battery (VRB) has been prepared with low capacity loss, low cost and high energy efficiency. The mechanical strength, vanadium ions permeability and performance of the membrane in the VRB single cell were characterized. Results showed that the SPEEK/SCCT membrane possessed low permeability of vanadium ions, accompanied by higher mechanical strength than the Nafion 212 membrane. The VRB single cell with SPEEK/SCCT membrane showed 7% higher coulombic efficiency (CE), 6% higher energy efficiency (EE) but lower capacity loss in comparison with the one with Nafion 212. The good cell performance, low capacity loss and high vanadium ions barrier properties of the blend membrane is of significant interest for VRB applications

One-Step Cationic Grafting of 4-Hydroxy-TEMPO and its Application in a Hybrid Redox Flow Battery with a Crosslinked PBI Membrane.

Science.gov (United States)

Chang, Zhenjun; Henkensmeier, Dirk; Chen, Ruiyong

2017-08-24

By using a one-step epoxide ring-opening reaction between 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy-TEMPO) and glycidyltrimethylammonium cation (GTMA + ), we synthesized a cation-grafted TEMPO (g + -TEMPO) and studied its electrochemical performance against a Zn 2+ /Zn anode in a hybrid redox flow battery. To conduct Cl - counter anions, a crosslinked methylated polybenzimidazole (PBI) membrane was prepared and placed between the catholyte and anolyte. Compared to 4-hydroxy-TEMPO, the positively charged g + - TEMPO exhibits enhanced reaction kinetics. Moreover, flow battery tests with g + -TEMPO show improved Coulombic, voltage, and energy efficiencies and cycling stability over 140 cycles. Crossover of active species through the membrane was not detected. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and Testing of Bi-Functional, P-Loop-Targeted MDM2 Inhibitors

National Research Council Canada - National Science Library

Prives, Carol L; Stockwell, Brent R

2007-01-01

Our proposal is to design and evaluate a novel class of bifunctional MDM2 inhibitors, based on the discovery that nucleotides can bind to the P-loop of MDM2 and cause its relocalization to the nucleolus...

Design and Testing of Bi-Functional, P-Loop-Targeted MDM2 Inhibitors

National Research Council Canada - National Science Library

Prives, Carol L

2006-01-01

This proposal is to design and evaluate a novel class of bifunctional MDM2 inhibitors, based on the discovery that nucleotides can bind to the P-loop of MDM2 and cause its relocalization to the nucleolus...

Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

KAUST Repository

Mazoyer, Etienne

2011-12-02

1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

Effects of organic additives with oxygen- and nitrogen-containing functional groups on the negative electrolyte of vanadium redox flow battery

International Nuclear Information System (INIS)

Liu, Jianlei; Liu, Suqin; He, Zhangxing; Han, Huiguo; Chen, Yong

2014-01-01

DL-malic acid and L-aspartic acid are investigated as additives for the negative electrolyte of vanadium redox flow battery (VFRB) to improve its stability and electrochemical performance. The stability experiments indicate that the addition of L-aspartic acid into the 2 M V(III) electrolyte can stabilize the electrolyte by delaying its precipitation. The results of cyclic voltammetry and electrochemical impedance spectroscopy show that the V(III) electrolyte with both additives demonstrates enhanced electrochemical activity and reversibility. The introduction of DL-malic acid and L-aspartic acid can increase the diffusion coefficient of V(III) species and facilitate the charge transfer of V(III)/V(II) redox reaction. Between the two additives, the effect of L-aspartic acid is more remarkable. Moreover, the VFRB cell employing negative electrolyte with L-aspartic acid exhibits excellent cycling stability and achieves higher average energy efficiency (76.4%) compared to the pristine cell (73.8%). The comparison results with the cell employing L-aspartic acid pre-treated electrode confirm that L-aspartic acid in the electrolyte can modify the electrode by constantly providing oxygen- and nitrogen-containing groups, leading to the enhancement of electrochemical performance

Hydrodeoxygenation and coupling of aqueous phenolics over bifunctional zeolite-supported metal catalysts.

Science.gov (United States)

Hong, Do-Young; Miller, Stephen J; Agrawal, Pradeep K; Jones, Christopher W

2010-02-21

Pt supported on HY zeolite is successfully used as a bifunctional catalyst for phenol hydrodeoxygenation in a fixed-bed configuration at elevated hydrogen pressures, leading to hydrogenation-hydrogenolysis ring-coupling reactions producing hydrocarbons, some with enhanced molecular weight.

Online Spectroscopic Study on the Positive and the Negative Electrolytes in Vanadium Redox Flow Batteries

Directory of Open Access Journals (Sweden)

Le Liu

2013-01-01

Full Text Available Traditional spectroscopic analysis based on the Beer-Lambert law cannot analyze the analyte with high concentration and interference between different compositions, such as the electrolyte in vanadium redox flow batteries (VRBs. Here we propose a new method for online detection of such analytes. We demonstrate experimentally that, by comparing the transmittance spectrum of the analyte with the spectra in a preprepared database using our intensity-corrected correlation coefficient (ICCC algorithm, parameters such as the state of charge (SOC of both the positive and the negative electrolytes in the VRB can be online monitored. This method could monitor the level of the electrolytes imbalance in the VRB, which is useful for further rebalancing the electrolyte and restoring the capacity loss of the VRB. The method also has the potential to be used in the online detection of other chemical reactions, in which the chemical reagents have high concentration and interferences between different compositions.

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

Science.gov (United States)

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.

Synergistic extraction of Am(III) using HTTA and bi-functional (DHDECMP) and mono-functional (TBP) donors

International Nuclear Information System (INIS)

Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

1999-01-01

The equilibrium constant (log Ks) for the organic phase synergistic reaction for Am(III)-HTTA system with bi-functional neutral donor di-hexyl di-ethyl carbamoylmethyl phosphonate (DHDECMP) was found to be about two orders of magnitude higher than that of the mono-functional neutral donor (TBP) with comparable basicity values. This log Ks value along with a large positive entropy change with DHDECMP compared to that with TBP confirms that the neutral donors like DHDECMP behave as bi-functional, in sharp contrast to its mono-functional behaviour in Pu(VI). (author)

A dynamic model-based estimate of the value of a vanadium redox flow battery for frequency regulation in Texas

International Nuclear Information System (INIS)

Fares, Robert L.; Meyers, Jeremy P.; Webber, Michael E.

2014-01-01

Highlights: • A model is implemented to describe the dynamic voltage of a vanadium flow battery. • The model is used with optimization to maximize the utility of the battery. • A vanadium flow battery’s value for regulation service is approximately $1500/kW. - Abstract: Building on past work seeking to value emerging energy storage technologies in grid-based applications, this paper introduces a dynamic model-based framework to value a vanadium redox flow battery (VRFB) participating in Texas’ organized electricity market. Our model describes the dynamic behavior of a VRFB system’s voltage and state of charge based on the instantaneous charging or discharging power required from the battery. We formulate an optimization problem that incorporates the model to show the potential value of a VRFB used for frequency regulation service in Texas. The optimization is implemented in Matlab using the large-scale, interior-point, nonlinear optimization algorithm, with the objective function gradient, nonlinear constraint gradients, and Hessian matrix specified analytically. Utilizing market prices and other relevant data from the Electric Reliability Council of Texas (ERCOT), we find that a VRFB system used for frequency regulation service could be worth approximately $1500/kW

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

Science.gov (United States)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Post-modified acid-base bifunctional MIL-101(Cr) for one-pot deacetalization-Knoevenagel reaction

Energy Technology Data Exchange (ETDEWEB)

Mu, Manman [Tianjin University, School of Science (China); Yan, Xilong; Li, Yang; Chen, Ligong, E-mail: lgchen@tju.edu.cn [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) (China)

2017-04-15

A novel and convenient approach for the construction of the bifunctional MIL-101 material bearing sulfonic acid and amino groups was established via the post-synthetic modification. This material possesses high BET surface area (1446 m{sup 2}/g) and large pore volume (0.77 cm{sup 3}/g). Significantly, this material could serve as a bifunctional heterogeneous catalyst and was initially employed for one-pot deacetalization-Knoevenagel reaction, exhibiting excellent catalytic performance (yield 99.74%). More importantly, it can be easily recovered and reused at least three times. Finally, our proposed catalytic mechanism indicated that amino and the sulfonic acid groups played a synergistic effect on this one-pot deacetalization-Knoevenagel reaction.

The Redox Proteome*

Science.gov (United States)

Go, Young-Mi; Jones, Dean P.

2013-01-01

The redox proteome consists of reversible and irreversible covalent modifications that link redox metabolism to biologic structure and function. These modifications, especially of Cys, function at the molecular level in protein folding and maturation, catalytic activity, signaling, and macromolecular interactions and at the macroscopic level in control of secretion and cell shape. Interaction of the redox proteome with redox-active chemicals is central to macromolecular structure, regulation, and signaling during the life cycle and has a central role in the tolerance and adaptability to diet and environmental challenges. PMID:23861437

Chloroplast Redox Poise

DEFF Research Database (Denmark)

Steccanella, Verdiana

the redox status of the plastoquinone pool and chlorophyll biosynthesis. Furthermore, in the plant cell, the equilibrium between redox reactions and ROS signals is also maintained by various balancing mechanisms among which the thioredoxin reductase-thioredoxin system (TR-Trx) stands out as a mediator......The redox state of the chloroplast is maintained by a delicate balance between energy production and consumption and is affected by the need to avoid increased production of reactive oxygen species (ROS). Redox power and ROS generated in the chloroplast are essential for maintaining physiological...... metabolic pathways and for optimizing chloroplast functions. The redox poise of photosynthetic electron transport components like plastoquinone is crucial to initiate signaling cascades and might also be involved in key biosynthetic pathways such as chlorophyll biosynthesis. We, therefore, explored...

Synthesis, characterization and use of ATRP bifunctional initiator with trichloromethyl end-groups

Czech Academy of Sciences Publication Activity Database

Toman, Luděk; Janata, Miroslav; Spěváček, Jiří; Masař, Bohumil; Vlček, Petr; Látalová, Petra

2002-01-01

Roč. 43, č. 2 (2002), s. 18-19 ISSN 0032-3934 R&D Projects: GA ČR GA203/01/0513 Institutional research plan: CEZ:AV0Z4050913 Keywords : bifunctional initiator * ATRP polymerization * trichloromethyl end-groups Subject RIV: CD - Macromolecular Chemistry

Neurodegeneration in D-bifunctional protein deficiency: diagnostic clues and natural history using serial magnetic resonance imaging

Energy Technology Data Exchange (ETDEWEB)

Khan, Aneal [University of Calgary, Department of Medical Genetics and Pediatrics, Alberta Children' s Hospital, Calgary, AB (Canada); Wei, Xing-Chang [University of Calgary, Department of Radiology, Alberta Children' s Hospital, Calgary, AB (Canada); Snyder, Floyd F. [Alberta Children' s Hospital, Biochemical Genetics Laboratory, Calgary, AB (Canada); Mah, Jean K. [University of Calgary, Division of Neurology, Department of Pediatrics, Calgary, AB (Canada); Waterham, Hans; Wanders, Ronald J.A. [University of Amsterdam, Academic Medical Center, Lab Genetic Metabolic Diseases, Amsterdam (Netherlands)

2010-12-15

We report serial neurodegenerative changes on neuroimaging in a rare peroxisomal disease called D-bifunctional protein deficiency. The pattern of posterior to anterior demyelination with white matter disease resembles X-linked adrenoleukodystrophy. We feel this case is important to (1) highlight that D-bifunctional protein deficiency should be considered in cases where the neuroimaging resembles X-linked adrenoleukodystrophy, (2) to show different stages of progression to help identify this disease using neuroimaging in children, and (3) to show that neuroimaging suggesting a leukodystrophy can warrant peroxisomal beta-oxidation studies in skin fibroblasts even when plasma very long chain fatty acids are normal. (orig.)

Redox Behavior of Fe2+/Fe3+ Redox Couple by Absorption Spectroscopy and Measurement

International Nuclear Information System (INIS)

Oh, J. Y.; Park, S.; Yun, J. I.

2010-01-01

Redox behavior has influences on speciation and other geochemical reactions of radionuclides such as sorption, solubility, and colloid formation, etc. It is one of the factors for evaluation of long-term safety assessment under high-level radioactive waste (HLW) disposal conditions. Accordingly, redox potential (Eh) measurement in aquatic system is important to investigate the redox conditions. Eh is usually measured with redox active electrodes (Pt, Au, glassy carbon, etc.). Nevertheless, Eh measurements by general methods using electrodes provide low accuracy and high uncertainty problem. Therefore, Eh calculated from the concentration of redox active elements with a proper complexing reagent by using UV-Vis absorption spectroscopy is progressed. Iron exists mostly as spent nuclear waste container material and in hydro-geologic minerals. In this system, iron controls the redox condition in near-field area and influences chemical behavior and speciation of radionuclides including redox sensitive actinides such as U, Np, and Pu. In the present work, we present the investigation on redox phenomena of iron in aquatic system by a combination of absorption spectroscopy and redox potential measurements

Multicomponent transport in membranes for redox flow batteries

Science.gov (United States)

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

T-REX on-demand redox targeting in live cells.

Science.gov (United States)

Parvez, Saba; Long, Marcus J C; Lin, Hong-Yu; Zhao, Yi; Haegele, Joseph A; Pham, Vanha N; Lee, Dustin K; Aye, Yimon

2016-12-01

This protocol describes targetable reactive electrophiles and oxidants (T-REX)-a live-cell-based tool designed to (i) interrogate the consequences of specific and time-resolved redox events, and (ii) screen for bona fide redox-sensor targets. A small-molecule toolset comprising photocaged precursors to specific reactive redox signals is constructed such that these inert precursors specifically and irreversibly tag any HaloTag-fused protein of interest (POI) in mammalian and Escherichia coli cells. Syntheses of the alkyne-functionalized endogenous reactive signal 4-hydroxynonenal (HNE(alkyne)) and the HaloTag-targetable photocaged precursor to HNE(alkyne) (also known as Ht-PreHNE or HtPHA) are described. Low-energy light prompts photo-uncaging (t 1/2 <1-2 min) and target-specific modification. The targeted modification of the POI enables precisely timed and spatially controlled redox events with no off-target modification. Two independent pathways are described, along with a simple setup to functionally validate known targets or discover novel sensors. T-REX sidesteps mixed responses caused by uncontrolled whole-cell swamping with reactive signals. Modification and downstream response can be analyzed by in-gel fluorescence, proteomics, qRT-PCR, immunofluorescence, fluorescence resonance energy transfer (FRET)-based and dual-luciferase reporters, or flow cytometry assays. T-REX targeting takes 4 h from initial probe treatment. Analysis of targeted redox responses takes an additional 4-24 h, depending on the nature of the pathway and the type of readouts used.

Mixed-Metal, Structural, and Substitution Effects of Polyoxometalates on Electrochemical Behavior in a Redox Flow Battery

International Nuclear Information System (INIS)

Pratt, Harry D.; Pratt, William R.; Fang, Xikui; Hudak, Nicholas S.; Anderson, Travis M.

2014-01-01

Graphical abstract: - Highlights: • Testing of a flow battery with polyoxometalates. • Coulombic efficiency of 83% for an iron-based compound. • Both size and charge density influence battery performance. - Abstract: A pair of redox flow batteries containing polyoxometalates was tested as part of an ongoing program in stationary energy storage. The iron-containing dimer, (SiFe 3 W 9 (OH) 3 O 34 ) 2 (OH) 3 11− , cycled between (SiFe 3 W 9 (OH) 3 O 34 ) 2 (OH) 3 11− /(SiFe 3 W 9 (OH) 3 O 34 ) 2 (OH) 3 14− and (SiFe 3 W 9 (OH) 3 O 34 ) 2 (OH) 3 17− /(SiFe 3 W 9 (OH) 3 O 34 ) 2 (OH) 3 14− for the positive and negative electrode, respectively. This compound demonstrated a coulombic efficiency of 83% after 20 cycles with an electrochemical yield (measured discharge capacity as a percentage of theoretical capacity) of 55%. Cyclic voltammetry on the Lindqvist ion, cis-V 2 W 4 O 19 4− , showed quasi-reversible vanadium electrochemistry, but tungsten reduction was mostly irreversible. In a flow cell configuration, cis-V 2 W 4 O 19 4− had a coulombic efficiency of 45% (for a two-electron process) and an electrochemical yield of 16% after 20 cycles. The poor performance of cis-V 2 W 4 O 19 4− was attributed primarily to its higher charge density. Collectively, the results showed that both polyoxometalate size and charge density are both important parameters to consider in battery material performance

Redox regulation of cell proliferation: Bioinformatics and redox proteomics approaches to identify redox-sensitive cell cycle regulators.

Science.gov (United States)

Foyer, Christine H; Wilson, Michael H; Wright, Megan H

2018-03-29

Plant stem cells are the foundation of plant growth and development. The balance of quiescence and division is highly regulated, while ensuring that proliferating cells are protected from the adverse effects of environment fluctuations that may damage the genome. Redox regulation is important in both the activation of proliferation and arrest of the cell cycle upon perception of environmental stress. Within this context, reactive oxygen species serve as 'pro-life' signals with positive roles in the regulation of the cell cycle and survival. However, very little is known about the metabolic mechanisms and redox-sensitive proteins that influence cell cycle progression. We have identified cysteine residues on known cell cycle regulators in Arabidopsis that are potentially accessible, and could play a role in redox regulation, based on secondary structure and solvent accessibility likelihoods for each protein. We propose that redox regulation may function alongside other known posttranslational modifications to control the functions of core cell cycle regulators such as the retinoblastoma protein. Since our current understanding of how redox regulation is involved in cell cycle control is hindered by a lack of knowledge regarding both which residues are important and how modification of those residues alters protein function, we discuss how critical redox modifications can be mapped at the molecular level. Crown Copyright © 2018. Published by Elsevier Inc. All rights reserved.

Collagen/chitosan based two-compartment and bi-functional dermal scaffolds for skin regeneration

Energy Technology Data Exchange (ETDEWEB)

Wang, Feng [Department of Plastic Surgery and Burns, Shenzhen Second People' s Hospital, Shenzhen 518035 (China); Wang, Mingbo [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); She, Zhending [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shenzhen Lando Biomaterials Co., Ltd., Shenzhen 518057 (China); Fan, Kunwu; Xu, Cheng [Department of Plastic Surgery and Burns, Shenzhen Second People' s Hospital, Shenzhen 518035 (China); Chu, Bin; Chen, Changsheng [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shi, Shengjun, E-mail: shengjunshi@yahoo.com [The Burns Department of Zhujiang Hospital, Southern Medical University, Guangzhou 510280 (China); Tan, Rongwei, E-mail: tanrw@landobiom.com [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shenzhen Lando Biomaterials Co., Ltd., Shenzhen 518057 (China)

2015-07-01

Inspired from the sophisticated bilayer structures of natural dermis, here, we reported collagen/chitosan based two-compartment and bi-functional dermal scaffolds. Two functions refer to mediating rapid angiogenesis based on recombinant human vascular endothelial growth factor (rhVEGF) and antibacterial from gentamicin, which were encapsulated in PLGA microspheres. The gentamicin and rhVEGF encapsulated PLGA microspheres were further combined with collagen/chitosan mixtures in low (lower layer) and high (upper layer) concentrations, and molded to generate the two-compartment and bi-functional scaffolds. Based on morphology and pore structure analyses, it was found that the scaffold has a distinct double layered porous and connective structure with PLGA microspheres encapsulated. Statistical analysis indicated that the pores in the upper layer and in the lower layer have great variations in diameter, indicative of a two-compartment structure. The release profiles of gentamicin and rhVEGF exceeded 28 and 49 days, respectively. In vitro culture of mouse fibroblasts showed that the scaffold can facilitate cell adhesion and proliferation. Moreover, the scaffold can obviously inhibit proliferation of Staphylococcus aureus and Serratia marcescens, exhibiting its unique antibacterial effect. The two-compartment and bi-functional dermal scaffolds can be a promising candidate for skin regeneration. - Highlights: • The dermal scaffold is inspired from the bilayer structures of natural dermis. • The dermal scaffold has two-compartment structures. • The dermal scaffold containing VEGF and gentamicin encapsulated PLGA microspheres • The dermal scaffold can facilitate cell adhesion and proliferation.

Collagen/chitosan based two-compartment and bi-functional dermal scaffolds for skin regeneration

International Nuclear Information System (INIS)

Wang, Feng; Wang, Mingbo; She, Zhending; Fan, Kunwu; Xu, Cheng; Chu, Bin; Chen, Changsheng; Shi, Shengjun; Tan, Rongwei

2015-01-01

Inspired from the sophisticated bilayer structures of natural dermis, here, we reported collagen/chitosan based two-compartment and bi-functional dermal scaffolds. Two functions refer to mediating rapid angiogenesis based on recombinant human vascular endothelial growth factor (rhVEGF) and antibacterial from gentamicin, which were encapsulated in PLGA microspheres. The gentamicin and rhVEGF encapsulated PLGA microspheres were further combined with collagen/chitosan mixtures in low (lower layer) and high (upper layer) concentrations, and molded to generate the two-compartment and bi-functional scaffolds. Based on morphology and pore structure analyses, it was found that the scaffold has a distinct double layered porous and connective structure with PLGA microspheres encapsulated. Statistical analysis indicated that the pores in the upper layer and in the lower layer have great variations in diameter, indicative of a two-compartment structure. The release profiles of gentamicin and rhVEGF exceeded 28 and 49 days, respectively. In vitro culture of mouse fibroblasts showed that the scaffold can facilitate cell adhesion and proliferation. Moreover, the scaffold can obviously inhibit proliferation of Staphylococcus aureus and Serratia marcescens, exhibiting its unique antibacterial effect. The two-compartment and bi-functional dermal scaffolds can be a promising candidate for skin regeneration. - Highlights: • The dermal scaffold is inspired from the bilayer structures of natural dermis. • The dermal scaffold has two-compartment structures. • The dermal scaffold containing VEGF and gentamicin encapsulated PLGA microspheres • The dermal scaffold can facilitate cell adhesion and proliferation

Redox sensor proteins for highly sensitive direct imaging of intracellular redox state.

Science.gov (United States)

Sugiura, Kazunori; Nagai, Takeharu; Nakano, Masahiro; Ichinose, Hiroshi; Nakabayashi, Takakazu; Ohta, Nobuhiro; Hisabori, Toru

2015-02-13

Intracellular redox state is a critical factor for fundamental cellular functions, including regulation of the activities of various metabolic enzymes as well as ROS production and elimination. Genetically-encoded fluorescent redox sensors, such as roGFP (Hanson, G. T., et al. (2004)) and Redoxfluor (Yano, T., et al. (2010)), have been developed to investigate the redox state of living cells. However, these sensors are not useful in cells that contain, for example, other colored pigments. We therefore intended to obtain simpler redox sensor proteins, and have developed oxidation-sensitive fluorescent proteins called Oba-Q (oxidation balance sensed quenching) proteins. Our sensor proteins derived from CFP and Sirius can be used to monitor the intracellular redox state as their fluorescence is drastically quenched upon oxidation. These blue-shifted spectra of the Oba-Q proteins enable us to monitor various redox states in conjunction with other sensor proteins. Copyright © 2015 Elsevier Inc. All rights reserved.

Efficient hydrodeoxygenation of biomass-derived ketones over bifunctional Pt-polyoxometalate catalyst.

Science.gov (United States)

Alotaibi, Mshari A; Kozhevnikova, Elena F; Kozhevnikov, Ivan V

2012-07-21

Acidic heteropoly salt Cs(2.5)H(0.5)PW(12)O(40) doped with Pt nanoparticles is a highly active and selective catalyst for one-step hydrogenation of methyl isobutyl and diisobutyl ketones to the corresponding alkanes in the gas phase at 100 °C with 97-99% yield via metal-acid bifunctional catalysis.

MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS

Energy Technology Data Exchange (ETDEWEB)

Beyenal, Haluk [WSU; McLEan, Jeff [JCVI; Majors, Paul [PNNL; Fredrickson, Jim [PNNL

2013-11-14

The Hanford 300 Area is a unique site due to periodic hydrologic influence of river water resulting in changes in groundwater elevation and flow direction. This area is also highly subject to uranium remobilization, the source of which is currently believed to be the region at the base of the vadose zone that is subject to period saturation due to the changes in the water levels in the Columbia River. We found that microbial processes and redox and abiotic reactions which operate at the microscale were critical to understanding factors controlling the macroscopic fate and transport of contaminants in the subsurface. The combined laboratory and field research showed how microscale conditions control uranium mobility and how biotic, abiotic and redox reactions relate to each other. Our findings extended the current knowledge to examine U(VI) reduction and immobilization using natural 300 Area communities as well as selected model organisms on redox-sensitive and redox-insensitive minerals. Using innovative techniques developed specifically to probe biogeochemical processes at the microscale, our research expanded our current understanding of the roles played by mineral surfaces, bacterial competition, and local biotic, abiotic and redox reaction rates on the reduction and immobilization of uranium.

Redox Regulation of Mitochondrial Function

Science.gov (United States)

Handy, Diane E.

2012-01-01

Abstract Redox-dependent processes influence most cellular functions, such as differentiation, proliferation, and apoptosis. Mitochondria are at the center of these processes, as mitochondria both generate reactive oxygen species (ROS) that drive redox-sensitive events and respond to ROS-mediated changes in the cellular redox state. In this review, we examine the regulation of cellular ROS, their modes of production and removal, and the redox-sensitive targets that are modified by their flux. In particular, we focus on the actions of redox-sensitive targets that alter mitochondrial function and the role of these redox modifications on metabolism, mitochondrial biogenesis, receptor-mediated signaling, and apoptotic pathways. We also consider the role of mitochondria in modulating these pathways, and discuss how redox-dependent events may contribute to pathobiology by altering mitochondrial function. Antioxid. Redox Signal. 16, 1323–1367. PMID:22146081

Loop Replacement Enhances the Ancestral Antibacterial Function of a Bifunctional Scorpion Toxin

Directory of Open Access Journals (Sweden)

Shangfei Zhang

2018-06-01

Full Text Available On the basis of the evolutionary relationship between scorpion toxins targeting K+ channels (KTxs and antibacterial defensins (Zhu S., Peigneur S., Gao B., Umetsu Y., Ohki S., Tytgat J. Experimental conversion of a defensin into a neurotoxin: Implications for origin of toxic function. Mol. Biol. Evol. 2014, 31, 546–559, we performed protein engineering experiments to modify a bifunctional KTx (i.e., weak inhibitory activities on both K+ channels and bacteria via substituting its carboxyl loop with the structurally equivalent loop of contemporary defensins. As expected, the engineered peptide (named MeuTXKα3-KFGGI remarkably improved the antibacterial activity, particularly on some Gram-positive bacteria, including several antibiotic-resistant opportunistic pathogens. Compared with the unmodified toxin, its antibacterial spectrum also enlarged. Our work provides a new method to enhance the antibacterial activity of bifunctional scorpion venom peptides, which might be useful in engineering other proteins with an ancestral activity.

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

Science.gov (United States)

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.

Neuronal differentiation is associated with a redox-regulated increase of copper flow to the secretory pathway.

Science.gov (United States)

Hatori, Yuta; Yan, Ye; Schmidt, Katharina; Furukawa, Eri; Hasan, Nesrin M; Yang, Nan; Liu, Chin-Nung; Sockanathan, Shanthini; Lutsenko, Svetlana

2016-02-16

Brain development requires a fine-tuned copper homoeostasis. Copper deficiency or excess results in severe neuro-pathologies. We demonstrate that upon neuronal differentiation, cellular demand for copper increases, especially within the secretory pathway. Copper flow to this compartment is facilitated through transcriptional and metabolic regulation. Quantitative real-time imaging revealed a gradual change in the oxidation state of cytosolic glutathione upon neuronal differentiation. Transition from a broad range of redox states to a uniformly reducing cytosol facilitates reduction of the copper chaperone Atox1, liberating its metal-binding site. Concomitantly, expression of Atox1 and its partner, a copper transporter ATP7A, is upregulated. These events produce a higher flux of copper through the secretory pathway that balances copper in the cytosol and increases supply of the cofactor to copper-dependent enzymes, expression of which is elevated in differentiated neurons. Direct link between glutathione oxidation and copper compartmentalization allows for rapid metabolic adjustments essential for normal neuronal function.

Heterogeneous redox reactions in groundwater flow systems - Investigation and application of two different coupled codes

Energy Technology Data Exchange (ETDEWEB)

Pfingsten, W.; Carnahan, C.L. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1995-05-01

Two simulators of reactive chemical transport are applied to a set of problems involving heterogeneous reactions of uranium species. The simulators use similar algorithms to compute the heterogeneous chemical equilibria, but they use different approaches to the computation of solute transport and to the coupling of transport with chemical reactions. One simulator (MCOTAC) sequentially couples calculations of static chemical equilibria to a random-walk simulation of solute advection and dispersion. The other simulator (THCC) directly couples mass action relations for chemical equilibria to finite-difference representations of the solute transport equations. The aim of the comparison was to demonstrate the applicability of the newly developed code MCOTAC to redox problems, and to identify and investigate general differences between the two types of codes within these applications. The chosen heterogeneous redox systems are hypothetically generate systems which provide numerical difficulties within the coupled code calculation. Uranium, an important component of heterogeneous redox systems consisting of uraniferous solids and natural groundwaters, was chosen as a main component in the example redox systems because of practical interest for performance assessment of geological repositories for nuclear wastes. The calculations show reasonable agreement, in general, between the two computational approaches. Specific areas of disagreement arise from numerical difficulties to each approach. Such `benchmarking` can enhance confidence in the overall performance of individual simulators while identifying aspects that may require further investigations and possible modifications. (author) figs., tabs., 7 refs.

Redox active polymer devices and methods of using and manufacturing the same

Science.gov (United States)

Johnson, Paul; Bautista-Martinez, Jose Antonio; Friesen, Cody; Switzer, Elise

2018-06-05

The disclosed technology relates generally to apparatus comprising conductive polymers and more particularly to tag and tag devices comprising a redox-active polymer film, and method of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Transient behavior of redox flow battery connected to circuit based on global phase structure

Science.gov (United States)

Mannari, Toko; Hikihara, Takashi

A Redox Flow Battery (RFB) is one of the promising energy storage systems in power grid. An RFB has many advantages such as a quick response, a large capacity, and a scalability. Due to these advantages, an RFB can operate in mixed time scale. Actually, it has been demonstrated that an RFB can be used for load leveling, compensating sag, and smoothing the output of the renewable sources. An analysis on transient behaviors of an RFB is a key issue for these applications. An RFB is governed by electrical, chemical, and fluid dynamics. The hybrid structure makes the analysis difficult. To analyze transient behaviors of an RFB, the exact model is necessary. In this paper, we focus on a change in a concentration of ions in the electrolyte, and simulate the change with a model which is mainly based on chemical kinetics. The simulation results introduces transient behaviors of an RFB in a response to a load variation. There are found three kinds of typical transient behaviors including oscillations. As results, it is clarified that the complex transient behaviors, due to slow and fast dynamics in the system, arise by the quick response to load.

Geochemistry of Natural Redox Fronts

International Nuclear Information System (INIS)

Hofmann, B.A.

1999-05-01

Redox fronts are important geochemical boundaries which need to be considered in safety assessment of deep repositories for radioactive waste. In most cases, selected host-rock formations will be reducing due to the presence of ferrous minerals, sulphides, etc. During construction and operation of the repository, air will be introduced into the formation. After repository closure, oxidising conditions may persist locally until all oxygen is consumed. In the case of high-level waste, radiolysis of water may provide an additional source of oxidants. Oxidising conditions within a repository are thus possible and potentially have a strong influence on the mobility of many elements. The rate of movement of redox fronts, the boundary between oxidising and reducing environments, and their influence on migrating radionuclides are thus important factors influencing repository performance. The present report is a review of elemental behaviour at natural redox fronts, based on published information and work of the author. Redox fronts are geochemically and geometrically variable manifestations of a global interface between generally oxidising geochemical milieux in contact with the atmosphere and generally reducing milieux in contact with rocks containing ferrous iron, sulphide and/or organic carbon. A classification of redox fronts based on a subdivision into continental near-surface, marine near-surface, and deep environments is proposed. The global redox interface is often located close to the surface of rocks and sediments and, sometimes, within bodies of water. Temperature conditions are close to ambient. A deeper penetration of the global redox front to depths of several kilometres is found in basins containing oxidised sediments (red beds) and in some hydrothermal circulation systems. Temperatures at such deep redox fronts may reach 200 o C. Both near-surface and deep redox fronts are sites of formation of economic deposits of redox-sensitive elements, particularly of

Redox signaling in plants.

Science.gov (United States)

Foyer, Christine H; Noctor, Graham

2013-06-01

Our aim is to deliver an authoritative and challenging perspective of current concepts in plant redox signaling, focusing particularly on the complex interface between the redox and hormone-signaling pathways that allow precise control of plant growth and defense in response to metabolic triggers and environmental constraints and cues. Plants produce significant amounts of singlet oxygen and other reactive oxygen species (ROS) as a result of photosynthetic electron transport and metabolism. Such pathways contribute to the compartment-specific redox-regulated signaling systems in plant cells that convey information to the nucleus to regulate gene expression. Like the chloroplasts and mitochondria, the apoplast-cell wall compartment makes a significant contribution to the redox signaling network, but unlike these organelles, the apoplast has a low antioxidant-buffering capacity. The respective roles of ROS, low-molecular antioxidants, redox-active proteins, and antioxidant enzymes are considered in relation to the functions of plant hormones such as salicylic acid, jasmonic acid, and auxin, in the composite control of plant growth and defense. Regulation of redox gradients between key compartments in plant cells such as those across the plasma membrane facilitates flexible and multiple faceted opportunities for redox signaling that spans the intracellular and extracellular environments. In conclusion, plants are recognized as masters of the art of redox regulation that use oxidants and antioxidants as flexible integrators of signals from metabolism and the environment.

Redox potential distribution of an organic-rich contaminated site obtained by the inversion of self-potential data

Science.gov (United States)

Abbas, M.; Jardani, A.; Soueid Ahmed, A.; Revil, A.; Brigaud, L.; Bégassat, Ph.; Dupont, J. P.

2017-11-01

Mapping the redox potential of shallow aquifers impacted by hydrocarbon contaminant plumes is important for the characterization and remediation of such contaminated sites. The redox potential of groundwater is indicative of the biodegradation of hydrocarbons and is important in delineating the shapes of contaminant plumes. The self-potential method was used to reconstruct the redox potential of groundwater associated with an organic-rich contaminant plume in northern France. The self-potential technique is a passive technique consisting in recording the electrical potential distribution at the surface of the Earth. A self-potential map is essentially the sum of two contributions, one associated with groundwater flow referred to as the electrokinetic component, and one associated with redox potential anomalies referred to as the electroredox component (thermoelectric and diffusion potentials are generally negligible). A groundwater flow model was first used to remove the electrokinetic component from the observed self-potential data. Then, a residual self-potential map was obtained. The source current density generating the residual self-potential signals is assumed to be associated with the position of the water table, an interface characterized by a change in both the electrical conductivity and the redox potential. The source current density was obtained through an inverse problem by minimizing a cost function including a data misfit contribution and a regularizer. This inversion algorithm allows the determination of the vertical and horizontal components of the source current density taking into account the electrical conductivity distribution of the saturated and non-saturated zones obtained independently by electrical resistivity tomography. The redox potential distribution was finally determined from the inverted residual source current density. A redox map was successfully built and the estimated redox potential values correlated well with in

Construction of Bifunctional Co/H-ZSM-5 Catalysts for the Hydrodeoxygenation of Stearic Acid to Diesel-range Alkanes.

Science.gov (United States)

Wu, Guangjun; Zhang, Nan; Dai, Weili; Guan, Naijia; Li, Landong

2018-04-27

Bifunctional Co/H-ZSM-5 zeolites were prepared by surface organometallic chemistry grafting route, namely by the stoichiometric reaction between cobaltocene and the Brønsted acid sites in zeolites, and applied to the model reaction of stearic acid catalytic hydrodeoxygenation. Cobalt species existed in the form of isolated Co2+ ions at exchange positions after grafting, transformed to CoO species on the surface of zeolite and stabilized inside zeolite channels upon calcination in air, and finally reduced to metallic cobalt species of homogeneous clusters of ca. 1.5 nm by hydrogen. During this process, the Brønsted acid sites of H-ZSM-5 zeolites could be preserved with acid strength slightly reduced. The as-prepared bifunctional catalyst exhibited a ~16 times higher activity in stearic acid hydrodeoxygenation (2.11 gSAgcat-1h-1) than the reference catalyst (0.13 gSAgcat-1h-1) prepared by solid-state ion exchange, and a high C18/C17 ratio of ~24 was achieved as well. The remarkable hydrodeoxygenation performance of bifunctional Co/H-ZSM-5 could be explained from the effective synergy between the uniformed metallic cobalt clusters and the Brønsted acid sites in H-ZSM-5 zeolite. The simplified reaction network and kinetics of stearic acid hydrodeoxygenation catalyzed by the as-prepared bifunctional Co/H-ZSM-5 zeolites were also investigated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Groundwater redox conditions and conductivity in a contaminant plume from geoelectrical investigations

Directory of Open Access Journals (Sweden)

V. Naudet

2004-01-01

Full Text Available Accurate mapping of the electrical conductivity and of the redox potential of the groundwater is important in delineating the shape of a contaminant plume. A map of redox potential in an aquifer is indicative of biodegradation of organic matter and of concentrations of redox-active components; a map of electrical conductivity provides information on the mineralisation of the groundwater. Both maps can be used to optimise the position of pumping wells for remediation. The self-potential method (SP and electrical resistivity tomography (ERT have been applied to the contaminant plume associated with the Entressen landfill in south-east France. The self-potential depends on groundwater flow (electrokinetic contribution and redox conditions ('electro-redox' contribution. Using the variation of the piezometric head in the aquifer, the electrokinetic contribution is removed from the SP signals. A good linear correlation (R2=0.85 is obtained between the residual SP data and the redox potential values measured in monitoring wells. This relationship is used to draw a redox potential map of the overall contaminated site. The electrical conductivity of the subsoil is obtained from 3D-ERT analysis. A good linear correlation (R2=0.91 is observed between the electrical conductivity of the aquifer determined from the 3D-ERT image and the conductivity of the groundwater measured in boreholes. This indicates that the formation factor is nearly homogeneous in the shallow aquifer at the scale of the ERT. From this correlation, a map of the pore water conductivity of the aquifer is obtained. Keywords: self-potential, redox potential, electrical resistivity tomography, fluid conductivity, contaminant plume

Computational design of molecules for an all-quinone redox flow battery† †Electronic supplementary information (ESI) available: The list of computationally predicted candidate quinone molecules with interesting redox properties. See DOI: 10.1039/c4sc03030c Click here for additional data file.

Science.gov (United States)

Er, Süleyman; Suh, Changwon; Marshak, Michael P.

2015-01-01

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 (QH2) (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. PMID:29560173

Bi-functional glycosyltransferases catalyze both extension and termination of pectic galactan oligosaccharides

DEFF Research Database (Denmark)

Laursen, Tomas; Stonebloom, Solomon H; Pidatala, Venkataramana R

2018-01-01

. Transfer of Arap to galactan prevents further addition of galactose residues, resulting in a lower degree of polymerization. We show that this dual activity occurs both in vitro and in vivo. The herein described bi-functionality of AtGALS1 may suggest that plants can produce the incredible structural...

Solvent extraction of uranium(VI), plutonium(VI) and americium(III) with HTTA/HPMBP using mono- and bi-functional neutral donors. Synergism and thermodynamics

International Nuclear Information System (INIS)

Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

2000-01-01

Synergistic extraction of hexavalent uranium and plutonium as well as trivalent americium was studied in HNO 3 with thenoyl, trifluoro-acetone (HTTA)/1-phenyl, 3-methyl, 4-benzoyl pyrazolone-5 (HPMBP) in combination with neutral donors viz. DPSO, TBP, TOPO (mono-functional) and DBDECMP, DHDECMP, CMPO (bi-functional) with wide basicity range using benzene as diluent. A linear correlation was observed when the equilibrium constant log Ks for the organic phase synergistic reaction of both U(VI) and Pu(VI) with either of the chelating agents HTTA or HPMBP was plotted vs. the basicity (log Kh) of the donor (both mono- and bi-functional) indicating bi-functional donors also behave as mono-functional. This was supported by the thermodynamic data (ΔG 0 , ΔH 0 , ΔS 0 ) obtained for these systems. The organic phase adduct formation reactions were identified for the above systems from the thermodynamic data. In the Am(III) HTTA system log K s values of bi-functional donors were found to be very high and deviate from the linear plot (log K s vs. log K h ) obtained for mono-functional donors, indicating that they function as bi-functional for the Am(III)/HTTA) system studied. This was supported by high +ve ΔS 0 values obtained for this system. (author)

Numerical study of the effects of carbon felt electrode compression in all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Oh, Kyeongmin; Won, Seongyeon; Ju, Hyunchul

2015-01-01

Highlights: • The effects of electrode compression on VRFB are examined. • The electronic conductivity is improved when the compression is increased. • The kinetic losses are similar regardless of the electrode compression level. • The vanadium distribution is more uniform within highly compressed electrode. - Abstract: The porous carbon felt electrode is one of the major components of all-vanadium redox flow batteries (VRFBs). These electrodes are necessarily compressed during stack assembly to prevent liquid electrolyte leakage and diminish the interfacial contact resistance among VRFB stack components. The porous structure and properties of carbon felt electrodes have a considerable influence on the electrochemical reactions, transport features, and cell performance. Thus, a numerical study was performed herein to investigate the effects of electrode compression on the charge and discharge behavior of VRFBs. A three-dimensional, transient VRFB model developed in a previous study was employed to simulate VRFBs under two degrees of electrode compression (10% vs. 20%). The effects of electrode compression were precisely evaluated by analysis of the solid/electrolyte potential profiles, transfer current density, and vanadium concentration distributions, as well as the overall charge and discharge performance. The model predictions highlight the beneficial impact of electrode compression; the electronic conductivity of the carbon felt electrode is the main parameter improved by electrode compression, leading to reduction in ohmic loss through the electrodes. In contrast, the kinetics of the redox reactions and transport of vanadium species are not significantly altered by the degree of electrode compression (10% to 20%). This study enhances the understanding of electrode compression effects and demonstrates that the present VRFB model is a valuable tool for determining the optimal design and compression of carbon felt electrodes in VRFBs.

Improving the electrocatalytic performance of carbon nanotubes for VO"2"+/VO_2"+ redox reaction by KOH activation

International Nuclear Information System (INIS)

Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

2017-01-01

Highlights: • KOH-activated carbon nanotubes (CNTs) was investigated as superior catalyst for VO"2"+/VO_2"+ redox reaction for vanadium redox flow battery (VRFB) for the first time. • KOH activation for CNTs can result in the chemical etching of surface and improved wettability, accelerating the mass transfer of vanadium ions. • KOH activation can introduce many oxygen-containing groups as active sites on the surface of CNTs. • KOH-activated CNTs as positive catalyst could increase the comprehensive energy storage performance of VRFB. - Abstract: In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO"2"+/VO_2"+ 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 VO"2"+/VO_2"+ 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 VO"2"+/VO_2"+ 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 VO"2"+/VO_2"+ redox reaction for VRFB system.

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

Science.gov (United States)

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 .

Determining Li+-Coupled Redox Targeting Reaction Kinetics of Battery Materials with Scanning Electrochemical Microscopy.

Science.gov (United States)

Yan, Ruiting; Ghilane, Jalal; Phuah, Kia Chai; Pham Truong, Thuan Nguyen; Adams, Stefan; Randriamahazaka, Hyacinthe; Wang, Qing

2018-02-01

The redox targeting reaction of Li + -storage materials with redox mediators is the key process in redox flow lithium batteries, a promising technology for next-generation large-scale energy storage. The kinetics of the Li + -coupled heterogeneous charge transfer between the energy storage material and redox mediator dictates the performance of the device, while as a new type of charge transfer process it has been rarely studied. Here, scanning electrochemical microscopy (SECM) was employed for the first time to determine the interfacial charge transfer kinetics of LiFePO 4 /FePO 4 upon delithiation and lithiation by a pair of redox shuttle molecules FcBr 2 + and Fc. The effective rate constant k eff was determined to be around 3.70-6.57 × 10 -3 cm/s for the two-way pseudo-first-order reactions, which feature a linear dependence on the composition of LiFePO 4 , validating the kinetic process of interfacial charge transfer rather than bulk solid diffusion. In addition, in conjunction with chronoamperometry measurement, the SECM study disproves the conventional "shrinking-core" model for the delithiation of LiFePO 4 and presents an intriguing way of probing the phase boundary propagations induced by interfacial redox reactions. This study demonstrates a reliable method for the kinetics of redox targeting reactions, and the results provide useful guidance for the optimization of redox targeting systems for large-scale energy storage.

Electronic Connection Between the Quinone and Cytochrome c Redox Pools and Its Role in Regulation of Mitochondrial Electron Transport and Redox Signaling

Science.gov (United States)

Sarewicz, Marcin; Osyczka, Artur

2015-01-01

Mitochondrial respiration, an important bioenergetic process, relies on operation of four membranous enzymatic complexes linked functionally by mobile, freely diffusible elements: quinone molecules in the membrane and water-soluble cytochromes c in the intermembrane space. One of the mitochondrial complexes, complex III (cytochrome bc1 or ubiquinol:cytochrome c oxidoreductase), provides an electronic connection between these two diffusible redox pools linking in a fully reversible manner two-electron quinone oxidation/reduction with one-electron cytochrome c reduction/oxidation. Several features of this homodimeric enzyme implicate that in addition to its well-defined function of contributing to generation of proton-motive force, cytochrome bc1 may be a physiologically important point of regulation of electron flow acting as a sensor of the redox state of mitochondria that actively responds to changes in bioenergetic conditions. These features include the following: the opposing redox reactions at quinone catalytic sites located on the opposite sides of the membrane, the inter-monomer electronic connection that functionally links four quinone binding sites of a dimer into an H-shaped electron transfer system, as well as the potential to generate superoxide and release it to the intermembrane space where it can be engaged in redox signaling pathways. Here we highlight recent advances in understanding how cytochrome bc1 may accomplish this regulatory physiological function, what is known and remains unknown about catalytic and side reactions within the quinone binding sites and electron transfers through the cofactor chains connecting those sites with the substrate redox pools. We also discuss the developed molecular mechanisms in the context of physiology of mitochondria. PMID:25540143

The use of polybenzimidazole membranes in vanadium redox flow batteries leading to increased coulombic efficiency and cycling performance

International Nuclear Information System (INIS)

Zhou, X.L.; Zhao, T.S.; An, L.; Wei, L.; Zhang, C.

2015-01-01

An issue with conventional vanadium redox flow batteries (VRFB) with Nafion membranes is the crossover of vanadium ions, resulting in low coulombic efficiency and rapid decay in capacity. In this work, a VRFB with a polybenzimidazole (PBI) membrane is tested and compared with the Nafion system. Results show that the PBI-based VRFB exhibits a substantially higher coulombic efficiency of up to 99% at current densities ranging from 20 mA cm −2 to 80 mA cm −2 . More importantly, it is demonstrated that the PBI-based VRFB has a capacity decay rate of as low as 0.3% per cycle, which is four times lower than that of the Nafion system (1.3% per cycle). The improved coulombic efficiency and cycling performance are attributed to the low crossover of vanadium ions through the PBI membrane

Novel composite membrane coated with a poly(diallyldimethylammonium chloride)/urushi semi-interpenetrating polymer network for non-aqueous redox flow battery application

Science.gov (United States)

Cho, Eunhae; Won, Jongok

2016-12-01

Novel composite membranes of a semi-interpenetrating network (semi-IPN) coated on the surfaces of a porous Celgard 2400 support are prepared and investigate for application in a non-aqueous redox flow battery (RFB). A natural polymer, urushi, is used for the matrix because of its high mechanical robustness, and poly(diallyldimethylammonium chloride) (PDDA) provides anionic exchange sites. The PDDA/urushi (P/U) semi-IPN film is prepared by the photo polymerization of urushiol in the presence of PDDA. The thin layer composed of the P/U semi-IPN on the porous support provides selectivity while maintaining the ion conductivity. The coulombic and energy efficiencies increase with increasing amounts of PDDA in the P/U semi-IPN layer, and the values reach 69.5% and 42.5%, respectively, for the one containing 40 wt% of PDDA. These values are substantially higher than those of the Neosepta AHA membrane and the Celgard membrane, indicating that the selective layer reduces the crossover of the redox active species through the membrane. This result implies that the formation of composite membranes using semi-IPN selective layers on the dimensionally stable porous membrane enable the successful use of a non-aqueous RFB for future energy storage systems.

Redox-sensitive structural change in the A-domain of HMGB1 and its implication for the binding to cisplatin modified DNA

International Nuclear Information System (INIS)

Wang, Jing; Tochio, Naoya; Takeuchi, Aya; Uewaki, Jun-ichi; Kobayashi, Naohiro; Tate, Shin-ichi

2013-01-01

Highlights: •The structure of the oxidized A-domain of human HMGB1 was solved. •Phe38 ring was flipped in the oxidized structure from that in the reduced form. •The flipped ring disables the intercalation into the cisplatinated lesions. •The functionally relevant redox-dependent structural change was described. -- Abstract: HMGB1 (high-mobility group B1) is a ubiquitously expressed bifunctional protein that acts as a nuclear protein in cells and also as an inflammatory mediator in the extracellular space. HMGB1 changes its functions according to the redox states in both intra- and extra-cellular environments. Two cysteines, Cys23 and Cys45, in the A-domain of HMGB1 form a disulfide bond under oxidative conditions. The A-domain with the disulfide bond shows reduced affinity to cisplatin modified DNA. We have solved the oxidized A-domain structure by NMR. In the structure, Phe38 has a flipped ring orientation from that found in the reduced form; the phenyl ring in the reduced form intercalates into the platinated lesion in DNA. The phenyl ring orientation in the oxidized form is stabilized through intramolecular hydrophobic contacts. The reorientation of the Phe38 ring by the disulfide bond in the A-domain may explain the reduced HMGB1 binding affinity towards cisplatinated DNA

Investigation on a-C:H:Me coated substrates as an alternative bipolar plate material in all-vanadium redox-flow batteries

International Nuclear Information System (INIS)

Richards, Justin Frederick

2015-01-01

A crucial aspect of advancing in renewable energies is the development of affordable decentralized storage systems for the local or regional distribution grid. A technology with great potential is the all-vanadium redox-flow battery (VRFB) with the distinct feature of individual scalable power and capacity. The present work focusses on one of the essential parts in the redox-flow cell; the bipolar plates. By the application of metallic substrates instead of state-of-the-arte graphite composite plates, the design of the cell isn't limited anymore to the mechanical properties or fabrication process of the material. Although metals possess high ductility, which eases the production of such plates, they are prone to corrosion in the high acidic environment of the battery electrolyte. Therefore in this study amorphous carbon coatings (a-C:H) are investigated for corrosion protection. To attain the need of high electrical conductivity the carbon matrices is doped with a metallic element. Preferably refractory metals such as titanium, vanadium, chromium and tungsten were investigated as possible dopants. The electrochemical tests of the samples revealed less degradation the higher the coating thickness was. This can be found on all metallic substrates (material number: 1.4301, 3.7165 and 3.3535). Regarding the hydrogen overpotential, which is an essential value for the suppression of side reactions on the anode, the dominating factor was found to be the sort of doping material as well as the composition of the metallic adhesive layer between coating and substrate. Pores in the coating originate from defects in the substrates as well as from contaminations during the coating process. To understand the degradation mechanism an in-situ-corrosion cell was developed. By the means of these results, delamination could be found to be the predominant factor concerning degradation mechanisms at cathodic potentials. The degradation is initialized at the defects or at the edges

The evolution of redox conditions and groundwater geochemistry in recharge-discharge environments on the Canadian Shield

International Nuclear Information System (INIS)

Gascoyne, M.

1996-10-01

Groundwater composition evolves along flow paths from recharge to discharge in response to interactions with bedrock and fracture-filling minerals, and dissolution of soluble (Cl-rich) salts in the rock matrix. The groundwater redox potential changes from oxidizing to reducing conditions due, initially, to rapid consumption of dissolved oxygen by organics in the upper ∼100 m of bedrock and, subsequently, interaction with Fe (II)-containing minerals. Measured Eh values of groundwaters at depth in the granitic Lac du Bonnet batholith indicate that biotite and chlorite control groundwater redox potential. This is supported by other geochemical characteristics such as absence of CH 4 , H 2 S, H 2 , NO 3 , low concentrations of Fe (II), and abundance of SO 4 . Further evidence of evolution of redox conditions is given by variations in U concentration ranging from up to 1000 μg/L in dilute near-surface waters to <1 μg/L in some deep, saline groundwaters. Groundwaters at about 400 m depth in a recharge area on the Lac du Bonnet batholith contain significantly more U than groundwaters further along the flow path or near surface in discharge areas. Uranium concentration is found to be a useful and sensitive indicator of redox conditions. (author)

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

Science.gov (United States)

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.

Effect of long-term fertilization on humic redox mediators in multiple microbial redox reactions.

Science.gov (United States)

Guo, Peng; Zhang, Chunfang; Wang, Yi; Yu, Xinwei; Zhang, Zhichao; Zhang, Dongdong

2018-03-01

This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2',4,4',5,5'- hexachlorobiphenyl (PCB 153 ) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB 153 dechlorination activity (1.03 μM PCB 153 removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms' metabolisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Perspectives in the development of hybrid bifunctional antitumour agents.

Science.gov (United States)

Musso, Loana; Dallavalle, Sabrina; Zunino, Franco

2015-08-15

In spite of the development of a large number of novel target-specific antitumour agents, the single-agent therapy is in general not able to provide an effective durable control of the malignant process. The limited efficacy of the available agents (both conventional cytotoxic and novel target-specific) reflects not only the expression of defence mechanisms, but also the complexity of tumour cell alterations and the redundancy of survival pathways, thus resulting in tumour cell ability to survive under stress conditions. A well-established strategy to improve the efficacy of antitumour therapy is the rational design of drug combinations aimed at achieving synergistic effects and overcoming drug resistance. An alternative strategy could be the use of agents designed to inhibit simultaneously multiple cellular targets relevant to tumour growth/survival. Among these novel agents are hybrid bifunctional drugs, i.e. compounds resulting by conjugation of different drugs or containing the pharmocophores of different drugs. This strategy has been pursued using various conventional or target-specific agents (with DNA damaging agents and histone deacetylase inhibitors as the most exploited compounds). A critical overview of the most representative compounds is provided with emphasis on the HDAC inhibitor-based hybrid agents. In spite of some promising results, the actual pharmacological advantages of the hybrid agents remain to be defined. This commentary summarizes the recent advances in this field and highlights the pharmacological basis for a rational design of hybrid bifunctional agents. Copyright © 2015. Published by Elsevier Inc.

REDOX IMAGING OF THE p53-DEPENDENT MITOCHONDRIAL REDOX STATE IN COLON CANCER EX VIVO

Science.gov (United States)

XU, HE N.; FENG, MIN; MOON, LILY; DOLLOFF, NATHAN; EL-DEIRY, WAFIK; LI, LIN Z.

2015-01-01

The mitochondrial redox state and its heterogeneity of colon cancer at tissue level have not been previously reported. Nor has how p53 regulates mitochondrial respiration been measured at (deep) tissue level, presumably due to the unavailability of the technology that has sufficient spatial resolution and tissue penetration depth. Our prior work demonstrated that the mitochondrial redox state and its intratumor heterogeneity is associated with cancer aggressiveness in human melanoma and breast cancer in mouse models, with the more metastatic tumors exhibiting localized regions of more oxidized redox state. Using the Chance redox scanner with an in-plane spatial resolution of 200 μm, we imaged the mitochondrial redox state of the wild-type p53 colon tumors (HCT116 p53 wt) and the p53-deleted colon tumors (HCT116 p53−/−) by collecting the fluorescence signals of nicotinamide adenine dinucleotide (NADH) and oxidized flavoproteins [Fp, including flavin adenine dinucleotide (FAD)] from the mouse xenografts snap-frozen at low temperature. Our results show that: (1) both tumor lines have significant degree of intratumor heterogeneity of the redox state, typically exhibiting a distinct bi-modal distribution that either correlates with the spatial core–rim pattern or the “hot/cold” oxidation-reduction patches; (2) the p53−/− group is significantly more heterogeneous in the mitochondrial redox state and has a more oxidized tumor core compared to the p53 wt group when the tumor sizes of the two groups are matched; (3) the tumor size dependence of the redox indices (such as Fp and Fp redox ratio) is significant in the p53−/− group with the larger ones being more oxidized and more heterogeneous in their redox state, particularly more oxidized in the tumor central regions; (4) the H&E staining images of tumor sections grossly correlate with the redox images. The present work is the first to reveal at the submillimeter scale the intratumor heterogeneity pattern

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

Science.gov (United States)

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.

Relating hyporheic fluxes, residence times, and redox-sensitive biogeochemical processes upstream of beaver dams

Science.gov (United States)

Briggs, Martin A.; Lautz, Laura; Hare, Danielle K.

2013-01-01

Abstract. Small dams enhance the development of patchy microenvironments along stream corridors by trapping sediment and creating complex streambed morphologies. This patchiness drives intricate hyporheic flux patterns that govern the exchange of O2 and redox-sensitive solutes between the water column and the stream bed. We used multiple tracer techniques, naturally occurring and injected, to evaluate hyporheic flow dynamics and associated biogeochemical cycling and microbial reactivity around 2 beaver dams in Wyoming (USA). High-resolution fiber-optic distributed temperature sensing was used to collect temperature data over 9 vertical streambed profiles and to generate comprehensive vertical flux maps using 1-dimensional (1-D) heat-transport modeling. Coincident with these locations, vertical profiles of hyporheic water were collected every week and analyzed for dissolved O2, pH, dissolved organic C, and several conservative and redox-sensitive solutes. In addition, hyporheic and net stream aerobic microbial reactivity were analyzed with a constant-rate injection of the biologically sensitive resazurin (Raz) smart tracer. The combined results revealed a heterogeneous system with rates of downwelling hyporheic flow organized by morphologic unit and tightly coupled to the redox conditions of the subsurface. Principal component analysis was used to summarize the variability of all redox-sensitive species, and results indicated that hyporheic water varied from oxic-stream-like to anoxic-reduced in direct response to the hydrodynamic conditions and associated residence times. The anaerobic transition threshold predicted by the mean O2 Damko

Chiral 2-Aminobenzimidazole as Bifunctional Catalyst in the Asymmetric Electrophilic Amination of Unprotected 3-Substituted Oxindoles

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Llorenç Benavent

2018-06-01

Full Text Available The use of readily available chiral trans-cyclohexanediamine-benzimidazole derivatives as bifunctional organocatalysts in the asymmetric electrophilic amination of unprotected 3-substituted oxindoles is presented. Different organocatalysts were evaluated; the most successful one contained a dimethylamino moiety (5. With this catalyst under optimized conditions, different oxindoles containing a wide variety of substituents at the 3-position were aminated in good yields and with good to excellent enantioselectivities using di-tert-butylazodicarboxylate as the aminating agent. The procedure proved to be also efficient for the amination of 3-substituted benzofuranones, although with moderate results. A bifunctional role of the catalyst, acting as Brønsted base and hydrogen bond donor, is proposed according to the experimental results observed.

A π-Conjugation Extended Viologen as a Two-Electron Storage Anolyte for Total Organic Aqueous Redox Flow Batteries.

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Luo, Jian; Hu, Bo; Debruler, Camden; Liu, Tianbiao Leo

2018-01-02

Extending the conjugation of viologen by a planar thiazolo[5,4-d]thiazole (TTz) framework and functionalizing the pyridinium with hydrophilic ammonium groups yielded a highly water-soluble π-conjugation extended viologen, 4,4'-(thiazolo[5,4-d]thiazole-2,5-diyl)bis(1-(3-(trimethylammonio)propyl)pyridin-1-ium) tetrachloride, [(NPr) 2 TTz]Cl 4  , as a novel two-electron storage anolyte for aqueous organic redox flow battery (AORFB) applications. Its physical and electrochemical properties were systematically investigated. Paired with 4-trimethylammonium-TEMPO (N Me -TEMPO) as catholyte, [(NPr) 2 TTz]Cl 4 enables a 1.44 V AORFB with a theoretical energy density of 53.7 Wh L -1 . A demonstrated [(NPr) 2 TTz]Cl 4 /N Me -TEMPO AORFB delivered an energy efficiency of 70 % and 99.97 % capacity retention per cycle. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox Pioneer: Professor Vadim N. Gladyshev.

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Hatfield, Dolph L

2016-07-01

Professor Vadim N. Gladyshev is recognized here as a Redox Pioneer, because he has published an article on antioxidant/redox biology that has been cited more than 1000 times and 29 articles that have been cited more than 100 times. Gladyshev is world renowned for his characterization of the human selenoproteome encoded by 25 genes, identification of the majority of known selenoprotein genes in the three domains of life, and discoveries related to thiol oxidoreductases and mechanisms of redox control. Gladyshev's first faculty position was in the Department of Biochemistry, the University of Nebraska. There, he was a Charles Bessey Professor and Director of the Redox Biology Center. He then moved to the Department of Medicine at Brigham and Women's Hospital, Harvard Medical School, where he is Professor of Medicine and Director of the Center for Redox Medicine. His discoveries in redox biology relate to selenoenzymes, such as methionine sulfoxide reductases and thioredoxin reductases, and various thiol oxidoreductases. He is responsible for the genome-wide identification of catalytic redox-active cysteines and for advancing our understanding of the general use of cysteines by proteins. In addition, Gladyshev has characterized hydrogen peroxide metabolism and signaling and regulation of protein function by methionine-R-sulfoxidation. He has also made important contributions in the areas of aging and lifespan control and pioneered applications of comparative genomics in redox biology, selenium biology, and aging. Gladyshev's discoveries have had a profound impact on redox biology and the role of redox control in health and disease. He is a true Redox Pioneer. Antioxid. Redox Signal. 25, 1-9.

Broad temperature adaptability of vanadium redox flow battery—Part 2: Cell research

International Nuclear Information System (INIS)

Xi, Jingyu; Xiao, Shuibo; Yu, Lihong; Wu, Lantao; Liu, Le; Qiu, Xinping

2016-01-01

Highlights: • VRFB can operate in a broad temperature range from −20 °C to 50 °C with high efficiency. • High temperatures reduce the ohmic and polarization resistances of VRFB. • The CE and capacity retention drop with temperature rising. • Operating at alternate temperatures gives extra damage to the VRFB. - Abstract: The operating temperature of vanadium redox flow battery (VRFB) will change with seasons and places. Hence, the broad temperature adaptability of VRFB is one of the key issues which affect its large-scale practical application. In our previous work, we have reported the impact of temperature (−35 °C–50 °C) on the static stability, physicochemical and electrochemical properties of five typical vanadium electrolytes (Electrochim. Acta, 2016, 187, 525). As a follow-up study, VRFB single cells are evaluated in this paper at a broad temperature range under current density of 40–200 mA cm −2 . The results show that VRFB can operate from −20 °C to 50 °C with acceptable energy efficiency under appropriate current densities (e.g. 65%–78% at 100 mA cm −2 ). Ohmic and polarization resistances of VRFB decrease with temperature while the voltage efficiency and electrolyte utilization present the opposite tendency. The fast crossover of the vanadium ions at high temperatures aggravates the capacity fading of the cell. Notably, VRFB suffers much more damage during alternate temperatures operation between moderate temperature and high temperature, which should be given special attention.

Structure and potential applications of amido lanthanide complexes chelated by bifunctional b-diketiminate ligand

Czech Academy of Sciences Publication Activity Database

Olejník, R.; Padělková, Z.; Fridrichová, A.; Horáček, Michal; Merna, J.; Růžička, A.

2014-01-01

Roč. 759, JUN 2014 (2014), s. 1-10 ISSN 0022-328X R&D Projects: GA ČR GAP106/10/0924 Institutional support: RVO:61388955 Keywords : Bifunctional b-diketiminates * lanthanides * hydroamination Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.173, year: 2014

Chemical synthesis, redox transformation, and identification of sonnerphenolic C, an antioxidant in Acer nikoense.

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Iwadate, Takehiro; Nihei, Ken-Ichi

2017-04-15

Sonnerphenolic C (3), which was predicted in a redox product of epirhododendrin (1) isolated from Acer nikoense, was synthesized for the first time via the epimeric separation of benzylidene acetal intermediates as a key step. From a similar synthetic route, 1 was obtained concisely. As a result of their antioxidative evaluation, only 3 revealed potent activity. The redox transformation of 1 into 3 was achieved in the presence of tyrosinase and vitamin C. Moreover, 3 was identified in the decoction of A. nikoense by HPLC analysis with the effective use of synthesized 3. Thus, a novel naturally occurring antioxidant 3 was developed through the sequential flow including redox prediction, chemical synthesis, evaluation of the activity, and identification as the natural product. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

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Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

2018-01-01

A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.

Effects of the electric field on ion crossover in vanadium redox flow batteries

International Nuclear Information System (INIS)

Yang, Xiao-Guang; Ye, Qiang; Cheng, Ping; Zhao, Tim S.

2015-01-01

Highlights: • Effects of the electric field on ion crossover and capacity decay in VRFB are studied. • The model enables the Donnan-potential jumps to be captured at electrode/membrane interfaces. • Electric field arises and affects ion crossover even at the open-circuit condition. • Enhancing electric-field-driven crossover can mitigate the capacity decay rate. - Abstract: A thorough understanding of the mechanisms of ion crossover through the membranes in vanadium redox flow batteries (VRFBs) is critically important in making improvements to the battery’s efficiency and cycling performance. In this work, we develop a 2-D VRFB model to investigate the mechanisms of ion crossover and the associated impacts it has on the battery’s performance. Unlike previously described models in the literature that simulated a single cell by dividing it into the positive electrode, membrane, and negative electrode regions, the present model incorporates all possible ion crossover mechanisms in the entire cell without a need to specify any interfacial boundary conditions at the membrane/electrode interfaces, and hence accurately captures the Donnan-potential jumps and steep gradient of species concentrations at the membrane/electrode interfaces. With our model, a particular emphasis is given to investigation of the effect of the electric field on vanadium ion crossover. One of the significant findings is that an electric field exists in the membrane even under the open-circuit condition, primarily due to the presence of the H + concentration gradient across the membrane. This finding suggests that vanadium ions can permeate through the membrane from H + -diluted to H + -concentrated sides via migration and convection. More importantly, it is found that the rate of vanadium ion crossover and capacity decay during charge and discharge vary with the magnitude of the electric field, which is influenced by the membrane properties and operating conditions. The simulations

High surface area carbon for bifunctional air electrodes applied in zinc-air batteries

Energy Technology Data Exchange (ETDEWEB)

Arai, H [on leave from NTT Laboratories (Japan); Mueller, S; Haas, O [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

Bifunctional air electrodes with high surface area carbon substrates showed low reduction overpotential, thus are promising for enhancing the energy efficiency and power capability of zinc-air batteries. The improved performance is attributed to lower overpotential due to diffusion of the reaction intermediate, namely the peroxide ion. (author) 1 fig., 2 refs.

Robust Control of PEP Formation Rate in the Carbon Fixation Pathway of C4 Plants by a Bi-functional Enzyme

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Hart Yuval

2011-10-01

Full Text Available Abstract Background C4 plants such as corn and sugarcane assimilate atmospheric CO2 into biomass by means of the C4 carbon fixation pathway. We asked how PEP formation rate, a key step in the carbon fixation pathway, might work at a precise rate, regulated by light, despite fluctuations in substrate and enzyme levels constituting and regulating this process. Results We present a putative mechanism for robustness in C4 carbon fixation, involving a key enzyme in the pathway, pyruvate orthophosphate dikinase (PPDK, which is regulated by a bifunctional enzyme, Regulatory Protein (RP. The robust mechanism is based on avidity of the bifunctional enzyme RP to its multimeric substrate PPDK, and on a product-inhibition feedback loop that couples the system output to the activity of the bifunctional regulator. The model provides an explanation for several unusual biochemical characteristics of the system and predicts that the system's output, phosphoenolpyruvate (PEP formation rate, is insensitive to fluctuations in enzyme levels (PPDK and RP, substrate levels (ATP and pyruvate and the catalytic rate of PPDK, while remaining sensitive to the system's input (light levels. Conclusions The presented PPDK mechanism is a new way to achieve robustness using product inhibition as a feedback loop on a bifunctional regulatory enzyme. This mechanism exhibits robustness to protein and metabolite levels as well as to catalytic rate changes. At the same time, the output of the system remains tuned to input levels.

Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

DEFF Research Database (Denmark)

Li, Hu; Khokarale, Santosh Govind; Kotni, Ramakrishna

2014-01-01

carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl...

A paclitaxel prodrug with bifunctional folate and albumin binding moieties for both passive and active targeted cancer therapy.

Science.gov (United States)

Shan, Lingling; Zhuo, Xin; Zhang, Fuwu; Dai, Yunlu; Zhu, Guizhi; Yung, Bryant C; Fan, Wenpei; Zhai, Kefeng; Jacobson, Orit; Kiesewetter, Dale O; Ma, Ying; Gao, Guizhen; Chen, Xiaoyuan

2018-01-01

Folate receptor (FR) has proven to be a valuable target for chemotherapy using folic acid (FA) conjugates. However, FA-conjugated chemotherapeutics still have low therapeutic efficacy accompanied with side effects, resulting from complications such as short circulation half-life, limited tumor delivery, as well as high kidney accumulation. Herein, we present a novel FA-conjugated paclitaxel (PTX) prodrug which was additionally conjugated with an Evans blue (EB) derivative for albumin binding. The resulting bifunctional prodrug prolonged blood circulation, enhanced tumor accumulation, and consequently improved tumor therapeutic efficacy. Methods: Fmoc-Cys(Trt)-OH was coupled onto PTX at the 7'-OH position for further synthesis of ester prodrug FA-PTX-EB. The targeting ability was investigated using confocal microscopy and flow cytometry. The pharmacokinetics of this bifunctional compound was also studied. Meanwhile, cell viability was evaluated in normal cells and three cancer cell lines by MTT assay. In vivo therapeutic effect was tested on FR-α overexpressing MDA-MB-231 tumor model. Results: Compared with free PTX, the FA-PTX, PTX-EB and FA-PTX-EB prodrugs increased circulation half-life in mice from 2.19 to 3.82, 4.41, and 7.51 h, respectively. Pharmacokinetics studies showed that the FA-PTX-EB delivered more PTX to tumors than FA-PTX and free PTX. In vitro and in vivo studies demonstrated that FA-EB-conjugated PTX induced potent antitumor activity. Conclusion: FA-PTX-EB showed prolonged blood circulation, enhanced drug accumulation in tumors, higher therapeutic index, and lower side effects than either free PTX or monofunctional FA-PTX and EB-PTX. The results support the potential of using EB for the development of long-acting therapeutics.

Redox-sensitive GFP fusions for monitoring the catalytic mechanism and inactivation of peroxiredoxins in living cells

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Verena Staudacher

2018-04-01

Full Text Available Redox-sensitive green fluorescent protein 2 (roGFP2 is a valuable tool for redox measurements in living cells. Here, we demonstrate that roGFP2 can also be used to gain mechanistic insights into redox catalysis in vivo. In vitro enzyme properties such as the rate-limiting reduction of wild type and mutant forms of the model peroxiredoxin PfAOP are shown to correlate with the ratiometrically measured degree of oxidation of corresponding roGFP2 fusion proteins. Furthermore, stopped-flow kinetic measurements of the oxidative half-reaction of PfAOP support the interpretation that changes in the roGFP2 signal can be used to map hyperoxidation-based inactivation of the attached peroxidase. Potential future applications of our system include the improvement of redox sensors, the estimation of absolute intracellular peroxide concentrations and the in vivo assessment of protein structure-function relationships that cannot easily be addressed with recombinant enzymes, for example, the effect of post-translational protein modifications on enzyme catalysis. Keywords: Peroxiredoxin, Redox sensor, roGFP2, H2O2, Plasmodium falciparum

Compromised redox homeostasis, altered nitroso-redox balance, and therapeutic possibilities in atrial fibrillation.

Science.gov (United States)

Simon, Jillian N; Ziberna, Klemen; Casadei, Barbara

2016-04-01

Although the initiation, development, and maintenance of atrial fibrillation (AF) have been linked to alterations in myocyte redox state, the field lacks a complete understanding of the impact these changes may have on cellular signalling, atrial electrophysiology, and disease progression. Recent studies demonstrate spatiotemporal changes in reactive oxygen species production shortly after the induction of AF in animal models with an uncoupling of nitric oxide synthase activity ensuing in the presence of long-standing persistent AF, ultimately leading to a major shift in nitroso-redox balance. However, it remains unclear which radical or non-radical species are primarily involved in the underlying mechanisms of AF or which proteins are targeted for redox modification. In most instances, only free radical oxygen species have been assessed; yet evidence from the redox signalling field suggests that non-radical species are more likely to regulate cellular processes. A wider appreciation for the distinction of these species and how both species may be involved in the development and maintenance of AF could impact treatment strategies. In this review, we summarize how redox second-messenger systems are regulated and discuss the recent evidence for alterations in redox regulation in the atrial myocardium in the presence of AF, while identifying some critical missing links. We also examine studies looking at antioxidants for the prevention and treatment of AF and propose alternative redox targets that may serve as superior therapeutic options for the treatment of AF. © The Author 2016. Published by Oxford University Press on behalf of the European Society of Cardiology.

Engineering redox balance through cofactor systems.

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