Durable electrooptic devices comprising ionic liquids

DOEpatents

Burrell, Anthony K [Los Alamos, NM; Agrawal, Anoop [Tucson, AZ; Cronin,; John, P [Tucson, AZ; Tonazzi, Juan C. L. [Tucson, AZ; Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM

2009-12-15

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

Durable Electrooptic Devices Comprising Ionic Liquids

DOEpatents

Burrell, Anthony K.; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark

2008-11-11

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

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

NASA Astrophysics Data System (ADS)

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 4+ may not be well suited for use in RFB technology.

The Use of Redox Mediators for Enhancing Utilization of Li2S Cathodes for Advanced Li-S Battery Systems.

PubMed

Meini, Stefano; Elazari, Ran; Rosenman, Ariel; Garsuch, Arnd; Aurbach, Doron

2014-03-06

The development of Li2S electrodes is a crucial step toward industrial manufacturing of Li-S batteries, a promising alternative to Li-ion batteries due to their projected two times higher specific capacity. However, the high voltages needed to activate Li2S electrodes, and the consequent electrolyte solution degradation, represent the main challenge. We present a novel concept that could make feasible the widespread application of Li2S electrodes for Li-S cell assembly. In this concept, the addition of redox mediators as additives to the standard electrolyte solution allows us to recover most of Li2S theoretical capacity in the activation cycle at potentials as low as 2.9 VLi, substantially lower than the typical potentials >4 VLi needed with standard electrolyte solution. Those novel additives permit us to preserve the electrolyte solution from being degraded, allowing us to achieve capacity as high as 500 mAhg(-1)Li2S after 150 cycles with no major structural optimization of the electrodes.

Liquid junction schottky barrier solar cell

DOEpatents

Williams, Richard

1980-01-01

A mixture of ceric ions (Ce.sup.+4) and cerous ions (Ce.sup.+3) in an aqueous electrolyte solution forms a Schottky barrier at the interface between an active region of silicon and the electrolyte solution. The barrier height obtained for hydrogenated amorphous silicon using the Ce.sup.+4 /Ce.sup.+3 redox couple is about 1.7 eV.

Thiocyanates as attractive redox-active electrolytes for high-energy and environmentally-friendly electrochemical capacitors.

PubMed

Gorska, Barbara; Bujewska, Paulina; Fic, Krzysztof

2017-03-15

This manuscript reports on the novel insight into the development of high voltage carbon/carbon electrochemical capacitors operating in aqueous solutions of alkali metals and ammonium thiocyanates (KSCN, NaSCN, LiSCN, and NH 4 SCN). The effect of salt concentration, electrode porosity and current collectors on the capacitance value, system stability, and power performance has been investigated. Therefore, thiocyanate-based electrolytes were recognized as cheap and highly conductive electrolytic solutions (up to 401 mS cm -1 for NH 4 SCN at RT) allowing a cell voltage of 1.6 V in a symmetric carbon/carbon system to be achieved. At the same time, they display an attractive redox activity, enhancing the energy of the device with a good performance during cycling.

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Electrochemical characterisation of a lithium-ion battery electrolyte based on mixtures of carbonates with a ferrocene-functionalised imidazolium electroactive ionic liquid.

PubMed

Forgie, John C; El Khakani, Soumia; MacNeil, Dean D; Rochefort, Dominic

2013-05-28

Electrolytic solutions of lithium-ion batteries can be modified with additives to improve their stability and safety. Electroactive molecules can be used as such additives to act as an electron (redox) shuttle between the two electrodes to prevent overcharging. The electroactive ionic liquid, 1-ferrocenylmethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (TFSI), was synthesised and its electrochemical properties were investigated when diluted with ethylene carbonate-diethyl carbonate solvent at various concentrations. Cyclic voltammetry data were gathered to determine the redox potential, diffusion coefficient and heterogeneous rate constants of the electroactive imidazolium TFSI ionic liquid in the carbonate solution. The properties of this molecule as an additive in lithium battery electrolytes were studied in standard coin cells with a metallic Li anode and a Li4Ti5O12 cathode.

Aqueous electrolytes for redox flow battery systems

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

Liu, Tianbiao; Li, Bin; Wei, Xiaoliang

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

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

PubMed Central

Navalpotro, Paula; Palma, Jesus; Anderson, Marc

2017-01-01

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

Sustainable electrical energy storage through the ferrocene/ferrocenium redox reaction in aprotic electrolyte.

PubMed

Zhao, Yu; Ding, Yu; Song, Jie; Li, Gang; Dong, Guangbin; Goodenough, John B; Yu, Guihua

2014-10-06

The large-scale, cost-effective storage of electrical energy obtained from the growing deployment of wind and solar power is critically needed for the integration into the grid of these renewable energy sources. Rechargeable batteries having a redox-flow cathode represent a viable solution for either a Li-ion or a Na-ion battery provided a suitable low-cost redox molecule soluble in an aprotic electrolyte can be identified that is stable for repeated cycling and does not cross the separator membrane to the anode. Here we demonstrate an environmentally friendly, low-cost ferrocene/ferrocenium molecular redox couple that shows about 95% energy efficiency and about 90% capacity retention after 250 full charge/discharge cycles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Wei, Xiaoliang; Xia, Gordon; Kirby, Brent W.

Aiming to explore low-cost redox flow battery systems, a novel iron-polysulfide (Fe/S) flow battery has been demonstrated in a laboratory cell. This system employs alkali metal ferri/ferrocyanide and alkali metal polysulfides as the redox electrolytes. When proper electrodes, such as pretreated graphite felts, are used, 78% energy efficiency and 99% columbic efficiency are achieved. The remarkable advantages of this system over current state-of-the-art redox flow batteries include: 1) less corrosive and relatively environmentally benign redox solutions used; 2) excellent energy and utilization efficiencies; 3) low cost for redox electrolytes and cell components. These attributes can lead to significantly reduced capitalmore » cost and make the Fe/S flow battery system a promising low-cost energy storage technology. The major drawbacks of the present cell design are relatively low power density and possible sulfur species crossover. Further work is underway to address these concerns.« less

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

PubMed

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

2017-10-02

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

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

Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai

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

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

PubMed

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.

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

PubMed

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

2016-12-28

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

Elucidating the role of methyl viologen as a scavenger of photoactivated electrons from photosystem I under aerobic and anaerobic conditions.

PubMed

Bennett, Tyler; Niroomand, Hanieh; Pamu, Ravi; Ivanov, Ilia; Mukherjee, Dibyendu; Khomami, Bamin

2016-03-28

We present detailed electrochemical investigations into the role of dissolved O2 in electrolyte solutions in scavenging photoactivated electrons from a uniform photosystem I (PS I) monolayer assembled on alkanethiolate SAM (self-assembled monolayer)/Au surfaces while using methyl viologen (MV(2+)) as the redox mediator. To this end, we report results for direct measurements of light induced photocurrent from uniform monolayer assemblies of PS I on C9 alkanethiolate SAM/Au surfaces. These measurements, apart from demonstrating the ability of dissolved O2 in the electrolyte medium to act as an electron scavenger, also reveal its essential role in driving the solution-phase methyl viologen to initiate light-induced directional electron transfer from an electron donor surface (Au) via surface assembled PS I trimers. Specifically, our systematic electrochemical measurements have revealed that the dissolved O2 in aqueous electrolyte solutions form a complex intermediate species with MV that plays the essential role in mediating redox pathways for unidirectional electron transfer processes. This critical insight into the redox-mediated electron transfer pathways allows for rational design of electron scavengers through systematic tuning of mediator combinations that promote such intermediate formation. Our current findings facilitate the incorporation of PS I-based bio-hybrid constructs as photo-anodes in future photoelectrochemical cells and bio-electronic devices.

Durable electrooptic devices comprising ionic liquids

DOEpatents

Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

2005-11-01

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N-), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N-) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

Redox flow batteries having multiple electroactive elements

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

Wang, Wei; Li, Liyu; Yang, Zhenguo

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

Hurdles to organic quinone flow cells. Electrode passivation by quinone reduction in acetonitrile Li electrolytes

NASA Astrophysics Data System (ADS)

Rueda-García, D.; Dubal, D. P.; Huguenin, F.; Gómez-Romero, P.

2017-05-01

The uses of quinones in Redox Flow Batteries (RFBs) has been mainly circumscribed to aqueous solutions (of derivatives with polar groups) despite a larger solubility and wider electrochemical window provided by organic media. The redox mechanism of quinones in protic media is simpler and better known than in aprotic media, where radical species are involved. This paper reports the behaviour of methyl-p-benzoquinone (MBQ) under electrochemical reduction conditions in a LiClO4sbnd CH3CN electrolyte and various working electrodes. We detected the reversible generation of a bright green coating on the working electrode and the subsequent formation of a polymer (the nature of which depends on the presence or absence of oxygen). These coatings prevent the regular redox process of methyl-p-benzoquinone from taking place on the surface of the electrode and is generated regardless of the electrode material used or the presence of O2 in solution. In addition to MBQ, the green passivating layer was also found for less sterically hindered quinones such as p-benzoquinone or 1,4-naphthoquinone, but not for anthraquinone. We have also shown the central role of Li+ in the formation of this green layer. This work provides important guidelines for the final use of quinones in RFBs with organic electrolytes.

Capacitance enhancement of polyaniline coated curved-graphene supercapacitors in a redox-active electrolyte

NASA Astrophysics Data System (ADS)

Chen, Wei; Rakhi, R. B.; Alshareef, H. N.

2013-05-01

We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles).We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles). Electronic supplementary information (ESI) available: Experimental section, supporting figures including SEM, TEM, XPS, BET, CV and CD curves and a summary table of capacitance. See DOI: 10.1039/c3nr00773a

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

NASA Astrophysics Data System (ADS)

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.

Double-membrane triple-electrolyte redox flow battery design

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

Yushan, Yan; Gu, Shuang; Gong, Ke

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

Organic non-aqueous cation-based redox flow batteries

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

Zhang, Lu; Huang, Jinhua; Burrell, Anthony

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

Nuclear magnetic resonance studies of the solvation structures of a high-performance nonaqueous redox flow electrolyte

NASA Astrophysics Data System (ADS)

Deng, Xuchu; Hu, Mary; Wei, Xiaoliang; Wang, Wei; Mueller, Karl T.; Chen, Zhong; Hu, Jian Zhi

2016-03-01

Understanding the solvation structures of electrolytes is important for developing nonaqueous redox flow batteries that hold considerable potential for future large scale energy storage systems. The utilization of an emerging ionic-derivatived ferrocene compound, ferrocenylmethyl dimethyl ethyl ammonium bis(trifluoromethanesulfonyl)imide (Fc1N112-TFSI), has recently overcome the issue of solubility in the supporting electrolyte. In this work, 13C, 1H and 17O NMR investigations were carried out using electrolyte solutions consisting of Fc1N112-TFSI as the solute and the mixed alkyl carbonate as the solvent. It was observed that the spectra of 13C experience changes of chemical shifts while those of 17O undergo linewidth broadening, indicating interactions between solute and solvent molecules. Quantum chemistry calculations of both molecular structures and chemical shifts (13C, 1H and 17O) are performed for interpreting experimental results and for understanding the detailed solvation structures. The results indicate that Fc1N112-TFSI is dissociated at varying degrees in mixed solvent depending on concentrations. At dilute solute concentrations, most Fc1N112+ and TFSI- are fully disassociated with their own solvation shells formed by solvent molecules. At saturated concentration, Fc1N112+-TFSI- contact ion pairs are formed and the solvent molecules are preferentially interacting with the Fc rings rather than interacting with the ionic pendant arm of Fc1N112-TFSI.

New Supercapacitors Based on the Synergetic Redox Effect between Electrode and Electrolyte

PubMed Central

Zhang, You; Cui, Xiuguo; Zu, Lei; Cai, Xiaomin; Liu, Yang; Wang, Xiaodong; Lian, Huiqin

2016-01-01

Redox electrolytes can provide significant enhancement of capacitance for supercapacitors. However, more important promotion comes from the synergetic effect and matching between the electrode and electrolyte. Herein, we report a novel electrochemical system consisted of a polyanilline/carbon nanotube composite redox electrode and a hydroquinone (HQ) redox electrolyte, which exhibits a specific capacitance of 7926 F/g in a three-electrode system when the concentration of HQ in H2SO4 aqueous electrolyte is 2 mol/L, and the maximum energy density of 114 Wh/kg in two-electrode symmetric configuration. Moreover, the specific capacitance retention of 96% after 1000 galvanostatic charge/discharge cycles proves an excellent cyclic stability. These ultrahigh performances of the supercapacitor are attributed to the synergistic effect both in redox polyanilline-based electrolyte and the redox hydroquinone electrode. PMID:28773855

Capacitance enhancement of polyaniline coated curved-graphene supercapacitors in a redox-active electrolyte.

PubMed

Chen, Wei; Rakhi, R B; Alshareef, H N

2013-05-21

We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50,000 cycles).

Investigation of a chemically regenerative redox cathode polymer electrolyte fuel cell using a phosphomolybdovanadate polyoxoanion catholyte

NASA Astrophysics Data System (ADS)

Gunn, Natasha L. O.; Ward, David B.; Menelaou, Constantinos; Herbert, Matthew A.; Davies, Trevor J.

2017-04-01

Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells (PEFCs), where the direct reduction of oxygen is replaced by an in-direct mechanism occurring outside of the cell, are attractive to study as they offer a solution to the cost and durability problems faced by conventional PEFCs. This study reports the first detailed characterization of a high performance complete CRRC PEFC system, where catholyte is circulated between the cathode side of the cell and an air-liquid oxidation reactor called the "regenerator". The catholyte is an aqueous solution of phosphomolybdovanadate polyoxoanion and is assessed in terms of its performance within both a small single cell and corresponding regenerator over a range of redox states. Two methods for determining regeneration rate are proposed and explored. Expressing the regeneration rate as a "chemical" current is suggested as a useful means of measuring re-oxidation rate with respect to the cell. The analysis highlights the present limitations to the technology and provides an indication of the maximum power density achievable, which is highly competitive with conventional PEFC systems.

K4[Fe(CN)6] immobilized anion sensitive protonated amine functionalized polysilsesquioxane films for ultra-low electrochemical detection of dsDNA.

PubMed

Silambarasan, Krishnamoorthy; Narendra Kumar, Alam Venugopal; Joseph, James

2016-03-14

Charge transport in polymeric films bound by redox reagents is a topic of current interest. The dynamics of electroinactive ions across the interface is studied by immobilizing ferrocyanide anion in a polysilsesquioxanes (PSQs) modified electrode. Redox reagents can stay in the polymeric film by either physical forces or electrostatic binding. The present work describes the immobilization of ferro/ferricyanide redox couples in PSQ films possessing protonated amine functional groups by electrostatic interactions. Charge transport in [Fe(CN)6](4-)-PSQs film was found to be anion dependent, and its formal potential value varied with the relative hydrophilic or hydrophobic nature of the anion used in the supporting electrolyte, unlike the observed dependence on solution cation for electrodes modified with metal hexacyanoferrates (Prussian Blue analogues). The [Fe(CN)6](4-) bound PSQs films were extensively characterized by varying different supporting electrolytes anions using cyclic voltammetry. The redox peak currents were linearly proportional to the square root of the scan rate, implying that the transport of charge carriers is accompanied with redox ion diffusion and electron hopping in a confined space. dsDNA molecules were found to interact with this polymer matrix through anionic phosphate groups. Both voltammetry and A.C. impedance spectroscopy studies revealed that these interactions could be exploited for the determination of ultra-low level (0.5 attomolar) of dsDNA present in aqueous solution.

Characterization of a membrane-based, electrochemically driven pumping system using aqueous electrolyte solutions.

PubMed

Norman, Mya A; Evans, Christine E; Fuoco, Anthony R; Noble, Richard D; Koval, Carl A

2005-10-01

Electrokinetic flow provides a mechanism for a variety of fluid pumping schemes. The design and characterization of an electrochemically driven pump that utilizes porous carbon electrodes, iodide/triiodide redox electrolytes, and Nafion membranes is described. Fluid pumping by the cell is reversible and controlled by the cell current. Chronopotentiometry experiments indicate that the total available fluid that can be pumped in a single electrolysis without gas evolution is determined solely by the initial concentration of electrolyte and the applied current. The magnitude of the fluid flow at a given current is determined by the nature of the cation in the electrolyte and by the water absorption properties of the Nafion membrane. For 1 M aqueous electrolytes, pumping rates ranging from 1 to 14 microL/min were obtained for current densities of 10-30 mA/cm2 of membrane area. Molar volume changes for the I3-/I- redox couple and for the alkali cation migration contribute little to the observed volumetric flow rates; the magnitude of the flow is dominated by the migration-induced flow of water.

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

NASA Astrophysics Data System (ADS)

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

2016-07-01

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

Functionalized carbon nanotube based hybrid electrochemical capacitors using neutral bromide redox-active electrolyte for enhancing energy density

NASA Astrophysics Data System (ADS)

Tang, Xiaohui; Lui, Yu Hui; Chen, Bolin; Hu, Shan

2017-06-01

A hybrid electrochemical capacitor (EC) with enhanced energy density is realized by integrating functionalized carbon nanotube (FCNT) electrodes with redox-active electrolyte that has a neutral pH value (1 M Na2SO4 and 0.5 M KBr mixed aqueous solution). The negative electrode shows an electric double layer capacitor-type behavior. On the positive electrode, highly reversible Br-/Br3- redox reactions take place, presenting a battery-type behavior, which contributes to increase the capacitance of the hybrid cell. The voltage window of the whole cell is extended up to 1.5 V because of the high over-potentials of oxygen and hydrogen evolution reactions in the neutral electrolyte. Compared with raw CNT, the FCNT has better wettability in the aqueous electrolyte and contributes to increase the electric double layer capacitance of the cell. As a result, the maximum energy density of 28.3 Wh kg-1 is obtained from the hybrid EC at 0.5 A g-1 without sacrificing its power density, which is around 4 times larger than that of the electrical double layer capacitor constructed by FCNT electrodes and 1 M Na2SO4 electrolyte. Moreover, the discharge capacity retained 86.3% of its initial performance after 10000 cycles of galvanostatic charge and discharge test (10 A/g), suggesting its long life cycle even at high current loading.

Method and apparatus for determining minority carrier diffusion length in semiconductors

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

Moore, A.R.

1984-02-21

Method and apparatus are provided for determining the diffusion length of minority carriers in semiconductor material, particularly amorphous silicon, which has a significantly small minority carrier diffusion length using the constant magnitude surface-photovoltage (SPV) method. Steady or modulated illumination at several wavelengths provides the light excitation on the surface of the material to generate the SPV. A manually controlled or automatic servo system maintains a constant predetermined value of the SPB for each wavelength. A probe electrode immersed in an electrolyte solution containing redox couples (preferably quinhydrone) having an oxidation-reduction potential (E) in the order of +0.6 to -1.65 voltsmore » couples the SPV to a measurement system. The redox couple solution functions to create a liquid Schottky barrier at the surface of the material. The Schottky barrier is contacted by merely placing the probe in the solution. The redox solution is placed over and in contact with the material to be tested and light is passed through the solution to generate the SPV. To compensate for colored redox solutions a portion of the redox solution not over the material is also illuminated for determining the color compensated light intensity. Steady red light is also used as an optical bias to reduce deleterious space-charge effects that occur in amorphous silicon.« less

Method and apparatus for determining minority carrier diffusion length in semiconductors

DOEpatents

Moore, Arnold R.

1984-02-21

Method and apparatus are provided for determining the diffusion length of minority carriers in semiconductor material, particularly amorphous silicon, which has a significantly small minority carrier diffusion length using the constant magnitude surface-photovoltage (SPV) method. Steady or modulated illumination at several wavelengths provides the light excitation on the surface of the material to generate the SPV. A manually controlled or automatic servo system maintains a constant predetermined value of the SPV for each wavelength. A probe electrode immersed in an electrolyte solution containing redox couples (preferably quinhydrone) having an oxidation-reduction potential (E) in the order of +0.6 to -1.65 volts couples the SPV to a measurement system. The redox couple solution functions to create a liquid Schottky barrier at the surface of the material. The Schottky barrier is contacted by merely placing the probe in the solution. The redox solution is placed over and in contact with the material to be tested and light is passed through the solution to generate the SPV. To compensate for colored redox solutions a portion of the redox solution not over the material is also illuminated for determining the color compensated light intensity. Steady red light is also used as an optical bias to reduce deleterious space-charge effects that occur in amorphous silicon.

Durable electrooptic devices comprising ionic liquids

DOEpatents

Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM; Burrell, Anthony K [Los Alamos, NM

2006-10-10

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes

NASA Astrophysics Data System (ADS)

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-01

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes.

PubMed

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-15

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

Multiple-membrane multiple-electrolyte redox flow battery design

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

Yan, Yushan; Gu, Shuang; Gong, Ke

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

Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

2016-09-01

Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

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

PubMed Central

2018-01-01

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

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

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

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

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

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

PubMed

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

2018-02-28

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

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

DOE PAGES

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

2018-01-17

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

Electrochemistry serving people and nature: high-energy ecocapacitors based on redox-active electrolytes.

PubMed

Frackowiak, Elzbieta; Fic, Krzysztof; Meller, Mikolaj; Lota, Grzegorz

2012-07-01

Positive Poles: A new type of electrochemical capacitor with two different aqueous solutions, separated by a Nafion membrane is described. High capacitance values as well as excellent energy/power characteristics are reported and discussed. The neutral character of the applied electrolytes makes this capacitor an environmentally friendly, easy to assemble, and cost-effective device for energy storage. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cost-driven materials selection criteria for redox flow battery electrolytes

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Self-discharge of electrochemical capacitors based on soluble or grafted quinone.

PubMed

Shul, Galyna; Bélanger, Daniel

2016-07-28

The self-discharge of hybrid electrochemical capacitors based on the redox activity of electrolyte additives or grafted species to the electrode material is investigated simultaneously for the cell and each individual electrode. Electrochemical capacitors using a redox-active electrolyte consisting in hydroquinone added to the electrolyte solution and a redox-active electrode based on anthraquinone-grafted carbon as a negative electrode are investigated. The results are analyzed by using Conway kinetic models and compared to those of a common electrochemical double layer capacitor. The self-discharge investigation is complemented by charge/discharge cycling and it is shown that processes affecting galvanostatic charge/discharge cycling and the self-discharge rate occurring at each electrode of an electrochemical capacitor are different but related to each other. The electrochemical capacitor containing hydroquinone in the electrolyte exhibits a much quicker self-discharge rate than that using a negative electrode based on grafted anthraquinone with a 50% decay of the cell voltage of the fully charged device in 0.6 and 6 h, respectively. The fast self-discharge of the former is due to the diffusion of benzoquinone molecules (formed at the positive electrode during charging) to the negative electrode, where they are reduced, causing a quick depolarization. The grafting of anthraquinone molecules on the carbon material of the negative electrode led to a much slower self-discharge, which nonetheless occurred, by the reaction of the reduced form of the grafted species with electrolyte species.

Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy

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

Murugesan, Vijayakumar; Han, Kee Sung; Hu, Jianzhi

2017-03-19

Electrolytes help harness the energy from electrochemical processes by serving as solvents and transport media for redox-active ions. Molecular-level interactions between ionic solutes and solvent molecules – commonly referred to as solvation phenomena – give rise to many functional properties of electrolytes such as ionic conductivity, viscosity, and stability. It is critical to understand the evolution of solvation phenomena as a function of competing counterions and solvent mixtures to predict and design the optimal electrolyte for a target application. Probing oxygen environments is of great interest as oxygens are located at strategic molecular sites in battery solvents and are directlymore » involved in inter- and intramolecular solvation interactions. NMR signals from 17O nuclei in battery electrolytes offer nondestructive bulk measurements of isotropic shielding, electric field gradient tensors, and transverse and longitudinal relaxation rates, which are excellent means for probing structure, bonding, and dynamics of both solute and solvent molecules. This article describes the use of 17O NMR spectroscopy in probing the solvation structures of various electrolyte systems ranging from transition metal ions in aqueous solution to lithium cations in organic solvent mixtures.« less

Energy-density enhancement of carbon-nanotube-based supercapacitors with redox couple in organic electrolyte.

PubMed

Park, Jinwoo; Kim, Byungwoo; Yoo, Young-Eun; Chung, Haegeun; Kim, Woong

2014-11-26

We demonstrate for the first time that the incorporation of a redox-active molecule in an organic electrolyte can increase the cell voltage of a supercapacitor. The redox molecule also contributes to increasing the cell capacitance by a faradaic redox reaction, and therefore the energy density of the supercapacitor can be significantly increased. More specifically, the addition of redox-active decamethylferrocene in an organic electrolyte results in an approximately 27-fold increase in the energy density of carbon-nanotube-based supercapacitors. The resulting high energy density (36.8 Wh/kg) stems from the increased cell voltage (1.1 V→2.1 V) and cell capacitance (8.3 F/g→61.3 F/g) resulting from decamethylferrocene addition. We found that the voltage increase is associated with the potential of the redox species relative to the electrochemical stability window of the supporting electrolyte. These results will be useful in identifying new electrolytes for high-energy-density supercapacitors.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Energy storage device including a redox-enhanced electrolyte

DOEpatents

Stucky, Galen; Evanko, Brian; Parker, Nicholas; Vonlanthen, David; Auston, David; Boettcher, Shannon; Chun, Sang-Eun; Ji, Xiulei; Wang, Bao; Wang, Xingfeng; Chandrabose, Raghu Subash

2017-08-08

An electrical double layer capacitor (EDLC) energy storage device is provided that includes at least two electrodes and a redox-enhanced electrolyte including two redox couples such that there is a different one of the redox couples for each of the electrodes. When charged, the charge is stored in Faradaic reactions with the at least two redox couples in the electrolyte and in a double-layer capacitance of a porous carbon material that comprises at least one of the electrodes, and a self-discharge of the energy storage device is mitigated by at least one of electrostatic attraction, adsorption, physisorption, and chemisorption of a redox couple onto the porous carbon material.

Enhanced performance of ultracapacitors using redox additive-based electrolytes

NASA Astrophysics Data System (ADS)

Jain, Dharmendra; Kanungo, Jitendra; Tripathi, S. K.

2018-05-01

Different concentrations of potassium iodide (KI) as redox additive had been added to 1 M sulfuric acid (H2SO4) electrolyte with an aim of enhancing the capacitance and energy density of ultracapacitors via redox reactions at the interfaces of electrode-electrolyte. Ultracapacitors were fabricated using chemically treated activated carbon as electrode with H2SO4 and H2SO4-KI as an electrolyte. The electrochemical performances of fabricated supercapacitors were investigated by impedance spectroscopy, cyclic voltammetry and charge-discharge techniques. The maximum capacitance ` C' was observed with redox additives-based electrolyte system comprising 1 M H2SO4-0.3 M KI (1072 F g- 1), which is very much higher than conventional 1 M H2SO4 (61.3 F g- 1) aqueous electrolyte-based ultracapacitors. It corresponds to an energy density of 20.49 Wh kg- 1 at 2.1 A g- 1 for redox additive-based electrolyte, which is six times higher as compared to that of pristine electrolyte (1 M H2SO4) having energy density of only 3.36 Wh kg- 1. The temperature dependence behavior of fabricated cell was also analyzed, which shows increasing pattern in its capacitance values in a temperature range of 5-70 °C. Under cyclic stability test, redox electrolyte-based system shows almost 100% capacitance retention up to 5000 cycles and even more. For comparison, ultracapacitors based on polymer gel electrolyte polyvinyl alcohol (PVA) (10 wt%)—{H2SO4 (1 M)-KI (0.3 M)} (90 wt%) have been fabricated and characterized with the same electrode materials.

Anion permselective membrane

NASA Technical Reports Server (NTRS)

Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

1984-01-01

Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

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

PubMed

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

2012-08-07

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

Negative-Electrode Catalysts for Fe/Cr Redox Cells

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N.

1987-01-01

Electrodes perform more consistently and less expensive. Surfaces catalyzed by bismuth and bismuth/lead developed for application on chromium electrode in iron/chromium redox electrochemical energy storage system. NASA Fe/Cr storage system incorporates two soluble electrodes consisting of acidified solutions of iron chloride (FeC13 and FeC12) and chromium chloride (CrC13 and CrC12) oxidized and reduced in power-conversion unit to store and produce electricity. Electrolytes circulated with pumps and stored in external tanks.

Redox Active Polymers as Soluble Nanomaterials for Energy Storage.

PubMed

Burgess, Mark; Moore, Jeffrey S; Rodríguez-López, Joaquín

2016-11-15

It is an exciting time for exploring the synergism between the chemical and dimensional properties of redox nanomaterials for addressing the manifold performance demands faced by energy storage technologies. The call for widespread adoption of alternative energy sources requires the combination of emerging chemical concepts with redesigned battery formats. Our groups are interested in the development and implementation of a new strategy for nonaqueous flow batteries (NRFBs) for grid energy storage. Our motivation is to solve major challenges in NRFBs, such as the lack of membranes that simultaneously allow fast ion transport while minimizing redox active species crossover between anolyte (negative electrolyte) and catholyte (positive electrolyte) compartments. This pervasive crossover leads to deleterious capacity fade and materials underutilization. In this Account, we highlight redox active polymers (RAPs) and related polymer colloids as soluble nanoscopic energy storing units that enable the simple but powerful size-exclusion concept for NRFBs. Crossover of the redox component is suppressed by matching high molecular weight RAPs with simple and inexpensive nanoporous commercial separators. In contrast to the vast literature on the redox chemistry of electrode-confined polymer films, studies on the electrochemistry of solubilized RAPs are incipient. This is due in part to challenges in finding suitable solvents that enable systematic studies on high polymers. Here, viologen-, ferrocene- and nitrostyrene-based polymers in various formats exhibit properties that make amenable their electrochemical exploration as solution-phase redox couples. A main finding is that RAP solutions store energy efficiently and reversibly while offering chemical modularity and size versatility. Beyond the practicality toward their use in NRFBs, the fundamental electrochemistry exhibited by RAPs is fascinating, showing clear distinctions in behavior from that of small molecules. Whereas RAPs conveniently translate the redox properties of small molecules into a nanostructure, they give rise to charge transfer mechanisms and electrolyte interactions that elicit distinct electrochemical responses. To understand how the electrochemical characteristics of RAPs depend on molecular features, including redox moiety, macromolecular size, and backbone structure, a range of techniques has been employed by our groups, including voltammetry at macro- and microelectrodes, rotating disk electrode voltammetry, bulk electrolysis, and scanning electrochemical microscopy. RAPs rely on three-dimensional charge transfer within their inner bulk, which is an efficient process and allows quantitative electrolysis of particles of up to ∼800 nm in radius. Interestingly, we find that interactions between neighboring pendants create unique opportunities for fine-tuning their electrochemical reactivity. Furthermore, RAP interrogation toward the single particle limit promises to shed light on fundamental charge storage mechanisms.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge.

PubMed

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D; Boettcher, Shannon W

2015-08-04

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg(-1) based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30-50 Wh kg(-1) is possible with optimization.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge

PubMed Central

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D.; Boettcher, Shannon W.

2015-01-01

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg−1 based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30–50 Wh kg−1 is possible with optimization. PMID:26239891

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

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

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

2013-11-01

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

POM-assisted electrochemical delignification and bleaching of chemical pulp

Treesearch

Helene Laroche; Mohini Sain; Carl Houtman; Claude Daneault

2001-01-01

A polyoxometalate-catalyzed electrochemical process has shown good selectivity in delignifying pulp. This breakthrough in redox catalysis shows promise for the development of a new environmentally benign technology for pulp bleaching. The electrochemical process, applied with a mildly alkaline electrolyte solution containing trace amounts of a vanadium-based...

Enhanced electrochemical performance of monoclinic WO3 thin film with redox additive aqueous electrolyte.

PubMed

Shinde, Pragati A; Lokhande, Vaibhav C; Chodankar, Nilesh R; Ji, Taeksoo; Kim, Jin Hyeok; Lokhande, Chandrakant D

2016-12-01

To achieve the highest electrochemical performance for supercapacitor, it is very essential to find out a suitable pair of an active electrode material and an electrolyte. In the present work, a simple approach is employed to enhance the supercapacitor performance of WO3 thin film. The WO3 thin film is prepared by a simple and cost effective chemical bath deposition method and its electrochemical performance is tested in conventional (H2SO4) and redox additive [H2SO4+hydroquinone (HQ)] electrolytes. Two-fold increment in electrochemical performance for WO3 thin film is observed in redox additive aqueous electrolyte compared to conventional electrolyte. WO3 thin film showed maximum specific capacitance of 725Fg(-1), energy density of 25.18Whkg(-1) at current density of 7mAcm(-2) with better cycling stability in redox electrolyte. This strategy provides the versatile way for designing the high performance energy storage devices. Copyright © 2016 Elsevier Inc. All rights reserved.

High Performance of Supercapacitor from PEDOT:PSS Electrode and Redox Iodide Ion Electrolyte

PubMed Central

Gao, Xing; Zu, Lei; Cai, Xiaomin; Li, Ce; Lian, Huiqin; Liu, Yang; Wang, Xiaodong; Cui, Xiuguo

2018-01-01

Insufficient energy density and poor cyclic stability is still challenge for conductive polymer-based supercapacitor. Herein, high performance electrochemical system has been assembled by combining poly (3,4-ethylenedioxythiophene) (PEDOT):poly (styrene sulfonate) (PSS) redox electrode and potassium iodide redox electrolyte, which provide the maximum specific capacity of 51.3 mAh/g and the retention of specific capacity of 87.6% after 3000 cycles due to the synergic effect through a simultaneous redox reaction both in electrode and electrolyte, as well as the catalytic activity for reduction of triiodide of the PEDOT:PSS. PMID:29772662

Iterative absolute electroanalytical approach to characterization of bulk redox conducting systems.

PubMed

Lewera, Adam; Miecznikowski, Krzysztof; Chojak, Malgorzata; Makowski, Oktawian; Golimowski, Jerzy; Kulesza, Pawel J

2004-05-15

A novel electroanalytical approach is proposed here, and it is demonstrated with the direct and simultaneous determination of two unknowns: the concentration of redox sites and the apparent diffusion coefficient for charge propagation in a single crystal of dodecatungstophosphoric acid. This Keggin-type polyoxometalate serves as a model bulk redox conducting inorganic material for solid-state voltammetry. The system has been investigated using an ultramicrodisk working electrode in the absence of external liquid supporting electrolyte. The analytical method requires numerical solution of the combination of two equations in which the first one describes current (or charge) in a well-defined (either spherical or linear) diffusional regime and the second general equation describes chronoamperometric (or normal pulse voltammetric current) under mixed (linear-spherical) conditions. The iterative approach is based on successive approximations through calculation and minimizing the least-squares error function. The method is fairly universal, and in principle, it can be extended to the investigation of other bulk systems including sol-gel processed materials, redox melts, and solutions on condition that they are electroactive and well behaved, they contain redox centers at sufficiently high level, and a number of electrons for the redox reaction considered is known.

Analytical expression for the tunnel current through the redox-mediated tunneling contact in the case of the adiabatic electron transfer at one of the working electrodes and any possible type of the electron transfer at the other electrode

NASA Astrophysics Data System (ADS)

Medvedev, Igor G.

2017-11-01

We study the tunnel current through a one-level redox molecule immersed into the electrolyte solution for the case when the coupling of the molecule to one of the working electrodes is strong while it is arbitrary to the other electrode. Using the Feynman-Vernon influence functional theory and the perturbation expansion of the effective action of the classical oscillator coupled both to the valence level of the redox molecule and to the thermal bath representing the classical fluctuations of the polarization of the solvent, we obtain, following the canonical way, the Langevin equation for the oscillator. It is found that for the aqueous electrolyte solution, the damping and the stochastic forces which arise due to the tunnel current are much smaller than those due to the thermal bath and therefore can be neglected. We estimate the higher-order corrections to the effective action and show that the Langevin dynamics takes place in this case for arbitrary parameters of the tunneling junction under the condition of the strong coupling of the redox molecule to one of the working electrodes. Then the steady-state coordinate distribution function of the oscillator resulting from the corresponding Fokker-Planck equation is the Boltzmann distribution function which is determined by the adiabatic free energy surface arising from the mean current-induced force. It enables us to obtain the expression for the tunnel current in the case when the coupling of the redox molecule to one of the working electrodes is strong while it is arbitrary to the other electrode.

Analytical expression for the tunnel current through the redox-mediated tunneling contact in the case of the adiabatic electron transfer at one of the working electrodes and any possible type of the electron transfer at the other electrode.

PubMed

Medvedev, Igor G

2017-11-21

We study the tunnel current through a one-level redox molecule immersed into the electrolyte solution for the case when the coupling of the molecule to one of the working electrodes is strong while it is arbitrary to the other electrode. Using the Feynman-Vernon influence functional theory and the perturbation expansion of the effective action of the classical oscillator coupled both to the valence level of the redox molecule and to the thermal bath representing the classical fluctuations of the polarization of the solvent, we obtain, following the canonical way, the Langevin equation for the oscillator. It is found that for the aqueous electrolyte solution, the damping and the stochastic forces which arise due to the tunnel current are much smaller than those due to the thermal bath and therefore can be neglected. We estimate the higher-order corrections to the effective action and show that the Langevin dynamics takes place in this case for arbitrary parameters of the tunneling junction under the condition of the strong coupling of the redox molecule to one of the working electrodes. Then the steady-state coordinate distribution function of the oscillator resulting from the corresponding Fokker-Planck equation is the Boltzmann distribution function which is determined by the adiabatic free energy surface arising from the mean current-induced force. It enables us to obtain the expression for the tunnel current in the case when the coupling of the redox molecule to one of the working electrodes is strong while it is arbitrary to the other electrode.

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

PubMed

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

2016-11-07

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

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

PubMed

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.

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

DOE PAGES

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

2015-11-20

We proposed and developed an all-iron redox flow battery 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. Our 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 Fe 2 (SO 4 ) 3 activemore » material and 1.2 m NaCl supporting electrolyte. Furthermore, 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.« less

Method and apparatus for determining minority carrier diffusion length in semiconductors

DOEpatents

Moore, Arnold R.

1984-01-01

Method and apparatus are provided for determining the diffusion length of minority carriers in semiconductor material, particularly amorphous silicon which has a significantly small minority carrier diffusion length using the constant magnitude surface-photovoltage (SPV) method. Steady or modulated illumination at several wavelengths provides the light excitation on the surface of the material to generate the SPV. A manually controlled or automatic servo system maintains a constant predetermined value of the SPV for each wavelength. A drop of a transparent electrolyte solution containing redox couples (preferably quinhydrone) having an oxidation-reduction potential (E) in the order of +0.6 to -1.65 volts couples the SPV to a measurement system. The drop of redox couple solution functions to create a liquid Schottky barrier at the surface of the material. Illumination light is passed through a transparent rod supported over the surface and through the drop of transparent electrolyte. The drop is held in the gap between the rod and the surface. Steady red light is also used as an optical bias to reduce deleterious space-charge effects that occur in amorphous silicon.

Electrolytes Based on TEMPO–Co Tandem Redox Systems Outperform Single Redox Systems in Dye‐sensitized Solar Cells

PubMed Central

Cong, Jiayan; Hao, Yan; Boschloo, Gerrit

2014-01-01

Abstract A new TEMPO–Co tandem redox system with TEMPO and Co(bpy)3 2+/3+ has been investigated for the use in dye‐sensitized solar cells (DSSCs). A large open‐circuit voltage (V OC) increase, from 862 mV to 965 mV, was observed in the tandem redox system, while the short‐circuit current density (J SC) was maintained. The conversion efficiency was observed to increase from 7.1 % for cells containing the single Co(bpy)3 2+/3+ redox couple, to 8.4 % for cells containing the TEMPO–Co tandem redox system. The reason for the increase in V OC and overall efficiency is ascribed to the involvement of partial regeneration of the sensitizing dye molecules by TEMPO. This assumption can be verified through the observed much faster regeneration dynamics exhibited in the presence of the tandem system. Using the tandem redox system, the faster recombination problem of the single TEMPO redox couple is resolved and the mass‐transport of the metal‐complex‐based electrolyte is also improved. This TEMPO–Co tandem system is so far the most effienct tandem redox electrolyte reported not involving iodine. The current results show a promising future for tandem system as replacements for single redox systems in electrolytes for DSSCs. PMID:25504818

Magnetic Cobalt Ferrite Nanocrystals For an Energy Storage Concentration Cell.

PubMed

Dai, Qilin; Patel, Ketan; Donatelli, Greg; Ren, Shenqiang

2016-08-22

Energy-storage concentration cells are based on the concentration gradient of redox-active reactants; the increased entropy is transformed into electric energy as the concentration gradient reaches equilibrium between two half cells. A recyclable and flow-controlled magnetic electrolyte concentration cell is now presented. The hybrid inorganic-organic nanocrystal-based electrolyte, consisting of molecular redox-active ligands adsorbed on the surface of magnetic nanocrystals, leads to a magnetic-field-driven concentration gradient of redox molecules. The energy storage performance of concentration cells is dictated by magnetic characteristics of cobalt ferrite nanocrystal carriers. The enhanced conductivity and kinetics of redox-active electrolytes could further induce a sharp concentration gradient to improve the energy density and voltage switching of magnetic electrolyte concentration cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolytes For Electrooptic Devices Comprising Ionic Liqu Ids

DOEpatents

Warner, Benjamin P.; McCleskey, T. Mark; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Burrell, Anthony K.

2005-02-08

Electrolyte solutions of soluble bifunctional redox dyes in molten salt solvent may be used to prepare electrooptic devices with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3 SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3 SO.sub.2).sub.2 N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3 CF.sub.2 SO.sub.2).sub.2 N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3 SO.sub.2).sub.3 C.sup.-).

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

PubMed Central

Wedege, Kristina; Azevedo, João; Khataee, Amirreza

2016-01-01

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

Quasi-solid state electrolytes for low-grade thermal energy harvesting using a cobalt redox couple.

PubMed

Taheri, Abuzar; MacFarlane, Douglas; Pozo-Gonzalo, Cristina; Pringle, Jennifer M

2018-06-06

Thermoelectrochemical cells, also known as thermocells, are electrochemical devices for the conversion of thermal energy directly to electricity. They are a promising method for harvesting low-grade waste heat from a variety of different natural and man-made sources. The development of solid or quasi-solid state electrolytes for thermocells could address the possible leakage problems of liquid electrolytes and make this technology more applicable for wearable devices. Here we report the gelation of an organic solvent-based electrolyte system containing a redox couple, for application in thermocell technologies. The effect of gelation of the liquid electrolyte, comprising a cobalt bipyridyl redox couple dissolved in 3-methoxypropionitrile (MPN), on the performance of thermocells was investigated. Polyvinylidene difluoride (PVDF) and poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP) were used for gelation of the electrolyte, and the influence of the different polymers on the mechanical properties was studied. The Seebeck coefficient and diffusivity of the cobalt redox couple were measured in both liquid and gelled electrolytes and the effect of gelation on the thermocell performance is reported. Finally, the cell performance was further improved by optimising the redox couple concentration and the separation between the hot and cold electrode, and the stability of the device over 25 hours of operation is demonstrated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Bio-Inspired, Heavy-Metal-Free, Dual-Electrolyte Liquid Battery towards Sustainable Energy Storage.

PubMed

Ding, Yu; Yu, Guihua

2016-04-04

Wide-scale exploitation of renewable energy requires low-cost efficient energy storage devices. The use of metal-free, inexpensive redox-active organic materials represents a promising direction for environmental-friendly, cost-effective sustainable energy storage. To this end, a liquid battery is designed using hydroquinone (H2BQ) aqueous solution as catholyte and graphite in aprotic electrolyte as anode. The working potential can reach 3.4 V, with specific capacity of 395 mA h g(-1) and stable capacity retention about 99.7% per cycle. Such high potential and capacity is achieved using only C, H and O atoms as building blocks for redox species, and the replacement of Li metal with graphite anode can circumvent potential safety issues. As H2BQ can be extracted from biomass directly and its redox reaction mimics the bio-electrochemical process of quinones in nature, using such a bio-inspired organic compound in batteries enables access to greener and more sustainable energy-storage technology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

PubMed

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

2015-11-05

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

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

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

PubMed

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

2016-06-13

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

Rebalancing electrolytes in redox flow battery systems

DOEpatents

Chang, On Kok; Pham, Ai Quoc

2014-12-23

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

A plasticized polymer-electrolyte-based photoelectrochemical solar cell

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

Mao, D.; Ibrahim, M.A.; Frank, A.J.

1998-01-01

A photoelectrochemical solar cell based on an n-GaAs/polymer-redox-electrolyte junction is reported. Di(ethylene glycol) ethyl ether acrylate containing ferrocene as a redox species and benzoin methyl ether as a photoinitiator is polymerized in situ. Propylene carbonate is used as a plasticizer to improve the conductivity of the polymer redox electrolyte. For thin (1 {micro}m) polymer electrolytes, the series resistance of the cell is negligible. However, the short-circuit photocurrent density of the cell at light intensities above 10 mW/cm{sup 2} is limited by mass transport of redox species within the polymer matrix. At a light intensity of 70 mW/cm{sup 2}, a moderatemore » light-to-electrical energy conversion efficiency (3.1%) is obtained. The interfacial charge-transfer properties of the cell in the dark and under illumination are studied.« less

Block Copolymer Patterns as Templates for the Electrocatalyzed Deposition of Nanostructures on Electrodes and for the Generation of Surfaces of Controlled Wettability.

PubMed

Chandaluri, Chanchayya Gupta; Pelossof, Gilad; Tel-Vered, Ran; Shenhar, Roy; Willner, Itamar

2016-01-20

ITO electrodes modified with a nanopatterned film of polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP, where the P2VP domains are quaternized with iodomethane, are used for selective deposition of redox-active materials. Electrochemical studies (cyclic voltammetry, Faradaic impedance measurements) indicate that the PS domains insulate the conductive surface toward redox labels in solution. In turn, the quaternized P2VP domains electrostatically attract negatively charged redox labels solubilized in the electrolyte solution, resulting in an effective electron transfer between the electrode and the redox label. This phenomenon is implemented for the selective deposition of the electroactive Prussian blue on the nanopatterned surface and for the electrochemical deposition of Au nanoparticles, modified with a monolayer of p-aminothiophenol/2-mercaptoethanesulfonic acid, on the quaternized P2VP domains. The patterned Prussian blue-modified surface enables controlling the wettability properties by the content of the electrochemically deposited Prussian blue. Controlled wettability is unattainable with the homopolymer-modified surface, attesting to the role of the nanopattern.

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

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

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

2015-01-01

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

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

DOE PAGES

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

2015-01-09

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

Grid Scale Energy Storage (Symposium EE8)

DTIC Science & Technology

2016-06-01

27709-2211 Grid-Scale Energy Storage, electrolytes, systems ntegration, Lithium - ion chemistry, Redox flow batteries REPORT DOCUMENTATION PAGE 11... Lithium - Ion Chemistry (4) Redox Flow Batteries Christopher J. Orendorff from Sandia National Laboratories kicked off the symposium on Tuesday...for redox flow batteries . SEI formation is a well-known process in standard lithium - ion battery operation; however, using aqueous electrolytes does

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

Deng, Xuchu; Hu, Mary; Wei, Xiaoliang

Understanding the solvation structures of electrolytes is important for developing nonaqueous redox flow batteries that hold considerable potential for future large scale energy storage systems. The utilization of an emerging ionic-derivative ferrocene compounds, ferrocenylmethyl dimethyl ethyl ammonium bis (triflyoromethanesulfonyl)imide (Fc1N112-TFSI), has recently overcome the issue of solubility in the supporting electrolyte. In this work, 13C1H and 17O NMR investigations were carried out using solvent. It was observed that the spectra of 13C experience changes of chemical shifts while those of 17O undergo line width broadening, indicating interactions between solute and solvent molecules

High-efficiency dye-sensitized solar cells with ferrocene-based electrolytes.

PubMed

Daeneke, Torben; Kwon, Tae-Hyuk; Holmes, Andrew B; Duffy, Noel W; Bach, Udo; Spiccia, Leone

2011-03-01

Dye-sensitized solar cells based on iodide/triiodide (I(-)/I(3)(-)) electrolytes are viable low-cost alternatives to conventional silicon solar cells. However, as well as providing record efficiencies of up to 12.0%, the use of I(-)/I(3)(-) in such solar cells also brings about certain limitations that stem from its corrosive nature and complex two-electron redox chemistry. Alternative redox mediators have been investigated, but these generally fall well short of matching the performance of conventional I(-)/I(3)(-) electrolytes. Here, we report energy conversion efficiencies of 7.5% (simulated sunlight, AM1.5, 1,000 W m(-2)) for dye-sensitized solar cells combining the archetypal ferrocene/ferrocenium (Fc/Fc(+)) single-electron redox couple with a novel metal-free organic donor-acceptor sensitizer (Carbz-PAHTDTT). These Fc/Fc(+)-based devices exceed the efficiency achieved for devices prepared using I(-)/I(3)(-) electrolytes under comparable conditions, revealing the great potential of ferrocene-based electrolytes in future dye-sensitized solar cells applications. This improvement results from a more favourable matching of the redox potential of the ferrocene couple with that of the new donor-acceptor sensitizer.

Ultrafast photodynamics of the indoline dye D149 adsorbed to porous ZnO in dye-sensitized solar cells.

PubMed

Rohwer, Egmont; Richter, Christoph; Heming, Nadine; Strauch, Kerstin; Litwinski, Christian; Nyokong, Tebello; Schlettwein, Derck; Schwoerer, Heinrich

2013-01-14

We investigate the ultrafast dynamics of the photoinduced electron transfer between surface-adsorbed indoline D149 dye and porous ZnO as used in the working electrodes of dye-sensitized solar cells. Transient absorption spectroscopy was conducted on the dye in solution, on solid state samples and for the latter in contact to a I(-)/I(3)(-) redox electrolyte typical for dye-sensitized solar cells to elucidate the effect of each component in the observed dynamics. D149 in a solution of 1:1 acetonitrile and tert-butyl alcohol shows excited-state lifetimes of 300±50 ps. This signature is severely quenched when D149 is adsorbed to ZnO, with the fastest component of the decay trace measured at 150±20 fs due to the charge-transfer mechanism. Absorption bands of the oxidized dye molecule were investigated to determine regeneration times which are in excess of 1 ns. The addition of the redox electrolyte to the system results in faster regeneration times, of the order of 1 ns. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring electrolyte concentrations in redox flow battery systems

DOEpatents

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

2015-03-17

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

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

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

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

PubMed Central

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; Li, Jinyang; Schwab, Mark J.; Brudvig, Gary W.; Taylor, André D.

2016-01-01

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme's oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage. PMID:27759005

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

DOE PAGES

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; ...

2016-10-19

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Impact of Backbone Tether Length and Structure on the Electrochemical Performance of Viologen Redox Active Polymers

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

Burgess, Mark; Chénard, Etienne; Hernández-Burgos, Kenneth

The design of chemically stable and electrochemically reversible redox active polymers (RAPs) is of great interest for energy storage technologies. Particularly, RAPs are new players for flow batteries relying on a size-exclusion based mechanism of electrolyte separation, but few studies have provided detailed molecular understanding of redox polymers in solution. Here, we use a systematic molecular design approach to investigate the impact of linker and redox-pendant electronic interactions on the performance of viologen RAPs. We used scanning electrochemical microscopy, cyclic voltammetry, bulk electrolysis, temperature-dependent absorbance, and spectroelectrochemistry to study the redox properties, charge transfer kinetics, and self-exchange of electrons throughmore » redox active dimers and their equivalent polymers. Stark contrast was observed between the electrochemical properties of viologen dimers and their corresponding polymers. Electron self-exchange kinetics in redox active dimers that only differ by their tether length and rigidity influences their charge transfer properties. Predictions from the Marcus Hush theory were consistent with observations in redox active dimers, but they failed to fully capture the behavior of macromolecular systems. For example, polymer bound viologen pendants, if too close in proximity, do not retain chemical reversibility. In contrast to polymer films, small modifications to the backbone structure decisively impact the bulk electrolysis of polymer solutions. This first comprehensive study highlights the careful balance between electronic interactions and backbone rigidity required to design RAPs with superior electrochemical performance.« less

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

PubMed

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.

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

PubMed

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

2015-07-20

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

Investigation of Charge Transfer Kinetics at Carbon/Hydroquinone Interfaces for Redox-Active-Electrolyte Supercapacitors.

PubMed

Park, Jinwoo; Kumar, Vipin; Wang, Xu; Lee, Pooi See; Kim, Woong

2017-10-04

The redox-active electrolyte supercapacitor (RAES) is a relatively new type of energy storage device. Simple addition of selected redox species in the electrolyte can greatly enhance the energy density of supercapacitors relative to traditional electric double layer capacitors (EDLCs) owing to redox reactions. Studies on the kinetics at the interface of the electrode and redox mediator are important when developing RAESs. In this work, we employ highly accurate scanning electrochemical microscopy (SECM) to extract the kinetic constants at carbon/hydroquinone interfaces. The charge transfer rate constants are 1.2 × 10 -2 and 1.3 × 10 -2 cm s -1 for the carbon nanotube/hydroquinone and reduced graphene oxide/hydroquinone interfaces, respectively. These values are higher than those obtained by the conventional cyclic voltammetry method, approximately by an order of magnitude. The evaluation of heterogeneous rate constants with SECM would be the cornerstone for understanding and developing high performance RAESs.

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

DOE PAGES

Li, Bin; Nie, Zimin; Vijayakumar, M.; ...

2015-02-24

Large-scale energy storage systems are crucial for substantial deployment of renewable energy sources. Energy storage systems with high energy density, high safety, and low cost and environmental friendliness are desired. To overcome the major limitations of the current aqueous redox flow battery systems, namely lower energy density (~25 Wh L -1) and presence of strong acids and/or other hazardous, a high energy density aqueous zinc/polyiodide flow battery (ZIB) is designed with near neutral ZnI 2 solutions as catholytes. The energy density of ZIB could reach 322 Wh L -1 at the solubility limit of ZnI 2 in water (~7 M).more » We demonstrate charge and discharge energy densities of 245.9 Wh/L and 166.7 Wh L-1 with ZnI 2 electrolyte at 5.0 M, respectively. The addition of ethanol (EtOH) in ZnI 2 electrolyte can effectively mitigate the growth of zinc dendrite at the anode and improve the stability of catholytes with wider temperature window (-20 to 50°C), which enable ZIB system to be a promising alternative as a high-energy and high- safety stationary energy storage system.« less

Symmetric redox supercapacitor based on micro-fabrication with three-dimensional polypyrrole electrodes

NASA Astrophysics Data System (ADS)

Sun, Wei; Zheng, Ruilin; Chen, Xuyuan

To achieve higher energy density and power density, we have designed and fabricated a symmetric redox supercapacitor based on microelectromechanical system (MEMS) technologies. The supercapacitor consists of a three-dimensional (3D) microstructure on silicon substrate micromachined by high-aspect-ratio deep reactive ion etching (DRIE) method, two sputtered Ti current collectors and two electrochemical polymerized polypyrrole (PPy) films as electrodes. Electrochemical tests, including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatical charge/discharge methods have been carried out on the single PPy electrodes and the symmetric supercapacitor in different electrolytes. The specific capacitance (capacitance per unit footprint area) and specific power (power per unit footprint area) of the PPy electrodes and symmetric supercapacitor can be calculated from the electrochemical test data. It is found that NaCl solution is a good electrolyte for the polymerized PPy electrodes. In NaCl electrolyte, single PPy electrodes exhibit 0.128 F cm -2 specific capacitance and 1.28 mW cm -2 specific power at 20 mV s -1 scan rate. The symmetric supercapacitor presents 0.056 F cm -2 specific capacitance and 0.56 mW cm -2 specific power at 20 mV s -1 scan rate.

Synthesis and Characterization of Cellulose-Based Hydrogels to Be Used as Gel Electrolytes

PubMed Central

Navarra, Maria Assunta; Dal Bosco, Chiara; Serra Moreno, Judith; Vitucci, Francesco Maria; Paolone, Annalisa; Panero, Stefania

2015-01-01

Cellulose-based hydrogels, obtained by tuned, low-cost synthetic routes, are proposed as convenient gel electrolyte membranes. Hydrogels have been prepared from different types of cellulose by optimized solubilization and crosslinking steps. The obtained gel membranes have been characterized by infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mechanical tests in order to investigate the crosslinking occurrence and modifications of cellulose resulting from the synthetic process, morphology of the hydrogels, their thermal stability, and viscoelastic-extensional properties, respectively. Hydrogels liquid uptake capability and ionic conductivity, derived from absorption of aqueous electrolytic solutions, have been evaluated, to assess the successful applicability of the proposed membranes as gel electrolytes for electrochemical devices. To this purpose, the redox behavior of electroactive species entrapped into the hydrogels has been investigated by cyclic voltammetry tests, revealing very high reversibility and ion diffusivity. PMID:26633528

Hybrid capacitors utilizing halogen-based redox reactions at interface between carbon positive electrode and aqueous electrolytes

NASA Astrophysics Data System (ADS)

Yamazaki, Shigeaki; Ito, Tatsuya; Murakumo, Yuka; Naitou, Masashi; Shimooka, Toshiharu; Yamagata, Masaki; Ishikawa, Masashi

2016-09-01

We propose novel hybrid capacitors (HCs) with electrolyte-involved redox reactions of bromide or iodide species by pretreatment of an activated carbon positive electrode. The treatment is simple; impregnation of pores at an activated carbon fiber cloth (ACFC) as a positive electrode with bromine- or iodine-containing water before cell assembly. The treated positive electrode is applied to a HC cell with a non-treated negative electrode of ACFC and its electrochemical performance is investigated by galvanostatic cycling and leakage current tests. Few studies on such "electrolytic" charge storage systems have provided acceptable capacitor performance because of inevitable self-discharge caused by diffusion of charged species form an electrode to the other one through an electrolyte. Nevertheless, our electrolyte-redox-based HCs show excellent performance without undesirable diffusion of charged species. Moreover, the present HC utilizing a bromide redox system fulfills a practical cell voltage of 1.8 V in spite of an aqueous electrolyte system. This high voltage provides excellent energy density, which is 5 times higher than that in a conventional aqueous electric double-layer capacitor (EDLC), and 1.2 times higher even than that in a 2.7 V-class non-aqueous EDLC, while keeping high charge-discharge rate capability.

Cascade redox flow battery systems

DOEpatents

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

2014-07-22

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

Efficient dye regeneration at low driving force achieved in triphenylamine dye LEG4 and TEMPO redox mediator based dye-sensitized solar cells.

PubMed

Yang, Wenxing; Vlachopoulos, Nick; Hao, Yan; Hagfeldt, Anders; Boschloo, Gerrit

2015-06-28

Minimizing the driving force required for the regeneration of oxidized dyes using redox mediators in an electrolyte is essential to further improve the open-circuit voltage and efficiency of dye-sensitized solar cells (DSSCs). Appropriate combinations of redox mediators and dye molecules should be explored to achieve this goal. Herein, we present a triphenylamine dye, LEG4, in combination with a TEMPO-based electrolyte in acetonitrile (E(0) = 0.89 V vs. NHE), reaching an efficiency of up to 5.4% under one sun illumination and 40% performance improvement compared to the previously and widely used indoline dye D149. The origin of this improvement was found to be the increased dye regeneration efficiency of LEG4 using the TEMPO redox mediator, which regenerated more than 80% of the oxidized dye with a driving force of only ∼0.2 eV. Detailed mechanistic studies further revealed that in addition to electron recombination to oxidized dyes, recombination of electrons from the conducting substrate and the mesoporous TiO2 film to the TEMPO(+) redox species in the electrolyte accounts for the reduced short circuit current, compared to the state-of-the-art cobalt tris(bipyridine) electrolyte system. The diffusion length of the TEMPO-electrolyte based DSSCs was determined to be ∼0.5 μm, which is smaller than the ∼2.8 μm found for cobalt-electrolyte based DSSCs. These results show the advantages of using LEG4 as a sensitizer, compared to previously record indoline dyes, in combination with a TEMPO-based electrolyte. The low driving force for efficient dye regeneration presented by these results shows the potential to further improve the power conversion efficiency (PCE) of DSSCs by utilizing redox couples and dyes with a minimal need of driving force for high regeneration yields.

Electrochemical Applications in Metal Bioleaching.

PubMed

Tanne, Christoph Kurt; Schippers, Axel

2017-12-10

Biohydrometallurgy comprises the recovery of metals by biologically catalyzed metal dissolution from solids in an aqueous solution. The application of this kind of bioprocessing is described as "biomining," referring to either bioleaching or biooxidation of sulfide metal ores. Acidophilic iron- and sulfur-oxidizing microorganisms are the key to successful biomining. However, minerals such as primary copper sulfides are recalcitrant to dissolution, which is probably due to their semiconductivity or passivation effects, resulting in low reaction rates. Thus, further improvements of the bioleaching process are recommendable. Mineral sulfide dissolution is based on redox reactions and can be accomplished by electrochemical technologies. The impact of electrochemistry on biohydrometallurgy affects processing as well as analytics. Electroanalysis is still the most widely used electrochemical application in mineralogical research. Electrochemical processing can contribute to bioleaching in two ways. The first approach is the coupling of a mineral sulfide to a galvanic partner or electrocatalyst (spontaneous electron transfer). This approach requires only low energy consumption and takes place without technical installations by the addition of higher redox potential minerals (mostly pyrite), carbonic material, or electrocatalytic ions (mostly silver ions). Consequently, the processed mineral (often chalcopyrite) is preferentially dissolved. The second approach is the application of electrolytic bioreactors (controlled electron transfer). The electrochemical regulation of electrolyte properties by such reactors has found most consideration. It implies the regulation of ferrous and ferric ion ratios, which further results in optimized solution redox potential, less passivation effects, and promotion of microbial activity. However, many questions remain open and it is recommended that reactor and electrode designs are improved, with the aim of finding options for simplified biohydrometallurgical processing. This chapter focuses on metal sulfide dissolution via bioleaching and does not include other biohydrometallurgical processes such as microbial metal recovery from solution.

Redox Mediators for Li-O2 Batteries: Status and Perspectives.

PubMed

Park, Jin-Bum; Lee, Seon Hwa; Jung, Hun-Gi; Aurbach, Doron; Sun, Yang-Kook

2018-01-01

Li-O 2 batteries have received much attention due to their extremely large theoretical energy density. However, the high overpotentials required for charging Li-O 2 batteries lower their energy efficiency and degrade the electrolytes and carbon electrodes. This problem is one of the main obstacles in developing practical Li-O 2 batteries. To solve this problem, it is important to facilitate the oxidation of Li 2 O 2 upon charging by using effective electrocatalysis. Using solid catalysts is not too effective for oxidizing the electronically isolating Li-peroxide layers. In turn, for soluble catalysts, red-ox mediators (RMs) are homogeneously dissolved in the electrolyte solutions and can effectively oxidize all of the Li 2 O 2 precipitated during discharge. RMs can decompose solid Li 2 O 2 species no matter their size, morphology, or thickness and thus dramatically increase energy efficiency. However, some negative side effects, such as the shuttle reactions of RMs and deterioration of the Li-metal occur. Therefore, it is necessary to study the activity and stability of RMs in Li-O 2 batteries in detail. Herein, recent studies related to redox mediators are reviewed and the mechanisms of redox reactions are illustrated. The development opportunities of RMs for this important battery technology are discussed and future directions are suggested. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An innovative concept of use of redox-active electrolyte in asymmetric capacitor based on MWCNTs/MnO2 and Fe2O3 thin films

PubMed Central

Chodankar, Nilesh R.; Dubal, Deepak P.; Lokhande, Abhishek C.; Patil, Amar M.; Kim, Jin H.; Lokhande, Chandrakant D.

2016-01-01

In present investigation, we have prepared a nanocomposites of highly porous MnO2 spongy balls and multi-walled carbon nanotubes (MWCNTs) in thin film form and tested in novel redox-active electrolyte (K3[Fe(CN)6] doped aqueous Na2SO4) for supercapacitor application. Briefly, MWCNTs were deposited on stainless steel substrate by “dip and dry” method followed by electrodeposition of MnO2 spongy balls. Further, the supercapacitive properties of these hybrid thin films were evaluated in hybrid electrolyte ((K3[Fe(CN)6 doped aqueous Na2SO4). Thus, this is the first proof-of-design where redox-active electrolyte is applied to MWCNTs/MnO2 hybrid thin films. Impressively, the MWCNTs/MnO2 hybrid film showed a significant improvement in electrochemical performance with maximum specific capacitance of 1012 Fg−1 at 2 mA cm−2 current density in redox-active electrolyte, which is 1.5-fold higher than that of conventional electrolyte (Na2SO4). Further, asymmetric capacitor based on MWCNTs/MnO2 hybrid film as positive and Fe2O3 thin film as negative electrode was fabricated and tested in redox-active electrolytes. Strikingly, MWCNTs/MnO2//Fe2O3 asymmetric cell showed an excellent supercapacitive performance with maximum specific capacitance of 226 Fg−1 and specific energy of 54.39 Wh kg−1 at specific power of 667 Wkg−1. Strikingly, actual practical demonstration shows lightning of 567 red LEDs suggesting “ready-to sell” product for industries. PMID:27982087

An innovative concept of use of redox-active electrolyte in asymmetric capacitor based on MWCNTs/MnO2 and Fe2O3 thin films.

PubMed

Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Patil, Amar M; Kim, Jin H; Lokhande, Chandrakant D

2016-12-16

In present investigation, we have prepared a nanocomposites of highly porous MnO 2 spongy balls and multi-walled carbon nanotubes (MWCNTs) in thin film form and tested in novel redox-active electrolyte (K 3 [Fe(CN) 6 ] doped aqueous Na 2 SO 4 ) for supercapacitor application. Briefly, MWCNTs were deposited on stainless steel substrate by "dip and dry" method followed by electrodeposition of MnO 2 spongy balls. Further, the supercapacitive properties of these hybrid thin films were evaluated in hybrid electrolyte ((K 3 [Fe(CN) 6 doped aqueous Na 2 SO 4 ). Thus, this is the first proof-of-design where redox-active electrolyte is applied to MWCNTs/MnO 2 hybrid thin films. Impressively, the MWCNTs/MnO 2 hybrid film showed a significant improvement in electrochemical performance with maximum specific capacitance of 1012 Fg -1 at 2 mA cm -2 current density in redox-active electrolyte, which is 1.5-fold higher than that of conventional electrolyte (Na 2 SO 4 ). Further, asymmetric capacitor based on MWCNTs/MnO 2 hybrid film as positive and Fe 2 O 3 thin film as negative electrode was fabricated and tested in redox-active electrolytes. Strikingly, MWCNTs/MnO 2 //Fe 2 O 3 asymmetric cell showed an excellent supercapacitive performance with maximum specific capacitance of 226 Fg -1 and specific energy of 54.39 Wh kg -1 at specific power of 667 Wkg -1 . Strikingly, actual practical demonstration shows lightning of 567 red LEDs suggesting "ready-to sell" product for industries.

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

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

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

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

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

PubMed

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

2017-02-01

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

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

DOE PAGES

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

2017-01-10

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

Enhanced electrochemical performance of in situ reduced graphene oxide-polyaniline nanotubes hybrid nanocomposites using redox-additive aqueous electrolyte

NASA Astrophysics Data System (ADS)

Devi, Madhabi; Kumar, A.

2018-02-01

Reduced graphene oxide (RGO)-polyaniline nanotubes (PAniNTs) nanocomposites have been synthesized by in situ reduction of GO. The morphology and structure of the nanocomposites are characterized by HRTEM, XRD and micro-Raman spectroscopy. The electrical and electrochemical performances of the nanocomposites are investigated for different RGO concentrations by conductivity measurements, cyclic voltammetry, charge-discharge and electrochemical impedance spectroscopy. Highest gravimetric specific capacitance of 448.71 F g-1 is obtained for 40 wt.% of RGO-PAniNTs nanocomposite as compared to 194.92 F g-1 for pure PAniNTs in 1 M KCl electrolyte. To further improve the electrochemical performance of the nanocomposite electrode, KI is used as redox-additive with 1 M KCl electrolyte. Highest gravimetric specific capacitance of 876.43 F g-1 and an improved cyclic stability of 91% as compared to 79% without KI after 5000 cycles is achieved for an optimized 0.1 M KI concentration. This is attributed to the presence of different ionic species of I- ions that give rise to a number of possible redox reactions improving the pseudocapacitance of the electrode. This improved capacitive performance is compared with that of catechol redox-additive in 1 M KCl electrolyte, and that of KI and catechol redox-additives added to 1 M H2SO4 electrolyte.

Preparation of redox polymer cathodes for thin film rechargeable batteries

DOEpatents

Skotheim, T.A.; Lee, H.S.; Okamoto, Yoshiyuki.

1994-11-08

The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

High performance solid-state electric double layer capacitor from redox mediated gel polymer electrolyte and renewable tamarind fruit shell derived porous carbon.

PubMed

Senthilkumar, S T; Selvan, R Kalai; Melo, J S; Sanjeeviraja, C

2013-11-13

The activated carbon was derived from tamarind fruit shell and utilized as electrodes in a solid state electrochemical double layer capacitor (SSEDLC). The fabricated SSEDLC with PVA (polyvinyl alcohol)/H2SO4 gel electrolyte delivered high specific capacitance and energy density of 412 F g(-1) and 9.166 W h kg(-1), respectively, at 1.56 A g(-1). Subsequently, Na2MoO4 (sodium molybdate) added PVA/H2SO4 gel electrolyte was also prepared and applied for SSEDLC, to improve the performance. Surprisingly, 57.2% of specific capacitance (648 F g(-1)) and of energy density (14.4 Wh kg(-1)) was increased while introducing Na2MoO4 as the redox mediator in PVA/H2SO4 gel electrolyte. This improved performance is owed to the redox reaction between Mo(VI)/Mo(V) and Mo(VI)/Mo(IV) redox couples in Na2MoO4/PVA/H2SO4 gel electrolyte. Similarly, the fabricated device shows the excellent capacitance retention of 93% for over 3000 cycles. The present work suggests that the Na2MoO4 added PVA/H2SO4 gel is a potential electrolyte to improve the performance instead of pristine PVA/H2SO4 gel electrolyte. Based on the overall performance, it is strongly believed that the combination of tamarind fruit shell derived activated carbon and Na2MoO4/PVA/H2SO4 gel electrolyte is more attractive in the near future for high performance SSEDLCs.

Transfer of highly hydrophilic ions from water to nitrobenzene, studied by three-phase and thin-film modified electrodes.

PubMed

Charreteur, Kevin; Quentel, François; Elleouet, Catherine; L'Her, Maurice

2008-07-01

The study by voltammetry of hydrophilic ion transfers across the interface between an aqueous solution and an immiscible organic solvent is limited by the presence of supporting electrolytes in both phases. Such a study is impossible for ions having a higher affinity for water than ions of the electrolytes. Indirectly, methods based on modified solid electrodes can be used; these are obtained by the deposition of an organic phase containing a molecule having redox properties, the modified electrode being in contact with an aqueous solution of the appropriate electrolyte. The three-phase electrode is very convenient for that purpose. However, this experimental tool also has its own limitation, due mainly to the redox species produced in the organic phase. The oxidized, or reduced, form of the redox molecule must have a very low affinity for water, as otherwise its transfer masks that of the ion under study. Ferrocene is almost useless because of the affinity of the ferrocenium cation for water, decamethylferrocene being a better choice. The present work illustrates how the use of lutetium bisphthalocyanines widely expands the possibilities, as these molecular sandwich complexes can be reduced as well as oxidized, the products of the reactions having a very low affinity for water. This made the determination of the Gibbs energy possible for the transfers of highly hydrophilic ions from water to nitrobenzene: Cl(-) (40 kJ mol(-1)), F(-) (57 kJ mol(-1)), H2PO4(-) (64 kJ mol(-1)). Nothing being really known about the transfer of F(-) or H2PO4(-) from water to organic solvents, these are the first values ever published. H(+), OH(-), and HSO4(-) have also been studied, showing that these species, which have a poor affinity for nitrobenzene, are prone to association reactions with the reduced or oxidized forms of the lutetium bisphthalocyanine.

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

Wei, Xiaoliang; Xu, Wu; Huang, Jinhua

Nonaqueous redox flow batteries hold the promise to achieve higher energy density ascribed to the broader voltage window than their aqueous counterparts, but their current performance is limited by low redox material concentration, poor cell efficiency, and inferior cycling stability. We report a new nonaqueous total-organic flow battery based on high concentrations of 9-fluorenone as negative and 2,5-di-tert-butyl-1-methoxy-4-[2’-methoxyethoxy]benzene as positive redox materials. The supporting electrolytes are found to greatly affect the cycling stability of flow cells through varying chemical stabilities of the charged radical species, especially the 9-fluorenone radical anions, as confirmed by electron spin resonance. Such an electrolyte optimizationmore » sheds light on mechanistic understandings of capacity fading in flow batteries employing organic radical-based redox materials and demonstrates that rational design of supporting electrolyte is vital for stable cyclability.« less

Evaluation and optimization of mass transport of redox species in silicon microwire-array photoelectrodes

PubMed Central

Xiang, Chengxiang; Meng, Andrew C.; Lewis, Nathan S.

2012-01-01

Physical integration of a Ag electrical contact internally into a metal/substrate/microstructured Si wire array/oxide/Ag/electrolyte photoelectrochemical solar cell has produced structures that display relatively low ohmic resistance losses, as well as highly efficient mass transport of redox species in the absence of forced convection. Even with front-side illumination, such wire-array based photoelectrochemical solar cells do not require a transparent conducting oxide top contact. In contact with a test electrolyte that contained 50 mM/5.0 mM of the cobaltocenium+/0 redox species in CH3CN–1.0 M LiClO4, when the counterelectrode was placed in the solution and separated from the photoelectrode, mass transport restrictions of redox species in the internal volume of the Si wire array photoelectrode produced low fill factors and limited the obtainable current densities to 17.6 mA cm-2 even under high illumination. In contrast, when the physically integrated internal Ag film served as the counter electrode, the redox couple species were regenerated inside the internal volume of the photoelectrode, especially in regions where depletion of the redox species due to mass transport limitations would have otherwise occurred. This behavior allowed the integrated assembly to operate as a two-terminal, stand-alone, photoelectrochemical solar cell. The current density vs. voltage behavior of the integrated photoelectrochemical solar cell produced short-circuit current densities in excess of 80 mA cm-2 at high light intensities, and resulted in relatively low losses due to concentration overpotentials at 1 Sun illumination. The integrated wire array-based device architecture also provides design guidance for tandem photoelectrochemical cells for solar-driven water splitting. PMID:22904185

Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

NASA Astrophysics Data System (ADS)

Basirun, Wan J.; Sookhakian, Mehran; Baradaran, Saeid; Mahmoudian, Mohammad R.; Ebadi, Mehdi

2013-09-01

Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO.

Organic Solar Cells Based on Electrodeposited Polyaniline Films

NASA Astrophysics Data System (ADS)

Inoue, Kei; Akiyama, Tsuyoshi; Suzuki, Atsushi; Oku, Takeo

2012-04-01

Polyaniline thin films as hole transporting layers were fabricated on transparent indium-tin-oxide electrodes by electrodeposition of aniline in an aqueous H2SO4 electrolyte solution. Emerald-green polyaniline films were obtained, which showed stable redox waves. A mixed solution of polythiophene and fullerene derivative was spin-coated onto the electrodeposited polyaniline film. After the modification of titanium oxide film on the surface of the polythiophene/fullerene layer, an aluminum electrode was fabricated by vacuum deposition. The obtained solar cells generated stable photocurrent and photovoltage under light illumination.

A biomimetic redox flow battery based on flavin mononucleotide

PubMed Central

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

2016-01-01

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

A biomimetic redox flow battery based on flavin mononucleotide

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

A biomimetic redox flow battery based on flavin mononucleotide.

PubMed

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

2016-10-21

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

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

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

Xiao, Jie; Liu, Jun; Pan, Huilin

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

Featuring of transient tunneling current by voltage pulse and application to an electrochemical biosensor

NASA Astrophysics Data System (ADS)

Yun, Jun Yeon; Lee, Won Cheol; Choi, Seong Wook; Park, Young June

2018-03-01

We suggest a voltage pulse method for detecting the transient tunneling current component (faradaic current component) in a metal/redox-active monolayer/electrolyte system. After applying the pulse to the metal electrode, the capacitive current prevails; therefore, it is difficult to extract the tunneling current, which carries information on the biochemical reactions occurring between the biomarkers in the electrolyte and the self-assembled monolayer (SAM) as the probe peptide system. Instead of waiting until the capacitive current diminishes, and thereby, the tunneling current also decreases, we try to extract the tunneling current in an early stage of the pulse. The method is based on the observation that the capacitive current becomes symmetrized in the positive and negative pulses after introducing the SAM on the metal electrode. When the energy level of the redox molecule is higher than the Fermi level of the metal under zero-bias condition, the tunneling current in the negative pulse can be extracted by subtracting the capacitive current obtained from the positive pulse, where the tunneling current is neglected. The experiment conducted for detecting trypsin as a biomarker shows that the method enhances the sensitivity and the specific-to-nonspecific ratio of the sensor device in the case of the nonspecific protein-abundant electrolyte solution, as evinced by cyclic voltammetry measurements in comparison.

Monitoring of oxidation steps of ascorbic acid redox reaction by kinetics-sensitive voltcoulometry in unsupported and supported aqueous solutions and real samples.

PubMed

Orlický, Jozef; Gmucová, Katarína; Thurzo, Ilja; Pavlásek, Juraj

2003-04-01

Aqueous solutions of ascorbic acid in unsupported and supported aqueous solutions and real samples were studied by the kinetics-sensitive double-step voltcoulommetric method with the aim to contribute to a better understanding of its behavior in biological systems. The data obtained from measurements made on analytes prepared in the laboratory, as well as those made on real samples (some commercial orange drinks, flash of the fresh fruits) point to the redox reaction of L-ascorbic acid (L-AH2) being very sensitive to both the presence of dissolved gaseous species (O2, CO2) and the ionic strenght in the analyte. Either the dissolved gaseous species, or the higher ionic strength caused by both the presence of supporting electrolyte and increased total concentration of ascorbic acid, respectively, give birth to the degradation of L-AH2. Naturally, the highest percentage of L-AH2 was spotted in fresh fruit.

Solvent effect on redox properties of hexanethiolate monolayer-protected gold nanoclusters.

PubMed

Su, Bin; Zhang, Meiqin; Shao, Yuanhua; Girault, Hubert H

2006-11-02

The capacitance of monolayer-protected gold nanoclusters (MPCs), C(MPC), in solution has been theoretically reconsidered from an electrostatic viewpoint, in which an MPC is considered as an isolated charged sphere within two dielectric layers, the intrinsic coating monolayer, and the bulk solvent. The model predicts that the bulk solvent provides an important contribution to C(MPC) and influences the redox properties of MPCs. This theoretical prediction is then examined experimentally by comparing the redox properties of MPCs in four organic solvents: 1,2-dichloroethane (DCE), dichloromethane (DCM), chlorobenzene (CB), and toluene (TOL), in all of which MPCs have excellent solubility. Furthermore, this set of organic solvents features a dielectric constant in a range from 10.37 (DCE) to 2.38 (TOL), which is wide enough to probe the solvent effect. In these organic solvents, tetrahexylammonium bis(trifluoromethylsulfonyl)imide (THATf2N) is used as the supporting electrolyte. Cyclic and differential pulse voltammetric results provide concrete evidence that, despite the monolayer protection, the solvent plays a significant effect on the properties of MPCs in solution.

Preferential Solvation of an Asymmetric Redox Molecule

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

Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.

2016-12-15

The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ionmore » pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.« less

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Enhancing Specific Energy and Power in Asymmetric Supercapacitors - A Synergetic Strategy based on the Use of Redox Additive Electrolytes

PubMed Central

Singh, Arvinder; Chandra, Amreesh

2016-01-01

The strategy of using redox additive electrolyte in combination with multiwall carbon nanotubes/metal oxide composites leads to a substantial improvements in the specific energy and power of asymmetric supercapacitors (ASCs). When the pure electrolyte is optimally modified with a redox additive viz., KI, ~105% increase in the specific energy is obtained with good cyclic stability over 3,000 charge-discharge cycles and ~14.7% capacitance fade. This increase is a direct consequence of the iodine/iodide redox pairs that strongly modifies the faradaic and non-faradaic type reactions occurring on the surface of the electrodes. Contrary to what is shown in few earlier reports, it is established that indiscriminate increase in the concentration of redox additives will leads to performance loss. Suitable explanations are given based on theoretical laws. The specific energy or power values being reported in the fabricated ASCs are comparable or higher than those reported in ASCs based on toxic acetonitrile or expensive ionic liquids. The paper shows that the use of redox additive is economically favorable strategy for obtaining cost effective and environmentally friendly ASCs. PMID:27184260

Characterization of poly methyl methaacrylate and reduced graphene oxide composite for application as electrolyte in dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Shrivatsav, Roshan; Mahalingam, Vignesh; Lakshmi Narayanan, E. R.; Naveen Balaji, N.; Balu, Murali; Krishna Prasad, R.; Kumaresan, Duraisamy

2018-04-01

Quasi-solid state iodide/triiodide redox electrolyte containing reduced graphene oxide and poly (methyl methaacrylate) (RGO-PMMA) composites for the fabrication of more durable, high performance dye sensitized solar cells are prepared. The morphological analysis of prepared RGO-PMMA composites showed formation of spherical like morphologies of RGO dispersed PMMA particles with their macroscopic inter-particle networks having voids. The x ray diffraction and electrical conductivity studies showed the addition of 1 wt% of filler RGO into amorphous PMMA matrix increased the electrical conductivity of the polymer composite about three orders of magnitude from 10‑7 and 10‑4 S cm‑1. Further, the photovoltaic current-voltage analysis of DSSCs with different RGO-PMMA composite based iodide/triiodide redox electrolytes showed the highest power conversion efficiency of 5.38% and the fill factor 0.63 for 2% RGO-PMMA electrolyte. The EIS analysis showed an increased recombination resistance (Rct2) at TiO2 electrode/dye/electrolyte interface due to the better electrical conductivity of RGO with good ionic conductivity in 2% RGO-PMMA composite based redox electrolyte boosted the generation of a high current density and fill factor in their DSSCs.

Green synthesis of in situ electrodeposited rGO/MnO2 nanocomposite for high energy density supercapacitors.

PubMed

Rusi; Majid, S R

2015-11-05

This paper presents the preparation of in situ electrodeposited rGO/MnO2 nanocomposite as a binder-free electrode for supercapacitor application. The work describes and evaluates the performance of prepared electrode via green and facile electrodeposition technique of in situ rGO/MnO2-glucose carbon nanocomposites. The carbon content in the composite electrode increased after GO and D (+) glucose solution has been added in the deposition electrolyte. This study found that a suitable concentration of D (+) glucose in the deposition electrolyte can slow down the nucleation process of MnO2 particles and lead to uniform and ultrathin nanoflakes structure. The optimize electrode exhibited low transfer resistance and resulted on excellent electrochemical performance in three electrolyte systems viz. Na2SO4, KOH and KOH/K3Fe(CN)6 redox electrolytes. The optimum energy density and power density were 1851 Whkg(-1) and 68 kWkg(-1) at current density of 20 Ag(-1) in mixed KOH/K3Fe(CN)6 electrolyte.

Green synthesis of in situ electrodeposited rGO/MnO2 nanocomposite for high energy density supercapacitors

NASA Astrophysics Data System (ADS)

Rusi; Majid, S. R.

2015-11-01

This paper presents the preparation of in situ electrodeposited rGO/MnO2 nanocomposite as a binder-free electrode for supercapacitor application. The work describes and evaluates the performance of prepared electrode via green and facile electrodeposition technique of in situ rGO/MnO2-glucose carbon nanocomposites. The carbon content in the composite electrode increased after GO and D (+) glucose solution has been added in the deposition electrolyte. This study found that a suitable concentration of D (+) glucose in the deposition electrolyte can slow down the nucleation process of MnO2 particles and lead to uniform and ultrathin nanoflakes structure. The optimize electrode exhibited low transfer resistance and resulted on excellent electrochemical performance in three electrolyte systems viz. Na2SO4, KOH and KOH/K3Fe(CN)6 redox electrolytes. The optimum energy density and power density were 1851 Whkg-1 and 68 kWkg-1 at current density of 20 Ag-1 in mixed KOH/K3Fe(CN)6 electrolyte.

Green synthesis of in situ electrodeposited rGO/MnO2 nanocomposite for high energy density supercapacitors

PubMed Central

Rusi; Majid, S. R.

2015-01-01

This paper presents the preparation of in situ electrodeposited rGO/MnO2 nanocomposite as a binder-free electrode for supercapacitor application. The work describes and evaluates the performance of prepared electrode via green and facile electrodeposition technique of in situ rGO/MnO2-glucose carbon nanocomposites. The carbon content in the composite electrode increased after GO and D (+) glucose solution has been added in the deposition electrolyte. This study found that a suitable concentration of D (+) glucose in the deposition electrolyte can slow down the nucleation process of MnO2 particles and lead to uniform and ultrathin nanoflakes structure. The optimize electrode exhibited low transfer resistance and resulted on excellent electrochemical performance in three electrolyte systems viz. Na2SO4, KOH and KOH/K3Fe(CN)6 redox electrolytes. The optimum energy density and power density were 1851 Whkg−1 and 68 kWkg−1 at current density of 20 Ag−1 in mixed KOH/K3Fe(CN)6 electrolyte. PMID:26537363

Molecular Materials for Nonaqueous Flow Batteries with a High Coulombic Efficiency and Stable Cycling.

PubMed

Milton, Margarita; Cheng, Qian; Yang, Yuan; Nuckolls, Colin; Hernández Sánchez, Raúl; Sisto, Thomas J

2017-12-13

This manuscript presents a working redox battery in organic media that possesses remarkable cycling stability. The redox molecules have a solubility over 1 mol electrons/liter, and a cell with 0.4 M electron concentration is demonstrated with steady performance >450 cycles (>74 days). Such a concentration is among the highest values reported in redox flow batteries with organic electrolytes. The average Coulombic efficiency of this cell during cycling is 99.868%. The stability of the cell approaches the level necessary for a long lifetime nonaqueous redox flow battery. For the membrane, we employ a low cost size exclusion cellulose membrane. With this membrane, we couple the preparation of nanoscale macromolecular electrolytes to successfully avoid active material crossover. We show that this cellulose-based membrane can support high voltages in excess of 3 V and extreme temperatures (-20 to 110 °C). These extremes in temperature and voltage are not possible with aqueous systems. Most importantly, the nanoscale macromolecular platforms we present here for our electrolytes can be readily tuned through derivatization to realize the promise of organic redox flow batteries.

Electrochemical behavior and pH stability of artificial salivas for corrosion tests.

PubMed

Queiroz, Gláucia Maria Oliveira de; Silva, Leandro Freitas; Ferreira, José Tarcísio Lima; Gomes, José Antônio da Cunha P; Sathler, Lúcio

2007-01-01

It is assumed that the compositions of artificial salivas are similar to that of human saliva. However, the use of solutions with different compositions in in vitro corrosion studies can lead dissimilar electrolytes to exhibit dissimilar corrosivity and electrochemical stability. This study evaluated four artificial salivas as regards pH stability with time, redox potentials and the polarization response of an inert platinum electrode. The tested solutions were: SAGF medium, Mondelli artificial saliva, UFRJ artificial saliva (prepared at the School of Pharmacy, Federal University of Rio de Janeiro, RJ, Brazil) and USP-RP artificial saliva (prepared at the School of Pharmaceutical Sciences of Ribeirão Preto, University of São Paulo, SP, Brazil). It was observed that pH variations were less than 1 unit during a 50-hour test. The SAGF medium, and the UFRJ and USP-RP solutions exhibited more oxidizing characteristics, whereas the Mondelli solution presented reducing properties. Anodic polarization revealed oxidation of the evaluated electrolytes at potentials below +600 mV SCE. It was observed that the UFRJ and USP-RP solutions presented more intense oxidation and reduction processes as compared to the Mondelli and SAGF solutions.

Advanced screening of electrode couples

NASA Technical Reports Server (NTRS)

Giner, J. D.; Cahill, K.

1980-01-01

The chromium (Cr(3+)/Cr(2+)) redox couple (electrolyte and electrode) was investigated to determine its suitability as negative electrode for the iron (Fe(3+)/Fe(2+))-chromium (Cr(3+)/Cr(2+)) redox flow battery. Literature search and laboratory investigation established that the solubility and stability of aqueous acidic solutions of chromium(3) chloride and chromium(2) chloride are sufficient for redox battery application. Four categories of electrode materials were tested; namely, metals and metalloid materials (elements and compounds), alloys, plated materials, and Teflon-bonded materials. In all, the relative performance of 26 candidate electrode materials was evaluated on the basis of slow scan rate linear sweep voltammetry in stirred solution. No single material tested gave both acceptable anodic an acceptable cathodic performance. However, the identification of lead as a good cathodic electrocatalyst and gold as a good anodic electrocatalyst led to the invention of the lead/gold combination electrocatalyst. This type of catalyst can be fabricated in several ways and appears to offer the advantages of each metal without the disadvantages associated with their use as single materials. This lead/gold electrocatalyst was tested by NASA-Lewis Research Center in complete, flowing, redox batteries comprising a stack of several cells. A large improvement in the battery's coulombic and energy efficiency was observed.

Organo-redox shuttle promoted protic ionic liquid electrolyte for supercapacitor

NASA Astrophysics Data System (ADS)

Sathyamoorthi, S.; Suryanarayanan, V.; Velayutham, D.

2015-01-01

Performance of activated charcoal based supercapacitor (SC) containing hydroquinone (HQ), as an organic redox shuttle, is evaluated in triethylammonium bis(trifluoromethane)sulfonimide (TEATFSI). Cyclic voltammograms of the SC show pseudocapacitive contribution of HQ and the galvanostatic charge-discharge measurement shows enhanced specific capacitance (72.0 F g-1) and specific energy (31.22 Wh Kg-1). The presence of HQ shows low charge transfer resistance, as confirmed by electrochemical impedance spectroscopy. Cyclic stability of the SC in the redox mediated electrolyte is comparable with that of the protic ionic liquid.

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

PubMed

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

2017-04-01

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

High Performance Hybrid Energy Storage with Potassium Ferricyanide Redox Electrolyte.

PubMed

Lee, Juhan; Choudhury, Soumyadip; Weingarth, Daniel; Kim, Daekyu; Presser, Volker

2016-09-14

We demonstrate stable hybrid electrochemical energy storage performance of a redox-active electrolyte, namely potassium ferricyanide in aqueous media in a supercapacitor-like setup. Challenging issues associated with such a system are a large leakage current and high self-discharge, both stemming from ion redox shuttling through the separator. The latter is effectively eliminated when using an ion exchange membrane instead of a porous separator. Other critical factors toward the optimization of a redox-active electrolyte system, especially electrolyte concentration and volume of electrolyte, have been studied by electrochemical methods. Finally, excellent long-term stability is demonstrated up to 10 000 charge/discharge cycles at 1.2 and 1.8 V, with a broad maximum stability window of up to 1.8 V cell voltage as determined via cyclic voltammetry. An energy capacity of 28.3 Wh/kg or 11.4 Wh/L has been obtained from such cells, taking the nonlinearity of the charge-discharge profile into account. The power performance of our cell has been determined to be 7.1 kW/kg (ca. 2.9 kW/L or 1.2 kW/m(2)). These ratings are higher compared to the same cell operated in aqueous sodium sulfate. This hybrid electrochemical energy storage system is believed to find a strong foothold in future advanced energy storage applications.

High-Temperature Controlled Redox Crystallization Studies

NASA Technical Reports Server (NTRS)

Williams, R. J.

1985-01-01

The crystallization of silicates containing redox sensitive ions (e.g., Fe, Ti, Ce) must be performed under controlled and known redox conditions in order to obtain the maximum scientific benefit from experimental study. Furthermore, many compositions crystallize dense phases which settle during ground-based experiments. This settling influences the texture and chemical evolution of the crystallizing system. The purpose of this investigation is to develop a test system in which controlled redox experiments can be performed in the microgravity environment. The system will use solid ceramic oxygen electrolyte cells for control, measurements, and production of the required redox conditions. A preliminary design for a prototype is developed, the electrolyte and furnace tested, and a tentative protocol for experiment developed. The control parameter is to be established and a laboratory prototype built.

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

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

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

Aqueous dye-sensitized solar cell electrolytes based on the ferricyanide-ferrocyanide redox couple.

PubMed

Daeneke, Torben; Uemura, Yu; Duffy, Noel W; Mozer, Attila J; Koumura, Nagatoshi; Bach, Udo; Spiccia, Leone

2012-03-02

Solar energy conversion efficiencies of over 4% have been achieved in DSCs constructed with aqueous electrolytes based on the ferricyanide-ferrocyanide redox couple, thereby avoiding the use of expensive, flammable and toxic solvents. This paradigm shift was made possible by the use of a hydrophobic organic carbazole dye. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene incorporated, N doped activated carbon as catalytic electrode in redox active electrolyte mediated supercapacitor

NASA Astrophysics Data System (ADS)

Gao, Zhiyong; Liu, Xiao; Chang, Jiuli; Wu, Dapeng; Xu, Fang; Zhang, Lingcui; Du, Weimin; Jiang, Kai

2017-01-01

Graphene incorporated, N doped activated carbons (GNACs) are synthesized by alkali activation of graphene-polypyrrole composite (G-PPy) at different temperatures for application as electrode materials of supercapacitors. Under optimal activation temperature of 700 °C, the resultant samples, labeled as GNAC700, owns hierarchically porous texture with high specific surface area and efficient ions diffusion channels, N, O functionalized surface with apparent pseudocapacitance contribution and high wettability, thus can deliver a moderate capacitance, a high rate capability and a good cycleability when used as supercapacitor electrode. Additionally, the GNAC700 electrode demonstrates high catalytic activity for the redox reaction of pyrocatechol/o-quinone pair in H2SO4 electrolyte, thus enables a high pseudocapacitance from electrolyte. Under optimal pyrocatechol concentration in H2SO4 electrolyte, the electrode capacitance of GNAC700 increases by over 4 folds to 512 F g-1 at 1 A g-1, an excellent cycleability is also achieved simultaneously. Pyridinic- N is deemed to be responsible for the high catalytic activity. This work provides a promising strategy to ameliorate the capacitive performances of supercapacitors via the synergistic interaction between redox-active electrolyte and catalytic electrodes.

Electroactive ionic liquids based on 2,5-ditert-butyl-1,4-dimethoxybenzene and triflimide anion as redox shuttle for Li4Ti5O12/LiFePO4 lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gélinas, Bruno; Bibienne, Thomas; Dollé, Mickael; Rochefort, Dominic

2017-12-01

In order to increase the solubility and oxidation potential of redox shuttles, electroactive ionic liquids (RILs) based on the modification of 1,4-dimethoxybenzene with triflimide anions were synthesized. We developed two synthetic routes to obtain these RILs in which the triflimide was either linked on the benzene ring or as a ether on 2,5-ditert-butyl-1,4-dimethoxybenzene (DDB). These RILs all have melting points below 100 °C, but above room temperature. The structural impact of electroactive anion was evaluated in this study by determining the redox potential and electrochemical stability. The electrochemical properties of these RILs were investigated by cyclic voltammetry and the diffusion coefficients were measured by double potential step chronoamperometry. The viscosity and ionic conductivity measurements of redox-active electrolyte were obtained at different temperatures and the RIL additives are shown to have a low impact on these electrolyte properties at concentrations up to 0.3 M. The charge-overcharge-discharge cycles of Li/LiFePO4 half-cells and Li4Ti5O12/LiFePO4 full cells with a 100% overcharge are presented using redox-active electrolyte (0.3 M concentration level) at 0.1 C rate. This study highlights the potential of electroactive ionic liquids as highly soluble and stable functional additives in Li-ion battery electrolytes.

Physical Organic Approach to Persistent, Cyclable, Low-Potential Electrolytes for Flow Battery Applications.

PubMed

Sevov, Christo S; Hickey, David P; Cook, Monique E; Robinson, Sophia G; Barnett, Shoshanna; Minteer, Shelley D; Sigman, Matthew S; Sanford, Melanie S

2017-03-01

The deployment of nonaqueous redox flow batteries for grid-scale energy storage has been impeded by a lack of electrolytes that undergo redox events at as low (anolyte) or high (catholyte) potentials as possible while exhibiting the stability and cycling lifetimes necessary for a battery device. Herein, we report a new approach to electrolyte design that uses physical organic tools for the predictive targeting of electrolytes that possess this combination of properties. We apply this approach to the identification of a new pyridinium-based anolyte that undergoes 1e - electrochemical charge-discharge cycling at low potential (-1.21 V vs Fc/Fc + ) to a 95% state-of-charge without detectable capacity loss after 200 cycles.

Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

PubMed

Byers, Joshua C; Paulose Nadappuram, Binoy; Perry, David; McKelvey, Kim; Colburn, Alex W; Unwin, Patrick R

2015-10-20

Single molecule electrochemical detection (SMED) is an extremely challenging aspect of electroanalytical chemistry, requiring unconventional electrochemical cells and measurements. Here, SMED is reported using a "quad-probe" (four-channel probe) pipet cell, fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barreled pipet and filling the open channels with electrolyte solution, and quasi-reference counter electrodes. A meniscus forms at the end of the probe covering the two working electrodes and is brought into contact with a substrate working electrode surface. In this way, a nanogap cell is produced whereby the two carbon electrodes in the pipet can be used to promote redox cycling of an individual molecule with the substrate. Anticorrelated currents generated at the substrate and tip electrodes, at particular distances (typically tens of nanometers), are consistent with the detection of single molecules. The low background noise realized in this droplet format opens up new opportunities in single molecule electrochemistry, including the use of ionic liquids, as well as aqueous solution, and the quantitative assessment and analysis of factors influencing redox cycling currents, due to a precisely known gap size.

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

PubMed

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2017-06-14

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

Leaching of Zinc Sulfide by Thiobacillus ferrooxidans: Experiments with a Controlled Redox Potential Indicate No Direct Bacterial Mechanism

PubMed Central

Fowler, T. A.; Crundwell, F. K.

1998-01-01

The role of Thiobacillus ferrooxidans in bacterial leaching of mineral sulfides is controversial. Much of the controversy is due to the fact that the solution conditions, especially the concentrations of ferric and ferrous ions, change during experiments. The role of the bacteria would be more easily discernible if the concentrations of ferric and ferrous ions were maintained at set values throughout the experimental period. In this paper we report results obtained by using the constant redox potential apparatus described previously (P. I. Harvey and F. K. Crundwell, Appl. Environ. Microbiol. 63:2586–2592, 1997). This apparatus is designed to control the redox potential in the leaching compartment of an electrolytic cell by reduction or oxidation of dissolved iron. By controlling the redox potential the apparatus maintains the concentrations of ferrous and ferric ions at their initial values. Experiments were conducted in the presence of T. ferrooxidans and under sterile conditions. Analysis of the conversion of zinc sulfide in the absence of the bacteria and analysis of the conversion of zinc sulfate in the presence of the bacteria produced the same results. This indicates that the only role of the bacteria under the conditions used is regeneration of ferric ions in solution. In this work we found no evidence that there is a direct mechanism for bacterial leaching. PMID:9758769

Enhanced electrochemical performance of nickel-cobalt-oxide@reduced graphene oxide//activated carbon asymmetric supercapacitors by the addition of a redox-active electrolyte.

PubMed

Lamiel, Charmaine; Lee, Yong Rok; Cho, Moo Hwan; Tuma, Dirk; Shim, Jae-Jin

2017-12-01

Supercapacitors are an emerging energy-storage system with a wide range of potential applications. In this study, highly porous nickel-cobalt-oxide@reduced graphene oxide (Ni-Co-O@RGO-s) nanosheets were synthesized as an active material for supercapacitors using a surfactant-assisted microwave irradiation technique. The RGO-modified nanocomposite showed a larger specific area, better conductivity, and lower resistivity than the unmodified nanocomposite because the RGO facilitated faster ion diffusion/transport for improved redox activity. The synergistic effect of Ni-Co-O@RGO-s resulted in a high capacitance of 1903Fg -1 (at 0.8Ag -1 ) in a mixed KOH/redox active K 3 Fe(CN) 6 electrolyte. The asymmetric Ni-Co-O@RGO-s//AC supercapacitor device yielded a high energy density and power density of 39Whkg -1 and 7500Wkg -1 , respectively. The porous structure and combination of redox couples from both the electrode and electrolyte provided a highly synergistic effect, which improved the performance of the supercapacitor device. Copyright © 2017 Elsevier Inc. All rights reserved.

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

PubMed

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

2014-12-03

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

n-MoSe2 photoelectrochemical halogen storage cell

NASA Astrophysics Data System (ADS)

Ang, P. G. P.; Sammells, A. F.

1982-01-01

In the study reported here, single-crystal n-MoSe2 photoanodes are investigated in a variety of halogen redox couples. The photoanode is prepared by allowing the silver epoxy cement to come into contact with the front surface of the crystal before being insulated from the redox electrolyte with paraffin wax. This photoanode is evaluated in bromine redox electrolytes in various pH ranges. In 1M HBr + 1M Br2 (pH, approximately zero), the initial open-circuit potential of the MoSe2 versus a platinum reference electrode in the same electrolyte is -130 mV in the dark and -480 mV under 200 mW/sq cm xenon illumination. It is noted that improved performance could be achieved with such crystals by subjecting them to an anodic polarization of around 1 volt from the initial resting potential, a current of about 5 mA/sq cm flowing in the dark.

Tracking Catalyst Redox States and Reaction Dynamics in Ni-Fe Oxyhydroxide Oxygen Evolution Reaction Electrocatalysts: The Role of Catalyst Support and Electrolyte pH.

PubMed

Görlin, Mikaela; Ferreira de Araújo, Jorge; Schmies, Henrike; Bernsmeier, Denis; Dresp, Sören; Gliech, Manuel; Jusys, Zenonas; Chernev, Petko; Kraehnert, Ralph; Dau, Holger; Strasser, Peter

2017-02-08

Ni-Fe oxyhydroxides are the most active known electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolytes and are therefore of great scientific and technological importance in the context of electrochemical energy conversion. Here we uncover, investigate, and discuss previously unaddressed effects of conductive supports and the electrolyte pH on the Ni-Fe(OOH) catalyst redox behavior and catalytic OER activity, combining in situ UV-vis spectro-electrochemistry, operando electrochemical mass spectrometry (DEMS), and in situ cryo X-ray absorption spectroscopy (XAS). Supports and pH > 13 strongly enhanced the precatalytic voltammetric charge of the Ni-Fe oxyhydroxide redox peak couple, shifted them more cathodically, and caused a 2-3-fold increase in the catalytic OER activity. Analysis of DEMS-based faradaic oxygen efficiency and electrochemical UV-vis traces consistently confirmed our voltammetric observations, evidencing both a more cathodic O 2 release and a more cathodic onset of Ni oxidation at higher pH. Using UV-vis, which can monitor the amount of oxidized Ni +3/+4 in situ, confirmed an earlier onset of the redox process at high electrolyte pH and further provided evidence of a smaller fraction of Ni +3/+4 in mixed Ni-Fe centers, confirming the unresolved paradox of a reduced metal redox activity with increasing Fe content. A nonmonotonic super-Nernstian pH dependence of the redox peaks with increasing Fe content-displaying Pourbaix slopes as steep as -120 mV/pH-suggested a two proton-one electron transfer. We explain and discuss the experimental pH effects using refined coupled (PCET) and decoupled proton transfer-electron transfer (PT/ET) schemes involving negatively charged oxygenate ligands generated at Fe centers. Together, we offer new insight into the catalytic reaction dynamics and associated catalyst redox chemistry of the most important class of alkaline OER catalysts.

Pulsating electrolyte flow in a full vanadium redox battery

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Command Surface of Self-Organizing Structures by Radical Polymers with Cooperative Redox Reactivity.

PubMed

Sato, Kan; Mizuma, Takahiro; Nishide, Hiroyuki; Oyaizu, Kenichi

2017-10-04

Robust radical-substituted polymers with ideal redox capability were used as "command surfaces" for liquid crystal orientation. The alignment of the smectic liquid crystal electrolytes with low-dimensional ion conduction pathways was reversible and readily switched in response to the redox states of the polymers. In one example, a charge storage device with a cooperative redox effect was fabricated. The bulk ionic conductivity of the cell was significantly decreased only after the electrode was fully charged, due to the anisotropic ionic conductivity of the electrolytes (ratio >10 3 ). The switching enabled both a rapid cell response and long charge retention. Such a cooperative command surface of self-assembled structures will give rise to new highly energy efficient supramolecular-based devices including batteries, charge carriers, and actuators.

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

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

We proposed and developed an all-iron redox flow battery 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. Our 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 Fe 2 (SO 4 ) 3 activemore » material and 1.2 m NaCl supporting electrolyte. Furthermore, 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.« less

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

Deng, Xuchu; Hu, Mary Y.; Wei, Xiaoliang

Understanding the solvation structures of electrolytes should prove conducive for the development of nonaqueous redox flow batteries that hold considerable potential for future large scale energy storage systems. The utilization of an emerging ionic-derivatived ferrocene compound, ferrocenylmethyl dimethyl ethyl ammonium bis(trifluoromethanesulfonyl)imide (Fc1N112-TFSI), has recently overcome the issue of solubility in the supporting electrolyte. In this work, 13C, 1H and 17O NMR investigations were carried out using electrolyte solutions consisting of Fc1N112-TFSI as the solute and the mixed alkyl carbonate as the solvent. It was observed that the spectra of 13C experience changes of chemical shifts while those of 17O undergomore » linewidth broadening, indicating interactions between solute and solvent molecules. Quantum chemistry calculations of both molecular structures and chemical shifts (13C, 1H and 17O) are performed for interpreting experimental results and of understanding the detailed solvation structures and molecular dynamics. The results indicate that Fc1N112-TFSI is dissociated at varying degrees in mixed solvent depending on concentrations. Solvent molecules encircle Fc1N112 and TFSI respectively as solvation shells, rapidly exchanging with both bulk solvent and TFSI. Additionally, the solvent with high dielectric constant is more capable of dissociating Fc1N112-TFSI molecules compared with those with low dielectric constant. At saturated concentration, contact ion pairs are formed and the solvent molecules are interacting with the Fc rings rather than interacting with the ionic pendant arm of Fc1N112-TFSI. These studies will contribute to the development of nonaqueous electrolytes of storage systems.« less

Spectroscopic detection of halogen bonding resolves dye regeneration in the dye-sensitized solar cell.

PubMed

Parlane, Fraser G L; Mustoe, Chantal; Kellett, Cameron W; Simon, Sarah J; Swords, Wesley B; Meyer, Gerald J; Kennepohl, Pierre; Berlinguette, Curtis P

2017-11-24

The interactions between a surface-adsorbed dye and a soluble redox-active electrolyte species in the dye-sensitized solar cell has a significant impact on the rate of regeneration of photo-oxidized dye molecules and open-circuit voltage of the device. Dyes must therefore be designed to encourage these interfacial interactions, but experimentally resolving how such weak interactions affect electron transfer is challenging. Herein, we use X-ray absorption spectroscopy to confirm halogen bonding can exist at the dye-electrolyte interface. Using a known series of triphenylamine-based dyes bearing halogen substituents geometrically positioned for reaction with halides in solution, halogen bonding was detected only in cases where brominated and iodinated dyes were photo-oxidized. This result implies that weak intermolecular interactions between photo-oxidized dyes and the electrolyte can impact device photovoltages. This result was unexpected considering the low concentration of oxidized dyes (less than 1 in 100,000) under full solar illumination.

Colloidal graphene quantum dots incorporated with a Cobalt electrolyte in a dye sensitized solar cell

NASA Astrophysics Data System (ADS)

Lim, Hyuna

The utilization of sun light as a renewable energy source has been pursued for a long time, but the ultimate goal of developing inexpensive and highly efficient photovoltaic devices remains elusive. To address this problem, colloidal graphene quantum dots (GQDs) were synthesized and used as a new sensitizer in dye sensitized solar cells (DSCs). Not only do the GQDs have a well-defined structure, but their large absorptivity, tunable bandgap, and size- and functional group-dependent redox potentials make them promising candidates for photovoltaic applications. Because volatile organic solvents in electrolyte solutions hinder long-term use and mass production of DSC devices, imidazolium based ionic liquids (ILs) were investigated. Cobalt-bipyridine complexes were successfully synthesized and characterized for use as new redox shuttles in DSCs. In the tested DSCs, J-V (current density-voltage) curves illustrate that the short circuit current and fill factor decrease significantly as the active area in the TiO2 photo anode increases. Dark current measurement indicated that the diode factor is bigger than one, which is different from the conventional p-n junction type solar cells, due to the high efficiency of photoelectron injection. The variation of the diode factor in dark and in light would show various types of recombination behaviors in DSCs. The performance of the DSC stained by GQDs incorporated with the cobalt redox couple was tested, but further study to improve the efficiency and to understand photochemical reaction in the DSCs is needed.

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

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

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

2014-09-03

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

Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection

DOEpatents

Richardson, Thomas J.; Ross, Philip N.

1999-01-01

A class of organic redox shuttle additives is described, preferably comprising nitrogen-containing aromatics compounds, which can be used in a high temperature (85.degree. C. or higher) electrochemical storage cell comprising a positive electrode, a negative electrode, and a solid polymer electrolyte to provide overcharge protection to the cell. The organic redox additives or shuttles are characterized by a high diffusion coefficient of at least 2.1.times.10.sup.-8 cm.sup.2 /second and a high onset potential of 2.5 volts or higher. Examples of such organic redox shuttle additives include an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene, and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1,2-dione.

A system using solid ceramic oxygen electrolyte cells to measure oxygen fugacities in gas-mixing systems

NASA Technical Reports Server (NTRS)

Williams, R. J.; Mullins, O.

1976-01-01

Details are given for the construction and operation of a 101.3 kN/sq m (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the high input impedance electronics necessary for measurements, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change relative to temperature and redox state. The calibration and maintenance of the system are discussed.

JSC systems using solid ceramic oxygen electrolyte cells to measure oxygen fugacites in gas-mixing systems

NASA Technical Reports Server (NTRS)

Williams, R. J.; Mullins, O.

1981-01-01

Details are given for the construction and operation of a 101.3 KN/sq meter (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change of temperature. A thermogravimetric analysis system employing these techniques of redox control and measurement is also described. The calibration and maintenance of the system are discussed.

High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

PubMed

Akhtar, M Shaheer; Kwon, Soonji; Stadler, Florian J; Yang, O Bong

2013-06-21

Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.

Investigation of multi-state charge-storage properties of redox-active organic molecules in silicon-molecular hybrid devices for DRAM and Flash applications

NASA Astrophysics Data System (ADS)

Gowda, Srivardhan Shivappa

Molecular electronics has recently spawned a considerable amount of interest with several molecules possessing charge-conduction and charge-storage properties proposed for use in electronic devices. Hybrid silicon-molecular technology has the promise of augmenting the current silicon technology and provide for a transitional path to future molecule-only technology. The focus of this dissertation work has been on developing a class of hybrid silicon-molecular electronic devices for DRAM and Flash memory applications utilizing redox-active molecules. This work exploits the ability of molecules to store charges with single-electron precision at room temperature. The hybrid devices are fabricated by forming self-assembled monolayers of redox-active molecules on Si and oxide (SiO2 and HfO2) surfaces via formation of covalent linkages. The molecules possess discrete quantum states from which electrons can tunnel to the Si substrate at discrete applied voltages (oxidation process, cell write), leaving behind a positively charged layer of molecules. The reduction (erase) process, which is the process of electrons tunneling back from Si to the molecules, neutralizes the positively charged molecular monolayer. Hybrid silicon-molecular capacitor test structures were electrically characterized with an electrolyte gate using cyclic voltammetry (CyV) and impedance spectroscopy (CV) techniques. The redox voltages, kinetics (write/erase speeds) and charge-retention characteristics were found to be strongly dependent on the Si doping type and densities, and ambient light. It was also determined that the redox energy states in the molecules communicate with the valence band of the Si substrate. This allows tuning of write and read states by modulating minority carriers in n- and p-Si substrates. Ultra-thin dielectric tunnel barriers (SiO2, HfO2) were placed between the molecules and the Si substrate to augment charge-retention for Flash memory applications. The redox response was studied as a function of tunnel oxide thickness, dielectric permittivity and energy barrier, and modified Butler-Volmer expressions were postulated to describe the redox kinetics. The speed vs. retention performance of the devices was improved via asymmetric layered tunnel barriers. The properties of molecules can be tailored by molecular design and synthetic chemistry. In this work, it was demonstrated that an alternate route to tune/enhance the properties of the hybrid device is to engineer the substrate (silicon) component. The molecules were attached to diode surfaces to tune redox voltages and improve charge-retention characteristics. N+ pockets embedded in P-Si well were utilized to obtain multiple states from a two-state molecule. The structure was also employed as a characterization tool in investigating the intrinsic properties of the molecules such as lateral conductivity within the monolayer. Redox molecules were also incorporated on an ultra thin gate-oxide of Si MOSFETs with the intent of studying the interaction of redox states with Si MOSFETs. The discrete molecular states were manifested in the drain current and threshold voltage characteristics of the device. This work demonstrates the multi-state modulation of Si-MOSFETs' drain current via redox-active molecular monolayers. Polymeric films of redox-active molecules were incorporated to improve the charge-density (ON/OFF ratio) and these structures may be employed for multi-state, low-voltage Flash memory applications. The most critical aspect of this research effort is to build a reliable and high density solid state memory technology. To this end, efforts were directed towards replacement of the electrolytic gate, which forms an extremely thin insulating double layer (˜10 nm) at the electrolyte-molecule interface, with a combination of an ultra-thin high-K dielectric layer and a metal gate. Several interesting observations were made in the research approaches towards integration and provided valuable insights into the electrolyte-redox systems. In summary, this work provides fundamental insights into the interaction of redox-energy states with silicon substrate and realistic approaches for exploiting the unique properties of the molecules that may enable solutions for nanoscale high density, low-voltage, long retention and multiple bit memory applications.

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

PubMed

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

2012-07-07

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

Recent developments in organic redox flow batteries: A critical review

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

TiO2 Photocatalysis in Aromatic "Redox Tag"-Guided Intermolecular Formal [2 + 2] Cycloadditions.

PubMed

Okada, Yohei; Maeta, Naoya; Nakayama, Kaii; Kamiya, Hidehiro

2018-05-04

Since the pioneering work by Macmillan, Yoon, and Stephenson, homogeneous photoredox catalysis has occupied a central place in new reaction development in the field of organic chemistry. While heterogeneous semiconductor photocatalysis has also been studied extensively, it has generally been recognized as a redox option in inorganic chemistry where such "photocatalysis" is most often used to catalyze carbon-carbon bond cleavage and not in organic chemistry where bond formation is usually the focal point. Herein, we demonstrate that titanium dioxide photocatalysis is a powerful redox option to construct carbon-carbon bonds by using intermolecular formal [2 + 2] cycloadditions as models. Synergy between excited electrons and holes generated upon irradiation is expected to promote the overall net redox neutral process. Key for the successful application is the use of a lithium perchlorate/nitromethane electrolyte solution, which exhibits remarkable Lewis acidity to facilitate the reactions of carbon-centered radical cations with carbon nucleophiles. The reaction mechanism is reasonably understood based on both intermolecular and intramolecular single electron transfer regulated by an aromatic "redox tag". Most of the reactions were completed in less than 30 min even in aqueous and/or aerobic conditions without the need for sacrificial reducing or oxidizing substrates generally required for homogeneous photoredox catalysis.

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2015-02-24

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

A small electron donor in cobalt complex electrolyte significantly improves efficiency in dye-sensitized solar cells

PubMed Central

Hao, Yan; Yang, Wenxing; Zhang, Lei; Jiang, Roger; Mijangos, Edgar; Saygili, Yasemin; Hammarström, Leif; Hagfeldt, Anders; Boschloo, Gerrit

2016-01-01

Photoelectrochemical approach to solar energy conversion demands a kinetic optimization of various light-induced electron transfer processes. Of great importance are the redox mediator systems accomplishing the electron transfer processes at the semiconductor/electrolyte interface, therefore affecting profoundly the performance of various photoelectrochemical cells. Here, we develop a strategy—by addition of a small organic electron donor, tris(4-methoxyphenyl)amine, into state-of-art cobalt tris(bipyridine) redox electrolyte—to significantly improve the efficiency of dye-sensitized solar cells. The developed solar cells exhibit efficiency of 11.7 and 10.5%, at 0.46 and one-sun illumination, respectively, corresponding to a 26% efficiency improvement compared with the standard electrolyte. Preliminary stability tests showed the solar cell retained 90% of its initial efficiency after 250 h continuous one-sun light soaking. Detailed mechanistic studies reveal the crucial role of the electron transfer cascade processes within the new redox system. PMID:28000672

High performance, flexible, poly(3,4-ethylenedioxythiophene) supercapacitors achieved by doping redox mediators in organogel electrolytes

NASA Astrophysics Data System (ADS)

Zhang, Huanhuan; Li, Jinyu; Gu, Cheng; Yao, Mingming; Yang, Bing; Lu, Ping; Ma, Yuguang

2016-11-01

The relatively low energy density is now a central issue hindering the development of supercapacitors as energy storage devices. Various approaches are thus developed to enhance the energy density, mainly centering on the fabrication of electrode materials or optimization of cell configurations. Compared with these approaches, modifications in electrolytes are much simple and versatile. Herein, we integrate the wide voltages endowed by organic electrolytes and the additional capacitances brought by redox mediators, to fabricate high energy density supercapacitors. On the basis of this idea, supercapacitors with poly(3,4-ethylenedioxythiophene) (PEDOT) as electrode material exhibit extended operating voltage of 1.5 V, extraordinary capacitance of 363 F g-1 and high energy density of 27.4 Wh kg-1. The redox mediators reported here, ferrocene and 4-oxo-2,2,6,6-tetramethylpiperidinooxy, are the first time being applied in supercapacitors, especially in the gel state. While providing additional faradaic capacitances, they also exhibit synergistic interaction with PEDOT and improve the cycling stability of supercapacitors.

High‐Performance Lithium‐Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt

PubMed Central

Ahn, Su Mi; Suk, Jungdon; Kim, Do Youb; Kim, Hwan Kyu

2017-01-01

Abstract To fabricate a sustainable lithium‐oxygen (Li‐O2) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO3) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV‐DEMS study confirms that the TMS‐LiNO3 electrolyte efficiently produces NO2 −, which initiates a redox shuttle reaction. Interestingly, this NO2 −/NO2 redox reaction derived from the LiNO3 salt is not very effective in solvents other than TMS. Compared with other common Li‐O2 solvents, TMS seems optimum solvent for the efficient use of LiNO3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO2 −/NO2 redox reaction, which results in a high‐performance Li‐O2 battery. PMID:29051863

High Energy Density Aqueous Electrochemical Capacitors with a KI-KOH Electrolyte.

PubMed

Wang, Xingfeng; Chandrabose, Raghu S; Chun, Sang-Eun; Zhang, Tianqi; Evanko, Brian; Jian, Zelang; Boettcher, Shannon W; Stucky, Galen D; Ji, Xiulei

2015-09-16

We report a new electrochemical capacitor with an aqueous KI-KOH electrolyte that exhibits a higher specific energy and power than the state-of-the-art nonaqueous electrochemical capacitors. In addition to electrical double layer capacitance, redox reactions in this device contribute to charge storage at both positive and negative electrodes via a catholyte of IOx-/I- couple and a redox couple of H2O/Had, respectively. Here, we, for the first time, report utilizing IOx-/I- redox couple for the positive electrode, which pins the positive electrode potential to be 0.4-0.5 V vs Ag/AgCl. With the positive electrode potential pinned, we can polarize the cell to 1.6 V without breaking down the aqueous electrolyte so that the negative electrode potential could reach -1.1 V vs Ag/AgCl in the basic electrolyte, greatly enhancing energy storage. Both mass spectroscopy and Raman spectrometry confirm the formation of IO3- ions (+5) from I- (-1) after charging. Based on the total mass of electrodes and electrolyte in a practically relevant cell configuration, the device exhibits a maximum specific energy of 7.1 Wh/kg, operates between -20 and 50 °C, provides a maximum specific power of 6222 W/kg, and has a stable cycling life with 93% retention of the peak specific energy after 14,000 cycles.

High-Performance Lithium-Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt.

PubMed

Ahn, Su Mi; Suk, Jungdon; Kim, Do Youb; Kang, Yongku; Kim, Hwan Kyu; Kim, Dong Wook

2017-10-01

To fabricate a sustainable lithium-oxygen (Li-O 2 ) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO 3 ) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO 3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV-DEMS study confirms that the TMS-LiNO 3 electrolyte efficiently produces NO 2 - , which initiates a redox shuttle reaction. Interestingly, this NO 2 - /NO 2 redox reaction derived from the LiNO 3 salt is not very effective in solvents other than TMS. Compared with other common Li-O 2 solvents, TMS seems optimum solvent for the efficient use of LiNO 3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO 2 - /NO 2 redox reaction, which results in a high-performance Li-O 2 battery.

Band edge engineering of oxide photoanodes for photoelectrochemical water splitting: Integration of subsurface dipoles with atomic-scale control

DOE PAGES

Hikita, Yasuyuki; Nishio, Kazunori; Seitz, Linsey C.; ...

2016-01-22

One of the crucial parameters dictating the efficiency of photoelectrochemical water-splitting is the semiconductor band edge alignment with respect to hydrogen and oxygen redox potentials. Despite the importance of metal oxides in their use as photoelectrodes, studies to control the band edge alignment in aqueous solution have been limited predominantly to compound semiconductors with modulation ranges limited to a few hundred mV. The ability to modulate the flat band potential of oxide photoanodes by as much as 1.3 V, using the insertion of subsurface electrostatic dipoles near a Nb-doped SrTiO 3/aqueous electrolyte interface is reported. Lastly, the tunable range achievedmore » far exceeds previous reports in any semiconductor/aqueous electrolyte system and suggests a general design strategy for highly efficient oxide photoelectrodes.« less

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

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

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

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

Bipolar electrochemistry.

PubMed

Fosdick, Stephen E; Knust, Kyle N; Scida, Karen; Crooks, Richard M

2013-09-27

A bipolar electrode (BPE) is an electrically conductive material that promotes electrochemical reactions at its extremities (poles) even in the absence of a direct ohmic contact. More specifically, when sufficient voltage is applied to an electrolyte solution in which a BPE is immersed, the potential difference between the BPE and the solution drives oxidation and reduction reactions. Because no direct electrical connection is required to activate redox reactions, large arrays of electrodes can be controlled with just a single DC power supply or even a battery. The wireless aspect of BPEs also makes it possible to electrosynthesize and screen novel materials for a wide variety of applications. Finally, bipolar electrochemistry enables mobile electrodes, dubbed microswimmers, that are able to move freely in solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of electrochemical actuation by polyaniline nanofibers

NASA Astrophysics Data System (ADS)

Mehraeen, Shayan; Alkan Gürsel, Selmiye; Papila, Melih; Çakmak Cebeci, Fevzi

2017-09-01

Polyaniline nanofibers have shown promising electrical and electrochemical properties which make them prominent candidates in the development of smart systems employing sensors and actuators. Their electrochemical actuation potential is demonstrated in this study. A trilayer composite actuator based on polyaniline nanofibers was designed and fabricated. Cross-linked polyvinyl alcohol was sandwiched between two polyaniline nanofibrous electrodes as ion-containing electrolyte gel. First, electrochemical behavior of a single electrode was studied, showing reversible redox peak pairs in 1 M HCl using a cyclic voltammetry technique. High aspect ratio polyaniline nanofibers create a porous network which facilitates ion diffusion and thus accelerates redox reactions. Bending displacement of the prepared trilayer actuator was then tested and reported under an AC potential stimulation as low as 0.5 V in a variety of frequencies from 50 to 1000 mHz, both inside 1 M HCl solution and in air. Decay of performance of the composite actuator in air is investigated and it is reported that tip displacement in a solution was stable and repeatable for 1000 s in all selected frequencies.

Multicomponent transport in membranes for redox flow batteries

NASA Astrophysics Data System (ADS)

Monroe, Charles

2015-03-01

Redox flow batteries (RFBs) incorporate separator membranes, which ideally prevent mixing of electrochemically active species while permitting crossover of inactive supporting ions. Understanding crossover and membrane selectivity may require multicomponent transport models that account for solute/solute interactions within the membrane, as well as solute/membrane interactions. Application of the Onsager-Stefan-Maxwell formalism allows one to account for all the dissipative phenomena that may accompany component fluxes through RFB membranes. The magnitudes of dissipative interactions (diffusional drag forces) are quantified by matching experimentally established concentration transients with theory. Such transients can be measured non-invasively using DC conductometry, but the accuracy of this method requires precise characterization of the bulk RFB electrolytes. Aqueous solutions containing both vanadyl sulfate (VOSO4) and sulfuric acid (H2SO4) are relevant to RFB technology. One of the first precise characterizations of aqueous vanadyl sulfate has been implemented and will be reported. To assess the viability of a separator for vanadium RFB applications with cell-level simulations, it is critical to understand the tendencies of various classes of membranes to absorb (uptake) active species, and to know the relative rates of active-species and supporting-electrolyte diffusion. It is also of practical interest to investigate the simultaneous diffusion of active species and supports, because interactions between solutes may ultimately affect the charge efficiency and power efficiency of the RFB system as a whole. A novel implementation of Barnes's classical model of dialysis-cell diffusion [Physics 5:1 (1934) 4-8] is developed to measure the binary diffusion coefficients and sorption equilibria for single solutes (VOSO4 or H2SO4) in porous membranes and cation-exchange membranes. With the binary diffusion and uptake measurement in hand, a computer simulation that extends the approach of Heintz, Wiedemann and Ziegler [J. Membrane Science 137:1-2 (1997) 121-132] is used to establish Onsager resistances that describe the drag forces VOSO4 and H2SO4 exert on each other as they interdiffuse. The ramifications of these interactions for different classes of membranes - and for RFB applications - will be discussed. NSF CBET-1253544.

Fluoroethylene Carbonate as a Directing Agent in Amorphous Silicon Anodes: Electrolyte Interface Structure Probed by Sum Frequency Vibrational Spectroscopy and Ab Initio Molecular Dynamics.

PubMed

Horowitz, Yonatan; Han, Hui-Ling; Soto, Fernando A; Ralston, Walter T; Balbuena, Perla B; Somorjai, Gabor A

2018-02-14

Fluorinated compounds are added to carbonate-based electrolyte solutions in an effort to create a stable solid electrolyte interphase (SEI). The SEI mitigates detrimental electrolyte redox reactions taking place on the anode's surface upon applying a potential in order to charge (discharge) the lithium (Li) ion battery. The need for a stable SEI is dire when the anode material is silicon as silicon cracks due to its expansion and contraction upon lithiation and delithiation (charge-discharge) cycles, consequently limiting the cyclability of a silicon-based battery. Here we show the molecular structures for ethylene carbonate (EC): fluoroethylene carbonate (FEC) solutions on silicon surfaces by sum frequency generation (SFG) vibrational spectroscopy, which yields vibrational spectra of molecules at interfaces and by ab initio molecular dynamics (AIMD) simulations at open circuit potential. Our AIMD simulations and SFG spectra indicate that both EC and FEC adsorb to the amorphous silicon (a-Si) through their carbonyl group (C═O) oxygen atom with no further desorption. We show that FEC additives induce the reorientation of EC molecules to create an ordered, up-right orientation of the electrolytes on the Si surface. We suggest that this might be helpful for Li diffusion under applied potential. Furthermore, FEC becomes the dominant species at the a-Si surface as the FEC concentration increases above 20 wt %. Our finding at open circuit potential can now initiate additive design to not only act as a sacrificial compound but also to produce a better suited SEI for the use of silicon anodes in the Li-ion vehicular industry.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Carbon nanosheets-based supercapacitors: Design of dual redox additives of 1, 4-dihydroxyanthraquinone and hydroquinone for improved performance

NASA Astrophysics Data System (ADS)

Xu, Dong; Sun, Xiao Na; Hu, Wei; Chen, Xiang Ying

2017-07-01

Using thiocarbanilide and Mg(OH)2 powders as carbon precursor and template, respectively, novel 2D carbon nanosheets with large area have been produced. Next, based on the cooperative effect, 1, 4-dihydroxyanthraquinone (DQ) and hydroquinone (HQ) regarded as efficient dual redox additives have been incorporated into the electrode carbon material and H2SO4 electrolyte, respectively, to largely elevate the capacitive performance of supercapacitors. More importantly, the cooperative effect results from the redox processes of DQ and HQ consecutively occurring in the electrode carbon material and aqueous H2SO4 electrolyte, respectively. Besides, the molar ratio of DQ and HQ exerts a crucial role in the determination of the electrochemical behaviors and eventually the optimum condition is the mass ratio of 1:1 concerning the DQ and porous carbon within solid electrode while retaining the HQ concentration as 20 mmol L-1 in 1 mol L-1 H2SO4 electrolyte. As a result, the maximum specific capacitance is achieved of 239 F g-1 at 3 A g-1, and furthermore the maximum energy density up to 21.1 Wh kg-1 is almost 3.5 times larger than that of the one without introducing any redox additive.

A supramolecular gel electrolyte formed from amide based co-gelator for quasi-solid-state dye-sensitized solar cell with boosted electron kinetic processes

NASA Astrophysics Data System (ADS)

Huo, Zhipeng; Wang, Lu; Tao, Li; Ding, Yong; Yi, Jinxin; Alsaedi, Ahmed; Hayat, Tasawar; Dai, Songyuan

2017-08-01

A supramolecular gel electrolyte (Tgel > 100 °C) is formed from N,N‧-1,8-octanediylbis-dodecanamide and iodoacetamide as two-component co-gelator, and introduced into the quasi-solid-state dye-sensitized solar cells (QS-DSSCs). The different morphologies of microscopic network between two-component and single-component gel electrolytes have influence on the diffusion of redox couple in gel electrolytes and further affect the electron kinetic processes in QS-DSSCs. Compared with the single-component gel electrolyte, the two-component gel electrolyte has less compact gel network and weaker steric hindrance effect, which provides more effective charge transport channel for the diffusion of I3/I- redox couple. Meanwhile, the sbnd NH2 groups of iodoacetamide molecules interact with Li+ and I3-, which also accelerate the transport of I3-/I- and decrease in the I3- concentration in the TiO2/electrolyte interface. As a result, nearly a 12% improvement in short-circuit photocurrent density (Jsc) and much higher open circuit potential (Voc) are found in the two-component gel electrolyte based QS-DSSC. Consequently, the QS-DSSC based on the supramolecular gel electrolyte obtains a 17% enhancement in the photoelectric conversion efficiency (7.32%) in comparison with the QS-DSSC based on the single-component gel electrolyte (6.24%). Furthermore, the degradations of these QS-DSSCs are negligible after one sun light soaking with UV cutoff filter at 50 °C for 1000 h.

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

PubMed

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

2017-11-02

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

Photocatalytic effect of anodic titanium oxide nanotubes on various cell culture media

NASA Astrophysics Data System (ADS)

Yu, Chun-Kang; Hu, Kan-Hung; Wang, Shing-Hoa; Hsu, Todd; Tsai, Huei-Ting; Chen, Chien-Chon; Liu, Shiu-Mei; Lin, Tai-Yuan; Chen, Chin-Hsing

2011-02-01

The use of titanium dioxide (TiO2) in photodynamic therapy for the treatment of cancer cells has been proposed following studies of cultured cancer cells. In this work, an ordered channel array of anodic titanium oxide (ATO) was fabricated by anodizing titanium foil. The ATO layer of nanotubes with diameters of 100 nm was made in NH4F electrolyte by anodization. The photocatalytic effect of ATO was examined on various culture media by ultraviolet A (UV-A) (366 nm) irradiation. After UV-A irradiation of the ATO layer, redox potential of Tris-HCl buffer (pH 7.5) and dilute acrylamide solution increased instantaneously. The redox potential of the serum-containing RPMI1640 medium also increased dramatically, while that of serum-containing MEM and DMEM media increased slightly. The UVA-induced high redox potential was correlated with the greater ability to break down plasmid DNA strands. These phenomena suggest that a culture medium, such as RPMI1640, with a greater ability to produce free radical may be associated with a stronger photocatalytic effect of ATO on cultured cancer cells reported previously.

Multifunctional Iodide-Free Polymeric Ionic Liquid for Quasi-Solid-State Dye-Sensitized Solar Cells with a High Open-Circuit Voltage.

PubMed

Lin, Yi-Feng; Li, Chun-Ting; Lee, Chuan-Pei; Leu, Yow-An; Ezhumalai, Yamuna; Vittal, R; Chen, Ming-Chou; Lin, Jiang-Jen; Ho, Kuo-Chuan

2016-06-22

A polymeric ionic liquid, poly(oxyethylene)-imide-imidazolium selenocyanate (POEI-IS), was newly synthesized and used for a multifunctional gel electrolyte in a quasi-solid-state dye-sensitized solar cell (QSS-DSSC). POEI-IS has several functions: (a) acts as a gelling agent for the electrolyte of the DSSC, (b) possesses a redox mediator of SeCN(-), which is aimed to form a SeCN(-)/(SeCN)3(-) redox couple with a more positive redox potential than that of traditional I(-)/I3(-), (c) chelates the potassium cations through the lone pair electrons of the oxygen atoms of its poly(oxyethylene)-imide-imidazolium (POEI-I) segments, and (d) obstructs the recombination of photoinjected electrons with (SeCN)3(-) ions in the electrolyte through its POEI-I segments. Thus, the POEI-IS renders a high open-circuit voltage (VOC) to the QSS-DSSC due to its functions of b-d and prolongs the stability of the cell due to its function of a. The QSS-DSSC with the gel electrolyte containing 30 wt % of the POEI-IS in liquid selenocyanate electrolyte exhibited a high VOC of 825.50 ± 3.51 mV and a high power conversion efficiency (η) of 8.18 ± 0.02%. The QSS-DSSC with 30 wt % POEI-IS retained up to 95% of its initial η after an at-rest stability test with the period of more than 1,000 h.

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

PubMed

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

2017-04-01

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

A simple, fast and accurate in-situ method to measure the rate of transport of redox species through membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Meddings, Nina; Owen, John R.; Garcia-Araez, Nuria

2017-10-01

Lithium ion conducting membranes are important to protect the lithium metal electrode and act as a barrier to crossover species such as polysulphides in Li-S systems, redox mediators in Li-O2 cells or dissolved cathode species or electrolyte oxidation products in high voltage Li-ion batteries. We present an in-situ method for measuring permeability of membranes to crossover redox species. The method employs a 'Swagelok' cell design equipped with a glassy carbon working electrode, in which redox species are placed initially in the counter electrode compartment only. Permeability through the membrane, which separates working and counter electrodes, is determined using a square wave voltammetry technique that allows the concentration of crossover redox species to be evaluated over time with very high precision. We test the method using a model and well-behaved electrochemical system to demonstrate its sensitivity, reproducibility and reliability relative to alternative approaches. This new method offers advantages in terms of small electrolyte volume, and simple, fast, quantitative and in-situ measurement.

A New Sealed Lithium-Peroxide Battery with a Co-Doped Li2O Cathode in a Superconcentrated Lithium Bis(fluorosulfonyl)amide Electrolyte

PubMed Central

Okuoka, Shin-ichi; Ogasawara, Yoshiyuki; Suga, Yosuke; Hibino, Mitsuhiro; Kudo, Tetsuichi; Ono, Hironobu; Yonehara, Koji; Sumida, Yasutaka; Yamada, Yuki; Yamada, Atsuo; Oshima, Masaharu; Tochigi, Eita; Shibata, Naoya; Ikuhara, Yuichi; Mizuno, Noritaka

2014-01-01

We propose a new sealed battery operating on a redox reaction between an oxide (O2−) and a peroxide (O22−) with its theoretical specific energy of 2570 Wh kg−1 (897 mAh g−1, 2.87 V) and demonstrate that a Co-doped Li2O cathode exhibits a reversible capacity over 190 mAh g−1, a high rate capability, and a good cyclability with a superconcentrated lithium bis(fluorosulfonyl)amide electrolyte in acetonitrile. The reversible capacity is largely dominated by the O2−/O22− redox reaction between oxide and peroxide with some contribution of the Co2+/Co3+ redox reaction. PMID:25023009

Capacitive behaviour of MnF2 and CoF2 submicro/nanoparticles synthesized via a mild ionic liquid-assisted route

NASA Astrophysics Data System (ADS)

Ma, Ruguang; Zhou, Yao; Yao, Lin; Liu, Guanghui; Zhou, Zhenzhen; Lee, Jong-Min; Wang, Jiacheng; Liu, Qian

2016-01-01

Submicro-/nano-sized MnF2 rods and hierarchical CoF2 cuboids are respectively synthesized via a facile precipitation method assisted by ionic liquid under a mild condition. The as-prepared MF2 (M = Mn, Co) submicro/nanoparticles exhibit impressive specific capacitance in 1.0 M KOH aqueous solution, especially at relatively high current densities, e.g. 91.2, 68.7 and 56.4 F g-1 for MnF2, and 81.7, 70.6 and 63.0 F g-1 for CoF2 at 5, 8 and 10 A g-1, respectively. The mechanism of striking capacitance of MF2 is clarified on the basis of analysing the cycled electrodes by different characterization techniques. Such remarkable capacitance is ascribed to the redox reactions between MF2 and MOOH in aqueous alkaline electrolytes, which can not be obtained in aqueous neutral electrolytes. This study for the first time provides direct evidences on the pseudocapacitance mechanism of MF2 in alkaline electrolytes and paves the way of application of transition metal fluorides as electrodes in supercapacitors.

Optically transparent cathode for Co(III/II) mediated dye-sensitized solar cells based on graphene oxide.

PubMed

Kavan, Ladislav; Yum, Jun-Ho; Graetzel, Michael

2012-12-01

Thin semitransparent films were fabricated on F-doped SnO(2) (FTO) from single-layer graphene oxide (GO) either pure or in a composite with graphene nanoplatelets. Electrocatalytic activity of prepared films was tested for the Co(bpy)(3)(3+/2+) redox couple in acetonitrile electrolyte solution. Pristine GO showed almost no activity, resembling the properties of basal plane pyrolytic graphite. However, electrochemical performance of graphene oxide improved dramatically upon chemical reduction with hydrazine and/or heat treatment. All GO-containing films were firmly bonded to FTO, which contrasted with the poor adhesion of sole graphene nanoplatelets to this support. The activity loss during long-term aging was considerably improved, too. Enhanced stability of GO-containing films together with high electrocatalytic activity is beneficial for application in a new generation of dye-sensitized solar cells employing Co(bpy)(3)(3+/2+) as the redox shuttle.

Reactively sputtered nickel nitride as electrocatalytic counter electrode for dye- and quantum dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Soo Kang, Jin; Park, Min-Ah; Kim, Jae-Yup; Ha Park, Sun; Young Chung, Dong; Yu, Seung-Ho; Kim, Jin; Park, Jongwoo; Choi, Jung-Woo; Jae Lee, Kyung; Jeong, Juwon; Jae Ko, Min; Ahn, Kwang-Soon; Sung, Yung-Eun

2015-05-01

Nickel nitride electrodes were prepared by reactive sputtering of nickel under a N2 atmosphere at room temperature for application in mesoscopic dye- or quantum dot- sensitized solar cells. This facile and reliable method led to the formation of a Ni2N film with a cauliflower-like nanostructure and tetrahedral crystal lattice. The prepared nickel nitride electrodes exhibited an excellent chemical stability toward both iodide and polysulfide redox electrolytes. Compared to conventional Pt electrodes, the nickel nitride electrodes showed an inferior electrocatalytic activity for the iodide redox electrolyte; however, it displayed a considerably superior electrocatalytic activity for the polysulfide redox electrolyte. As a result, compared to dye-sensitized solar cells (DSCs), with a conversion efficiency (η) = 7.62%, and CdSe-based quantum dot-sensitized solar cells (QDSCs, η = 2.01%) employing Pt counter electrodes (CEs), the nickel nitride CEs exhibited a lower conversion efficiency (η = 3.75%) when applied to DSCs, but an enhanced conversion efficiency (η = 2.80%) when applied to CdSe-based QDSCs.

Energize Electrochemical Double Layer Capacitor by Introducing an Ambipolar Organic Redox Radical in Electrolyte.

PubMed

Wang, Yonggang; Hu, Lintong; Zhang, Yue; Shi, Chao; Guo, Kai; Zhai, Tianyou; Li, Huiqiao

2018-05-24

Carbon based electrochemical double layer capacitors (EDLCs) generally exhibit high power and long life, but low energy density/capacitance. Pore/morphology optimization and pseudocapacitive materials modification of carbon materials have been used to improve electrode capacitance, but leading to the consumption of tap density, conductivity and stability. Introducing soluble redox mediators into electrolyte is a promising alternative to improve the capacitance of electrode. However, it is difficult to find one redox mediator that can provide additional capacitance for both positive and negative electrodes simultaneously. Here, an ambipolar organic radical, 2, 2, 6, 6-tetramethylpiperidinyloxyl (TEMPO) is first introduced to the electrolyte, which can substantially contribute additional pseudocapacitance by oxidation at the positive electrode and reduction at the negative electrode simultaneously. The EDLC with TEMPO mediator delivers an energy density as high as 51 Wh kg-1, 2.4 times of the capacitor without TEMPO, and a long cycle stability over 4000 cycles. The achieved results potentially point a new way to improve the energy density of EDLCs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition metal redox and Mn disproportional reaction in LiMn0.5Fe0.5PO4 electrodes cycled with aqueous electrolyte

NASA Astrophysics Data System (ADS)

Zhuo, Zengqing; Hu, Jiangtao; Duan, Yandong; Yang, Wanli; Pan, Feng

2016-07-01

We performed soft x-ray absorption spectroscopy (sXAS) and a quantitative analysis of the transition metal redox in the LiMn0.5Fe0.5PO4 electrodes upon electrochemical cycling. In order to circumvent the complication of the surface reactions with organic electrolyte at high potential, the LiMn0.5Fe0.5PO4 electrodes are cycled with aqueous electrolyte. The analysis of the transitional metal L-edge spectra allows a quantitative determination of the redox evolution of Mn and Fe during the electrochemical cycling. The sXAS analysis reveals the evolving Mn oxidation states in LiMn0.5Fe0.5PO4. We found that electrochemically inactive Mn2+ is formed on the electrode surface during cycling. Additionally, the signal indicates about 20% concentration of Mn4+ at the charged state, providing a strong experimental evidence of the disproportional reaction of Mn3+ to Mn2+ and Mn4+ on the surface of the charged LiMn0.5Fe0.5PO4 electrodes.

Iodine/iodide-free dye-sensitized solar cells.

PubMed

Yanagida, Shozo; Yu, Youhai; Manseki, Kazuhiro

2009-11-17

Dye-sensitized solar cells (DSSCs) are built from nanocrystalline anatase TiO(2) with a 101 crystal face (nc-TiO(2)) onto which a dye is absorbed, ruthenium complex sensitizers, fluid I(-)/I(3)(-) redox couples with electrolytes, and a Pt-coated counter electrode. DSSCs have now reached efficiencies as high as 11%, and G24 Innovation (Cardiff, U.K.) is currently manufacturing them for commercial use. These devices offer several distinct advantages. On the basis of the electron lifetime and diffusion coefficient in the nc-TiO(2) layer, DSSCs maintain a diffusion length on the order of several micrometers when the dyed-nc-TiO(2) porous layer is covered by redox electrolytes of lithium and/or imidazolium iodide and their polyiodide salts. The fluid iodide/iodine (I(-)/I(3)(-)) redox electrolytes can infiltrate deep inside the intertwined nc-TiO(2) layers, promoting the mobility of the nc-TiO(2) layers and serving as a hole-transport material of DSSCs. As a result, these materials eventually give a respectable photovoltaic performance. On the other hand, fluid I(-)/I(3)(-) redox shuttles have certain disadvantages: reduced performance control and long-term stability and incompatibility with some metallic component materials. The I(-)/I(3)(-) redox shuttle shows a significant loss in short circuit current density and a slight loss in open circuit voltage, particularly in highly viscous electrolyte-based DSSC systems. Iodine can also act as an oxidizing agent, corroding metals, such as the grid metal Ag and the Pt mediator on the cathode, especially in the presence of water and oxygen. In addition, the electrolytes (I(-)/I(3)(-)) can absorb visible light (lambda = approximately 430 nm), leading to photocurrent loss in the DSSC. Therefore, the introduction of iodide/iodine-free electrolytes or hole-transport materials (HTMs) could lead to cost-effective alternatives to TiO(2) DSSCs. In this Account, we discuss the iodide/iodine-free redox couple as a substitute for the fluid I(-)/I(3)(-) redox shuttle. We also review the adaptation of solid-state HTMs to the iodide/iodine-free solid-state DSSCs with an emphasis on their pore filling and charge mobility in devices and the relationship of those values to the performance of the resulting iodide/iodine-free DSSCs. We demonstrate how the structures of the sensitizing dye molecules and additives of lithium or imidazolium salts influence device performance. In addition, the self-organizing molecular interaction for electronic contact of HTMs to dye molecules plays an important role in unidirectional charge diffusion at interfaces. The poly(3,4-ethylenedioxythiophene) (PEDOT)-based DSSCs, which we obtain through photoelectrochemical polymerization (PEP) using 3-alkylthiophen-bearing ruthenium dye, HRS-1, and bis-EDOT, demonstrates the importance of nonbonding interface contact (e.g., pi-pi-stacking) for the successful inclusion of HTMs.

Redox doping behaviour of poly(3,4-ethylenedithiothiophene) - The counterion effect

NASA Astrophysics Data System (ADS)

Domagala, Wojciech; Palutkiewicz, Dawid; Cortizo-Lacalle, Diego; Kanibolotsky, Alexander L.; Skabara, Peter J.

2011-07-01

Poly(3,4-ethylenedithiothiophene) - PEDTT, an alkylene sulphur derivative of PEDOT, presents itself as an interesting polymer with a number of disparate redox and chromic properties compared to its close analogue - PEDOT. In this study we present the results of an investigation into the electrochemical doping process of PEDTT, using four different electrolyte solutions, differing in anion content of the chosen salt. The results show that the anion identity plays a key role in the redox reactions accompanying these processes in what could be interpreted as anion ionochromism. In situ UV-Vis spectroelectrochemical experiments reveal an intriguing double electrochromic transition of PEDTT films during their oxidative doping, going from golden-yellow through green to pomegranate - a quality not so common within the family of electroactive conjugated polymers. The evolution of each UV-Vis spectrum over a potential range indicates that different redox states of the polymer are responsible for the chromatic changes. In the reduction half-cycle, the dedoping process of PEDTT appears to follow a path dissimilar to the p-doping one, featuring only one, direct electrochromic transition of the film's colour, bypassing the green state, and a distinct two-step bleaching process of doping-induced charge carrier bands. The observed electrochemical and spectral phenomena have been accredited to the specific redox behaviour of doping-induced radical cation and cationic defect states interacting with the dithioalkylene sulphur atom.

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

PubMed

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

2017-02-13

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

Lithium-ion batteries with intrinsic pulse overcharge protection

DOEpatents

Chen, Zonghai; Amine, Khalil

2013-02-05

The present invention relates in general to the field of lithium rechargeable batteries, and more particularly relates to the positive electrode design of lithium-ion batteries with improved high-rate pulse overcharge protection. Thus the present invention provides electrochemical devices containing a cathode comprising at least one primary positive material and at least one secondary positive material; an anode; and a non-aqueous electrolyte comprising a redox shuttle additive; wherein the redox potential of the redox shuttle additive is greater than the redox potential of the primary positive material; the redox potential of the redox shuttle additive is lower than the redox potential of the secondary positive material; and the redox shuttle additive is stable at least up to the redox potential of the secondary positive material.

Surface Redox Chemistry of Immobilized Nanodiamond: Effects of Particle Size and Electrochemical Environment

NASA Astrophysics Data System (ADS)

Gupta, S.; McDonald, B.; Carrizosa, S. B.

2017-07-01

The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 μm << 1000 nm < 100 nm < 10 nm ≤ 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN) 6 3+ ) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites ( sp 2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox processes in the presence of specific redox-active molecules via feedback mechanism. Apparently, FcMeOH+ tended to have electrostatic affinity for negatively charged ND surface functionalities, corroborated by present experiments. We also attempted to study biocatalytic process using model metalloprotein (cytochrome c; Cyt c) immobilized on ND particles for investigating interfacial electron transfer kinetics and compared with those of functionalized graphene (graphene oxide; GO and reduced GO). The findings are discussed in terms of interplay of sp 3-bonded C (ND core) and sp 2-bonded C (ND shell and graphene-based systems).

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

PubMed

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

2018-01-10

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

New strategy and easy fabrication of solid-state supercapacitor based on polypyrrole and nitrile rubber.

PubMed

Lee, Sangyool; Lee, Youngkwan; Cho, Mi-Suk; Nam, Jae-Do

2008-09-01

Solid state redox supercapacitors were fabricated using a solid polymer electrolyte, nitrile butadiene rubber (NBR)-KCI and chemically deposited polypyrrole (PPy) as the conducting polymer electrodes on both surfaces of a NBR film. The optimal conditions for the preparation of the PPy/NBR electrode were confirmed as functions of the uptake of pyrrole monomer into the NBR matrix as well as the immersion time in an oxidant solution. The morphology of the PPy-NBR-KCI capacitor was observed using scanning electron microscopy. The performance of the capacitors was characterized using a galvanostatic charge-discharge technique.

Electropolymerization of high stable poly(3,4-ethylenedioxythiophene) in ionic liquids and its potential applications in electrochemical capacitor

NASA Astrophysics Data System (ADS)

Liu, Keke; Hu, Zhenglong; Xue, Rong; Zhang, Jianrong; Zhu, Junjie

2008-05-01

Poly(3,4-ethylenedioxythiophene) (PEDOT) has been successfully electropolymerized using a purified 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) as both the growth medium and the supporting electrolyte. The electrochemical performance of the PEDOT thin film was investigated in 1 mol L-1 H2SO4 solution. It possesses nearly ideal capacitive property, and its specific capacitance is about 130 F g-1. Compared with other conducting polymers, enhanced cycling lifetime (up to 70,000 cycles), which is close to that of active carbon materials, was observed on repetitive redox cycling.

Toward a Molecular Understanding of Energetics in Li–S Batteries Using Nonaqueous Electrolytes: A High-Level Quantum Chemical Study

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

Assary, Rajeev S.; Curtiss, Larry A.; Moore, Jeffrey S.

2014-06-05

The Li-S battery (secondary cell or redox flow) technology is a promising future alternative to the present lithium intercalation-based energy storage and, therefore, a molecular level understanding of the chemical processes and properties such as stability of intermediates, reactivity of polysulfides and reactivity towards the non-aqueous electrolytes in the Li-S batteries is of great interest. In this paper, quantum chemical methods (G4MP2, MP2, and B3LYP) were utilized to compute reduction potentials of lithium polysulfides and polysulfide molecular clusters, energetics of disproportionation and association reactions of likely intermediates, and their reactions with ether-based electrolytes. Based on the computed reaction energetics inmore » solution, a probable mechanism during the discharge process for polysulfide anions and lithium polysulfides in solution is proposed and likely intermediates such as S42-,S32-, S22-, and S31- radical were identified. Additionally, the stability and reactivity of propylene carbonate and tetraglyme solvent molecules were assessed against the above-mentioned intermediates and other reactive species by computing the reaction energetics required to initiate the solvent decomposition reactions in solution. Calculations suggest that the propylene carbonate molecule is unstable against the polysulfide anions such as S22-, S32-, and S42- (ΔH† < 0.8 eV) and highly reactive towards Li2S2 and Li2S3. Even though the tetraglyme solvent molecule exhibits increased stability towards polysulfide anions compared to propylene carbonate, this molecule too is vulnerable to nucleophilic attack from Li2S2 and Li2S3 species in solutions. Hence, a long- term stability of the ether molecules is unlikely if high concentration of these reactive intermediates present in the Li-S energy storage systems.« less

A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized β-polytype porous silicon carbide electrodes.

PubMed

Kim, Myeongjin; Yoo, Jeeyoung; Kim, Jooheon

2017-05-23

A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo 2 O 4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo 2 O 4 ) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g -1 at a scan rate of 5 mV s -1 in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe 3 O 4 nanoparticles and SiCF (SiCF/Fe 3 O 4 ) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g -1 at a scan rate of 5 mV s -1 . Therefore, by pairing the SiCF/MgCo 2 O 4 positive electrode and the SiCF/Fe 3 O 4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g -1 at a scan rate of 5 mV s -1 ) and energy density (maximum energy density of 72.79 Wh kg -1 at a power density of 727.96 W kg -1 ).

A Long-Life Lithium-Air Battery in Ambient Air with a Polymer Electrolyte Containing a Redox Mediator.

PubMed

Guo, Ziyang; Li, Chao; Liu, Jingyuan; Wang, Yonggang; Xia, Yongyao

2017-06-19

Lithium-air batteries when operated in ambient air generally exhibit poor reversibility and cyclability, because of the Li passivation and Li 2 O 2 /LiOH/Li 2 CO 3 accumulation in the air electrode. Herein, we present a Li-air battery supported by a polymer electrolyte containing 0.05 m LiI, in which the polymer electrolyte efficiently alleviates the Li passivation induced by attacking air. Furthermore, it is demonstrated that I - /I 2 conversion in polymer electrolyte acts as a redox mediator that facilitates electrochemical decomposition of the discharge products during recharge process. As a result, the Li-air battery can be stably cycled 400 times in ambient air (relative humidity of 15 %), which is much better than previous reports. The achievement offers a hope to develop the Li-air battery that can be operated in ambient air. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

A mixed acid based vanadium-cerium redox flow battery with a zero-gap serpentine architecture

NASA Astrophysics Data System (ADS)

Leung, P. K.; Mohamed, M. R.; Shah, A. A.; Xu, Q.; Conde-Duran, M. B.

2015-01-01

This paper presents the performance of a vanadium-cerium redox flow battery using conventional and zero-gap serpentine architectures. Mixed-acid solutions based on methanesulfonate-sulfate anions (molar ratio 3:1) are used to enhance the solubilities of the vanadium (>2.0 mol dm-3) and cerium species (>0.8 mol dm-3), thus achieving an energy density (c.a. 28 Wh dm-3) comparable to that of conventional all-vanadium redox flow batteries (20-30 Wh dm-3). Electrochemical studies, including cyclic voltammetry and galvanostatic cycling, show that both vanadium and cerium active species are suitable for energy storage applications in these electrolytes. To take advantage of the high open-circuit voltage (1.78 V), improved mass transport and reduced internal resistance are facilitated by the use of zero-gap flow field architecture, which yields a power density output of the battery of up to 370 mW cm-2 at a state-of-charge of 50%. In a charge-discharge cycle at 200 mA cm-2, the vanadium-cerium redox flow battery with the zero-gap architecture is observed to discharge at a cell voltage of c.a. 1.35 V with a coulombic efficiency of up to 78%.

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

NASA Astrophysics Data System (ADS)

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.

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

Ghimire, Govinda; Coceancigh, Herman; Yi, Yi

This study reports the electrochemical behavior and catalytic property of electrode-supported thin films of polystyrene- block-poly(2-(acryloyloxy)ethyl ferrocenecarboxylate) (PS- b-PAEFc) in an ethanol (EtOH) solution. The electrochemical properties of PS- b-PAEFc films with different PAEFc volume fractions (f PAEFc = 0.47, 0.30, and 0.17) in 0.1 M ethanolic sodium hexafluorophosphate were compared with those in an acetonitrile (MeCN) solution of 0.1 M tetrabutylammonium hexafluorophosphate. Pristine PS- b-PAEFc films did not afford significant faradaic currents in the EtOH solution because EtOH is a nonsolvent for both PS and PAEFc. However, the films could be rendered redox-active in the EtOH solution by applyingmore » potentials in the MeCN solution to induce the redox-associated incorporation of the supporting electrolytes into the films. Atomic force microscopy images verified the stability of PAEFc microdomains upon electrochemical measurements in these solutions. Cyclic voltammograms measured in the EtOH solution for PS- b-PAEFc with the larger f PAEFc were diffusion-controlled regardless of ellipsometric film thickness (23 – 152 nm) at relatively slow scan rates, in contrast to those in the MeCN solution that were controlled by surface-confined redox species. The electron propagation efficiency in the EtOH solution was significantly lower than that in the MeCN solution due to the poorer swelling of the films, which limited the migration of counter ions and the collisional motions of the ferrocene moieties. PS- b-PAEFc films were applied as electrochemically-responsive heterogeneous catalysts based on the ferrocenium moieties for Michael addition reaction between methyl vinyl ketone and ethyl 2-oxocyclopentanecarboxylate (E2OC) in 0.1 M NaPF 6/EtOH. The catalytic activities of thin films were similar regardless of f PAEFc, suggesting that the catalytic reaction took place for the reactants that could penetrate through the film and reach PAEFc microdomains communicable with the underlying electrode. Interestingly, the permeability of PS-b-PAEFc films provided a means to control the reaction selectivity, as suggested by negligible reaction of E2OC with trans-4-phenyl-3-buten-2-one.« less

The effects of amine/nitro/hydroxyl groups on the benzene rings of redox additives on the electrochemical performance of carbon-based supercapacitors.

PubMed

Huang, Xuan; Wang, Qian; Chen, Xiang Ying; Zhang, Zhong Jie

2016-04-21

In this work, a series of porous carbon materials with hierarchical porosities have been synthesized via a template carbonization method, in which cheap CaCO3 serves as a template and glucose as a carbon precursor. During the carbonization process, CO2 produced by the decomposition of the CaCO3 template can act as an internal activating agent, significantly improving microporosity and mesoporosity. All the carbon materials obtained by regulating the ratio of glucose to CaCO3 exhibit the amorphous features with a low graphitization degree. Among them, the carbon-1 : 2 sample shows a high BET surface area of up to 818.5 m(2) g(-1) and a large total pore volume of 1.78 cm(3) g(-1) as well as a specific capacitance of 107.0 F g(-1) at 1 A g(-1). In addition, a series of hydroquinone (HQ), p-aminophenol (PAP) and p-nitrophenol (PNP) as novel redox additives that can produce pseudo-capacitances have been added into the KOH electrolyte for promoting the total capacitive performances via redox reactions at the electrode-electrolyte interface. As expected, a 2.5-fold increase in the galvanostatic capacitance of 240.0 F g(-1) in the HQ-0.5 electrolyte occurs, compared with the conventional KOH electrolyte. Similarly, the PAP-0.5 electrolyte and the PNP-0.5 electrolyte also show a high specific capacitance of 184.0 F g(-1) at 2 A g(-1) (156.6 F g(-1) at 3 A g(-1)) and 153.0 F g(-1) at 3 A g(-1), respectively. Additionally, the three kinds of electrolytes exhibit excellent cyclic stability. The remarkable improvement of supercapacitors is attributed to the quick reversible Faradaic reactions of amine and hydroxyl groups adhering to the phenyl rings, which largely accelerates electron migration and brings additional pseudocapacitive contribution for carbon-based supercapacitors.

Voltammetry and conductivity of a polyether-pyridinium room temperature molten salt electrolyte and of its polymer electrolyte solutions in polydimethylsiloxane

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

Pyati, R.; Murray, R.W.

1996-02-01

This report describes the synthesis, microelectrode voltammetry, and ionic conductivity of a new room temperature molten salt N-(methoxy(ethoxy){sub 2}ethyl)pyridinium p-toluene sulfonate (abbreviated as[Py(E{sub 3}M){sup +}][Tos{sup {minus}}]) and of its solution in a hydroxy-terminated polydimethylsiloxane. Both ionically conductive liquids (conductivity = 1 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1}) exhibit voltammetric potential windows of about 1.5 V. The negative potential limit is determined by the reduction of the [Py(E{sub 3}M){sup +}] pyridinium species, with subsequent radical coupling to form a voltammetrically observed viologen dimer. The estimated diffusivities of the [Py(E{sub 3}M){sup +}] species, of a diethyleneglycol-tailed ferrocene redox solute studied, andmore » by application of Nernst-Einstein relation to the ionic charge carriers, all lie in the 10{sup {minus}7} to 10{sup {minus}8} cm{sup 2}/s range. Viscosities and glass transition thermal observations are reported as is the fit of the temperature dependencies of ionic conductivity in [Py(E{sub 3}M){sup +}][Tos{sup {minus}}] and in [Py(E{sub 3}M){sup +}][TOS{sup {minus}}]/PDMS mixtures to Vogel-Tamman-Fulcher predictions.« less

Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries through Electrolytes

DOE PAGES

Tao, Ran; Bi, Xuanxuan; Li, Shu; ...

2017-02-13

Lithium batteries are one of the most advance energy storage devices in the world and have attracted extensive research interests. However, lithium dendrite growth was a safety issue which handicapped the application of pure lithium metal in the negative electrode. In this paper, two solvents, propylene carbonate (PC) and 2-methyl-tetrahydrofuran (2MeTHF), and four Li + salts, LiPF 6, LiAsF 6, LiBF 4 and LiClO 4 were investigated in terms of their effects on the kinetics of lithium dendrite formation in eight electrolyte solutions. The kinetic parameters of charge transfer step (exchange current density, j 0, transfer coefficient, α) of Limore » +/Li redox system, the mass transfer parameters of Li + (transfer number of Li +, t Li+, diffusion coefficient of Li +, D Li+), and the conductivity (κ) of each electrolyte were studied separately. The results demonstrate that the solvents play a critical role in the measured j 0, t Li+, D Li+, and κ of the electrolyte, while the choice of Li + salts only slightly affect the measured parameters. Finally, the understanding of the kinetics will gain insight into the mechanism of lithium dendrite formation and provide guidelines to the future application of lithium metal.« less

Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries through Electrolytes

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

Tao, Ran; Bi, Xuanxuan; Li, Shu

Lithium batteries are one of the most advance energy storage devices in the world and have attracted extensive research interests. However, lithium dendrite growth was a safety issue which handicapped the application of pure lithium metal in the negative electrode. In this paper, two solvents, propylene carbonate (PC) and 2-methyl-tetrahydrofuran (2MeTHF), and four Li + salts, LiPF 6, LiAsF 6, LiBF 4 and LiClO 4 were investigated in terms of their effects on the kinetics of lithium dendrite formation in eight electrolyte solutions. The kinetic parameters of charge transfer step (exchange current density, j 0, transfer coefficient, α) of Limore » +/Li redox system, the mass transfer parameters of Li + (transfer number of Li +, t Li+, diffusion coefficient of Li +, D Li+), and the conductivity (κ) of each electrolyte were studied separately. The results demonstrate that the solvents play a critical role in the measured j 0, t Li+, D Li+, and κ of the electrolyte, while the choice of Li + salts only slightly affect the measured parameters. Finally, the understanding of the kinetics will gain insight into the mechanism of lithium dendrite formation and provide guidelines to the future application of lithium metal.« less

The Li-ion rechargeable battery: a perspective.

PubMed

Goodenough, John B; Park, Kyu-Sung

2013-01-30

Each cell of a battery stores electrical energy as chemical energy in two electrodes, a reductant (anode) and an oxidant (cathode), separated by an electrolyte that transfers the ionic component of the chemical reaction inside the cell and forces the electronic component outside the battery. The output on discharge is an external electronic current I at a voltage V for a time Δt. The chemical reaction of a rechargeable battery must be reversible on the application of a charging I and V. Critical parameters of a rechargeable battery are safety, density of energy that can be stored at a specific power input and retrieved at a specific power output, cycle and shelf life, storage efficiency, and cost of fabrication. Conventional ambient-temperature rechargeable batteries have solid electrodes and a liquid electrolyte. The positive electrode (cathode) consists of a host framework into which the mobile (working) cation is inserted reversibly over a finite solid-solution range. The solid-solution range, which is reduced at higher current by the rate of transfer of the working ion across electrode/electrolyte interfaces and within a host, limits the amount of charge per electrode formula unit that can be transferred over the time Δt = Δt(I). Moreover, the difference between energies of the LUMO and the HOMO of the electrolyte, i.e., electrolyte window, determines the maximum voltage for a long shelf and cycle life. The maximum stable voltage with an aqueous electrolyte is 1.5 V; the Li-ion rechargeable battery uses an organic electrolyte with a larger window, which increase the density of stored energy for a given Δt. Anode or cathode electrochemical potentials outside the electrolyte window can increase V, but they require formation of a passivating surface layer that must be permeable to Li(+) and capable of adapting rapidly to the changing electrode surface area as the electrode changes volume during cycling. A passivating surface layer adds to the impedance of the Li(+) transfer across the electrode/electrolyte interface and lowers the cycle life of a battery cell. Moreover, formation of a passivation layer on the anode robs Li from the cathode irreversibly on an initial charge, further lowering the reversible Δt. These problems plus the cost of quality control of manufacturing plague development of Li-ion rechargeable batteries that can compete with the internal combustion engine for powering electric cars and that can provide the needed low-cost storage of electrical energy generated by renewable wind and/or solar energy. Chemists are contributing to incremental improvements of the conventional strategy by investigating and controlling electrode passivation layers, improving the rate of Li(+) transfer across electrode/electrolyte interfaces, identifying electrolytes with larger windows while retaining a Li(+) conductivity σ(Li) > 10(-3) S cm(-1), synthesizing electrode morphologies that reduce the size of the active particles while pinning them on current collectors of large surface area accessible by the electrolyte, lowering the cost of cell fabrication, designing displacement-reaction anodes of higher capacity that allow a safe, fast charge, and designing alternative cathode hosts. However, new strategies are needed for batteries that go beyond powering hand-held devices, such as using electrode hosts with two-electron redox centers; replacing the cathode hosts by materials that undergo displacement reactions (e.g. sulfur) by liquid cathodes that may contain flow-through redox molecules, or by catalysts for air cathodes; and developing a Li(+) solid electrolyte separator membrane that allows an organic and aqueous liquid electrolyte on the anode and cathode sides, respectively. Opportunities exist for the chemist to bring together oxide and polymer or graphene chemistry in imaginative morphologies.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Surface and interface sciences of Li-ion batteries. -Research progress in electrode-electrolyte interface-

NASA Astrophysics Data System (ADS)

Minato, Taketoshi; Abe, Takeshi

2017-12-01

The application potential of Li-ion batteries is growing as demand increases in different fields at various stages in energy systems, in addition to their conventional role as power sources for portable devices. In particular, applications in electric vehicles and renewable energy storage are increasing for Li-ion batteries. For these applications, improvements in battery performance are necessary. The Li-ion battery produces and stores electric power from the electrochemical redox reactions between the electrode materials. The interface between the electrodes and electrolyte strongly affects the battery performance because the charge transfer causing the electrode redox reaction begins at this interface. Understanding of the surface structure, electronic structure, and chemical reactions at the electrode-electrolyte interface is necessary to improve battery performance. However, the interface is located between the electrode and electrolyte materials, hindering the experimental analysis of the interface; thus, the physical properties and chemical processes have remained poorly understood until recently. Investigations of the physical properties and chemical processes at the interface have been performed using advanced surface science techniques. In this review, current knowledge and future research prospects regarding the electrode-electrolyte interface are described for the further development of Li-ion batteries.

6.5% efficient perovskite quantum-dot-sensitized solar cell.

PubMed

Im, Jeong-Hyeok; Lee, Chang-Ryul; Lee, Jin-Wook; Park, Sang-Won; Park, Nam-Gyu

2011-10-05

Highly efficient quantum-dot-sensitized solar cell is fabricated using ca. 2-3 nm sized perovskite (CH(3)NH(3))PbI(3) nanocrystal. Spin-coating of the equimolar mixture of CH(3)NH(3)I and PbI(2) in γ-butyrolactone solution (perovskite precursor solution) leads to (CH(3)NH(3))PbI(3) quantum dots (QDs) on nanocrystalline TiO(2) surface. By electrochemical junction with iodide/iodine based redox electrolyte, perovskite QD-sensitized 3.6 μm-thick TiO(2) film shows maximum external quantum efficiency (EQE) of 78.6% at 530 nm and solar-to-electrical conversion efficiency of 6.54% at AM 1.5G 1 sun intensity (100 mW cm(-2)), which is by far the highest efficiency among the reported inorganic quantum dot sensitizers.

Self bleaching photoelectrochemical-electrochromic device

DOEpatents

Bechinger, Clemens S.; Gregg, Brian A.

2002-04-09

A photoelectrochemical-electrochromic device comprising a first transparent electrode and a second transparent electrode in parallel, spaced relation to each other. The first transparent electrode is electrically connected to the second transparent electrode. An electrochromic material is applied to the first transparent electrode and a nanoporous semiconductor film having a dye adsorbed therein is applied to the second transparent electrode. An electrolyte layer contacts the electrochromic material and the nanoporous semiconductor film. The electrolyte layer has a redox couple whereby upon application of light, the nanoporous semiconductor layer dye absorbs the light and the redox couple oxidizes producing an electric field across the device modulating the effective light transmittance through the device.

Mass transport enhancement in redox flow batteries with corrugated fluidic networks

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Selectivity and Sensitivity of Ultrathin Monolayer Electrodes

NASA Astrophysics Data System (ADS)

Cheng, Quan

The objective of this work is to build a molecular architecture on the electrode surface with a well-defined morphology and desirable electrochemical characteristics. The goal is accomplished by means of self-assembly of thioctic acid, a sulfur-terminated organic molecule with a short alkyl chain and a hydrophilic carboxylic headgroup, on a gold electrode. Characterization of the monolayer structure and the electrochemical response of the monolayer electrodes is performed by means of capacitance measurements and voltammetry. Investigation of the capacitance of the self-assembled monolayers provides insight into the macroscopic permeability of the films and reveals that penetration of solvent/ions into the thioctic acid monolayer film occurs extensively. Voltammetric results demonstrate that permselectivity of the monolayer electrode can be obtained as a result of the induced electrostatic interactions between the monolayer interface and the electroactive species. Measurement of the voltammetric response of the redox probes at the monolayers as a function of the electrolyte concentration and composition is used to qualitatively analyze the effect of electrolyte on response. A model describing the role of the interfacial charge in the electrochemical response of the monolayers as a function of the solution composition and surface smoothness is proposed. A strategy is developed to further explore the applications of the monolayer electrodes to control the electrochemical response of the biological molecules such as catecholamines. The ability to control the surface hydrophobicity of the monolayer electrodes through coadsorption of thioctic acid and hexanethiol, to display different electrochemical properties towards biological molecules is tested. The optimum conditions for detection of the biological molecules on the monolayer electrodes are discussed. In order to pursue selective analysis in microenvironments, the thioctic acid monolayer formed on the ultramicroelectrodes (UME) is investigated, demonstrating high permselectivity and high sensitivity of the monolayer modified UMEs. Because of the more effective mass transport to the UMEs, effects of electrolyte on the monolayer response can be characterized facilely. Amperometric pH sensing on the thioctic acid UMEs using a redox mediator is discussed. Finally, the thioctic acid monolayer microelectrode is applied to investigate direct electrochemistry of a redox protein, cytochrome c. A sketch for developing a biosensor via mediation effects using the monolayer assembly is proposed.

Enabling rechargeable non-aqueous Mg-O2 battery operations with dual redox mediators.

PubMed

Dong, Qi; Yao, Xiahui; Luo, Jingru; Zhang, Xizi; Hwang, Hajin; Wang, Dunwei

2016-12-11

Dual redox mediators (RMs) were introduced for Mg-O 2 batteries. 1,4-Benzoquinone (BQ) facilitates the discharge with an overpotential reduction of 0.3 V. 5,10,15,20-Tetraphenyl-21H,23H-porphine cobalt(ii) (Co(ii)TPP) facilitates the recharge with an overpotential decrease of up to 0.3 V. Importantly, the two redox mediators are compatible in the same DMSO-based electrolyte.

Low-temperature thermally regenerative electrochemical system

DOEpatents

Loutfy, R.O.; Brown, A.P.; Yao, N.P.

1982-04-21

A thermally regenerative electrochemical system is described including an electrochemical cell with two water-based electrolytes separated by an ion exchange membrane, at least one of the electrolytes containing a complexing agent and a salt of a multivalent metal whose respective order of potentials for a pair of its redox couples is reversible by a change in the amount of the ocmplexing agent in the electrolyte, the complexing agent being removable by distillation to cause the reversal.

Low temperature thermally regenerative electrochemical system

DOEpatents

Loutfy, Raouf O.; Brown, Alan P.; Yao, Neng-Ping

1983-01-01

A thermally regenerative electrochemical system including an electrochemical cell with two water-based electrolytes separated by an ion exchange membrane, at least one of the electrolytes containing a complexing agent and a salt of a multivalent metal whose respective order of potentials for a pair of its redox couples is reversible by a change in the amount of the complexing agent in the electrolyte, the complexing agent being removable by distillation to cause the reversal.

Tin, Bismuth, and Tin-Bismuth Alloy Electrodeposition from Chlorometalate Salts in Deep Eutectic Solvents.

PubMed

Vieira, Luciana; Burt, Jennifer; Richardson, Peter W; Schloffer, Daniel; Fuchs, David; Moser, Alwin; Bartlett, Philip N; Reid, Gillian; Gollas, Bernhard

2017-06-01

The electrodeposition of tin, bismuth, and tin-bismuth alloys from Sn II and Bi III chlorometalate salts in the choline chloride/ethylene glycol (1:2 molar ratio) deep eutectic solvent was studied on glassy carbon and gold by cyclic voltammetry, rotating disc voltammetry, and chronoamperometry. The Sn II -containing electrolyte showed one voltammetric redox process corresponding to Sn II /Sn 0 . The diffusion coefficient of [SnCl 3 ] - , detected as the dominating species by Raman spectroscopy, was determined from Levich and Cottrell analyses. The Bi III -containing electrolyte showed two voltammetric reduction processes, both attributed to Bi III /Bi 0 . Dimensionless current/time transients revealed that the electrodeposition of both Sn and Bi on glassy carbon proceeded by 3D-progressive nucleation at a low overpotential and changed to instantaneous at higher overpotentials. The nucleation rate of Bi on glassy carbon was considerably smaller than that of Sn. Elemental Sn and Bi were electrodeposited on Au-coated glass slides from their respective salt solutions, as were Sn-Bi alloys from a 2:1 Sn II /Bi III solution. The biphasic Sn-Bi alloys changed from a Bi-rich composition to a Sn-rich composition by making the deposition potential more negative.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

"Why not stoichiometry" versus "Stoichiometry--why not?" Part II: GATES in context with redox systems.

PubMed

Michałowska-Kaczmarczyk, Anna Maria; Asuero, Agustin G; Toporek, Marcin; Michałowski, Tadeusz

2015-01-01

Redox equilibria and titration play an important role in chemical analysis, and the formulation of an accurate mathematical description is a challenge. This article is devoted to static and (mainly) dynamic redox systems; the dynamic systems are represented by redox titrations. An overview addresses earlier approaches to static redox systems (redox diagram plots, including Pourbaix diagrams) and to titration redox systems, thereby covering a gap in the literature. After this short review, the generalized approach to electrolytic systems (GATES) is introduced, with generalized electron balance (GEB) as its inherent part within GATES/GEB. Computer simulation, performed according to GATES/GEB, enables following the changes in potential and pH of the solution, together with chemical speciation at each step of a titration, thus providing better insight into this procedure. The undeniable advantages of GATES/GEB over earlier approaches are indicated. Formulation of GEB according to two approaches (I and II) is presented on the respective examples. A general criterion distinguishing between non-redox and redox systems is presented. It is indicated that the formulation of GEB according to Approach II does not need the knowledge of oxidation degrees of particular elements; knowledge of the composition, expressed by chemical formula of the species and its charge, is sufficient for this purpose. Approach I to GEB, known also as the "short" version of GEB, is applicable if oxidation degrees for all elements of the system are known beforehand. The roles of oxidants and reductants are not ascribed to particular components forming a system and to the species thus formed. This is the complete opposite of earlier approaches to redox titrations, based on the stoichiometric redox reaction, formulated for this purpose. GEB, perceived as a law of matter conservation, is fully compatible with other (charge and concentration) balances related to the system in question. The applicability of GATES/GEB in optimization a priori of chemical analyses made with use of redox titration is indicated. The article is illustrated with many examples of static and dynamic redox systems. The related plots are obtained from calculations made according to iterative computer programs. This way, GATES/GEB enables seeing details invisible in real experiments.

A ZnO nanowire bio-hybrid solar cell

NASA Astrophysics Data System (ADS)

Yaghoubi, Houman; Schaefer, Michael; Yaghoubi, Shayan; Jun, Daniel; Schlaf, Rudy; Beatty, J. Thomas; Takshi, Arash

2017-02-01

Harvesting solar energy as a carbon free source can be a promising solution to the energy crisis and environmental pollution. Biophotovoltaics seek to mimic photosynthesis to harvest solar energy and to take advantage of the low material costs, negative carbon footprint, and material abundance. In the current study, we report on a combination of zinc oxide (ZnO) nanowires with monolayers of photosynthetic reaction centers which are self-assembled, via a cytochrome c linker, as photoactive electrode. In a three-probe biophotovoltaics cell, a photocurrent density of 5.5 μA cm-2 and photovoltage of 36 mV was achieved, using methyl viologen as a redox mediator in the electrolyte. Using ferrocene as a redox mediator a transient photocurrent density of 8.0 μA cm-2 was obtained, which stabilized at 6.4 μA cm-2 after 20 s. In-depth electronic structure characterization using photoemission spectroscopy in conjunction with electrochemical analysis suggests that the fabricated photoactive electrode can provide a proper electronic path for electron transport all the way from the conduction band of the ZnO nanowires, through the protein linker to the RC, and ultimately via redox mediator to the counter electrode.

Redox shuttles having an aromatic ring fused to a 1,1,4,4-tetrasubstituted cyclohexane ring

DOEpatents

Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

2015-12-01

An electrolyte includes an alkali metal salt; an aprotic solvent; and a redox shuttle additive including an aromatic compound having at least one aromatic ring fused with at least one non-aromatic ring, the aromatic ring having two or more oxygen or phosphorus-containing substituents.

Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion

DOE PAGES

Zarkesh, Ryan A.; Ichimura, Andrew S.; Monson, Todd C.; ...

2016-02-01

We used the redox-active bis(imino)acenapthene (BIAN) ligand to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN) 3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Ultimately, complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.

Effects of TiO2 and TiC Nanofillers on the Performance of Dye Sensitized Solar Cells Based on the Polymer Gel Electrolyte of a Cobalt Redox System.

PubMed

Venkatesan, Shanmuganathan; Liu, I-Ping; Chen, Li-Tung; Hou, Yi-Chen; Li, Chiao-Wei; Lee, Yuh-Lang

2016-09-21

Polymer gel electrolytes (PGEs) of cobalt redox system are prepared for dye sensitized solar cell (DSSC) applications. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is used as a gelator of an acetonitrile (ACN) liquid electrolyte containing tris(2,2'-bipyridine)cobalt(II/III) redox couple. Titanium dioxide (TiO2) and titanium carbide (TiC) nanoparticles are utilized as nanofillers (NFs) of this PGE, and the effects of the two NFs on the conductivity of the PGEs, charge-transfer resistances at the electrode/PGE interface, and the performance of the gel-state DSSCs are studied and compared. The results show that the presence of TiC NFs significantly increases the conductivity of the PGE and decreases the charge-transfer resistance at the Pt counter-electrode (CE)/PGE interface. Therefore, the gel-state DSSC utilizing TiC NFs can achieve a conversion efficiency (6.29%) comparable to its liquid counterpart (6.30%), and, furthermore, the cell efficiency can retain 94% of its initial value after a 1000 h stability test at 50 °C. On the contrary, introduction of TiO2 NFs in the PGE causes a decrease of cell performances. It shows that the presence of TiO2 NFs increases the charge-transfer resistance at the Pt CE/PGE interface, induces the charge recombination at the photoanode/PGE interface, and, furthermore, causes a dye desorption in a long-term-stability test. These results are different from those reported for the iodide redox system and are ascribed to a specific attractive interaction between TiO2 and cobalt redox ions.

Effects of Additives on Electrochemical Growth of Cu Film on Co/SiO2/Si Substrate by Alternating Underpotential Deposition of Pb and Surface-Limited Redox Replacement by Cu

NASA Astrophysics Data System (ADS)

Fang, J. S.; Lin, L. Y.; Wu, C. L.; Cheng, Y. L.; Chen, G. S.

2017-11-01

The effects of additives to an acidic electrolyte for electrochemical deposition of copper film to prevent corrosion of the Co/SiO2/Si substrate have been investigated. A sacrificial Pb layer was formed by underpotential deposition (UPD), then a Cu layer was prepared using surface-limited redox replacement (SLRR) to exchange the UPD-Pb layer in an acidic copper electrolyte with trisodium citrate, sodium perchlorate, and ethylenediamine as additives. The additives significantly affected the replacement of UPD-Pb by Cu and prevented galvanic corrosion of the Co/SiO2/Si substrate in the acidic Cu electrolyte. The results showed that both sodium perchlorate and ethylenediamine reduced the corrosion of the Co substrate and resulted in Cu film with low electrical resistivity. However, residual Pb was present in the Cu film when using trisodium citrate, as the citrate ions slowed copper displacement. The proposed sequential UPD-Pb and SLRR-Cu growth method may enable electrochemical deposition for fabrication of Cu interconnects on Co substrate from acidic Cu electrolyte.

Background electrolytes and pH effects on selenate adsorption using iron-impregnated granular activated carbon and surface binding mechanisms.

PubMed

Zhang, Ning; Gang, Daniel Dianchen; McDonald, Louis; Lin, Lian-Shin

2018-03-01

Iron-impregnated granular activated carbon (Fe-GAC) has been shown effective for selenite adsorptive removal from aqueous solutions, but similar effectiveness was not observed with selenate. This study examined the effects of background electrolytes and pH on selenate adsorption on to Fe-GAC, and surface bindings to elucidate the selenate adsorption mechanisms. The decrease magnitude of selenate adsorption capacity under three background electrolytes followed the order: LiCl > NaCl > KCl, as ionic strength increased from 0.01 to 0.1 M. Larger adsorption capacity differences among the three electrolytes were observed under the higher ionic strengths (0.05 and 0.1 M) than those under 0.01 M. Multiplet peak fittings of high resolution X-ray photoelectron spectra for O1s and Fe2p 3/2 indicated the presence of iron (III) on adsorbent surface. pH variations during the adsorbent preparation within 3-8 in NaCl solutions did not cause appreciable changes in the iron redox state and composition. Raman spectra showed the formation of both monodentate and bidentate inner sphere complexes under pHs <7 and a mixture of outer sphere and inner sphere complexes at pH 8. These results explained the lower selenate adsorption under alkaline conditions. Mechanisms for monodentate and bidentate formations and a stable six-member ring structure were proposed. Two strategies were recommended for modifying Fe-GAC preparation procedure to enhance the selenate adsorption: (1) mixed-metal oxide coatings to increase the point of zero charge (pH zpc ); and (2) ferrous iron coating to initially reduce selenate followed by selenite adsorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

In-situ growth of MnO2 crystals under nanopore-constraint in carbon nanofibers and their electrochemical performance

PubMed Central

Le, TrungHieu; Yang, Ying; Yu, Liu; Huang, Zheng-hong; Kang, Feiyu

2016-01-01

Growing MnO2 nanocrystals in the bulk of porous carbon nanofibers is conducted in a KMnO4 aqueous solution aimed to enhance the electrochemical performance of MnO2. The rate of redox reaction between KMnO4 and carbon was controlled by the concentration of KMnO4 in a neutral solution. The MnO2 nanoparticles grow along with (211) crystal faces when the redox reaction happens on the surface of fibers under 1D constraint, while the nanoparticles grow along with (200) crystal faces when the redox reaction happens in the bulk of fibers under 3D constraint. The composite, where MnO2 nanoparticles are formed in the bulk under a constraint, yields an electrode material for supercapacitors showing good electron transport, rapid ion penetration, fast and reversible Faradaic reaction, and excellent rate performance. The capacitance of the composite electrode could be 1282 F g−1 under a current density of 0.2 A g−1 in 1 M Na2SO4 electrolyte. A symmetric supercapacitor delivers energy density of 36 Wh kg−1 with power density of 39 W kg−1, and can maintain 7.5 Wh kg−1 at 10.3 kW kg−1. It exhibits an excellent electrochemical cycling stability with 101% initial capacitance and 95% columbic efficiency even after 1000 cycles of charge/discharge. PMID:27869184

The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

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

Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David

Here, we report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performancemore » in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.« less

The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes.

PubMed

Giovannitti, Alexander; Maria, Iuliana P; Hanifi, David; Donahue, Mary J; Bryant, Daniel; Barth, Katrina J; Makdah, Beatrice E; Savva, Achilleas; Moia, Davide; Zetek, Matyáš; Barnes, Piers R F; Reid, Obadiah G; Inal, Sahika; Rumbles, Garry; Malliaras, George G; Nelson, Jenny; Rivnay, Jonathan; McCulloch, Iain

2018-05-08

We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

DOE PAGES

Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David; ...

2018-04-24

Here, we report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performancemore » in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.« less

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

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

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

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

Iron and Manganese Pyrophosphates as Cathodes for Lithium-Ion Batteries

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

Zhou, Hui; Upreti, Shailesh; Chernova, Natasha A.

2015-10-15

The mixed-metal phases, (Li{sub 2}Mn{sub 1-y}Fe{sub y}P{sub 2}O{sub 7}, 0 {le} y {le} 1), were synthesized using a 'wet method', and found to form a solid solution in the P2{sub 1}/a space group. Both thermogravimetric analysis and magnetic susceptibility measurements confirm the 2+ oxidation state for both the Mn and Fe. The electrochemical capacity improves as the Fe concentration increases, as do the intensities of the redox peaks of the cyclic voltammogram, indicating higher lithium-ion diffusivity in the iron phase. The two Li{sup +} ions in the three-dimensional tunnel structure of the pyrophosphate phase allows for the cycling of moremore » than one lithium per redox center. Cyclic voltammograms show a second oxidation peak at 5 V and 5.3 V, indicative of the extraction of the second lithium ion, in agreement with ab initio computation predictions. Thus, electrochemical capacities exceeding 200 Ah/kg may be achieved if a stable electrolyte is found.« less

Oxidovanadium(IV/V) complexes as new redox mediators in dye-sensitized solar cells: a combined experimental and theoretical study.

PubMed

Apostolopoulou, Andigoni; Vlasiou, Manolis; Tziouris, Petros A; Tsiafoulis, Constantinos; Tsipis, Athanassios C; Rehder, Dieter; Kabanos, Themistoklis A; Keramidas, Anastasios D; Stathatos, Elias

2015-04-20

Corrosiveness is one of the main drawbacks of using the iodide/triiodide redox couple in dye-sensitized solar cells (DSSCs). Alternative redox couples including transition metal complexes have been investigated where surprisingly high efficiencies for the conversion of solar to electrical energy have been achieved. In this paper, we examined the development of a DSSC using an electrolyte based on square pyramidal oxidovanadium(IV/V) complexes. The oxidovanadium(IV) complex (Ph4P)2[V(IV)O(hybeb)] was combined with its oxidized analogue (Ph4P)[V(V)O(hybeb)] {where hybeb(4-) is the tetradentate diamidodiphenolate ligand [1-(2-hydroxybenzamido)-2-(2-pyridinecarboxamido)benzenato}and applied as a redox couple in the electrolyte of DSSCs. The complexes exhibit large electron exchange and transfer rates, which are evident from electron paramagnetic resonance spectroscopy and electrochemistry, rendering the oxidovanadium(IV/V) compounds suitable for redox mediators in DSSCs. The very large self-exchange rate constant offered an insight into the mechanism of the exchange reaction most likely mediated through an outer-sphere exchange mechanism. The [V(IV)O(hybeb)](2-)/[V(V)O(hybeb)](-) redox potential and the energy of highest occupied molecular orbital (HOMO) of the sensitizing dye N719 and the HOMO of [V(IV)O(hybeb)](2-) were calculated by means of density functional theory electronic structure calculation methods. The complexes were applied as a new redox mediator in DSSCs, while the cell performance was studied in terms of the concentration of the reduced and oxidized form of the complexes. These studies were performed with the commercial Ru-based sensitizer N719 absorbed on a TiO2 semiconducting film in the DSSC. Maximum energy conversion efficiencies of 2% at simulated solar light (AM 1.5; 1000 W m(-2)) with an open circuit voltage of 660 mV, a short-circuit current of 5.2 mA cm(-2), and a fill factor of 0.58 were recorded without the presence of any additives in the electrolyte.

MnO2 nanotubes assembled on conductive graphene/polyester composite fabric as a three-dimensional porous textile electrode for flexible electrochemical capacitors.

PubMed

Jin, Chun; Jin, Li-Na; Guo, Mei-Xia; Liu, Ping; Zhang, Jia-Nan; Bian, Shao-Wei

2017-12-15

A three-dimensional (3D) electrode material was successfully synthesized through a facile ZnO-assisted hydrothermal process in which vertical MnO 2 nanotube arrays were in situ grown on the conductive graphene/polyester composite fabric. The morphology and structure of MnO 2 nanotubes/graphene/polyester textile electrode were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The 3D electrode structure facilitates to achieve the maximum number of active sites for the pesudocapacitance redox reaction, fast electrolyte ion transportation and short ion diffusion path. The electrochemical measurements showed that the electrode possesses good capacitance capacity which reached 498F/g at a scan rate of 2mV/s in Na 2 SO 4 electrolyte solution. The electrode also showed stable electrochemical performances under the conditions of long-term cycling, and mechanical bending and twisting. Copyright © 2017 Elsevier Inc. All rights reserved.

Electrochemical annealing of nanoporous gold by application of cyclic potential sweeps

PubMed Central

Sharma, Abeera; Bhattarai, Jay K.; Alla, Allan J.; Demchenko, Alexei V.; Stine, Keith J.

2015-01-01

An electrochemical method for annealing the pore sizes of nanoporous gold is reported. The pore sizes of nanoporous gold can be increased by electrochemical cycling with the upper potential limit being just at the onset of gold oxide formation. This study has been performed in electrolyte solutions including potassium chloride, sodium nitrate and sodium perchlorate. Scanning electron microscopy images have been used for ligament and pore size analysis. We examine the modifications of nanoporous gold due to annealing using electrochemical impedance spectroscopy, and cyclic voltammetry and offer a comparison of the surface coverage using the gold oxide stripping method as well as the method in which electrochemically accessible surface area is determined by using a diffusing redox probe. The effect of additives adsorbed on the nanoporous gold surface when subjected to annealing in different electrolytes as well as the subsequent structural changes in nanoporous gold are also reported. The effect of the annealing process on the application of nanoporous gold as a substrate for glucose electro-oxidation is briefly examined. PMID:25649027

Electrochemical Characterization and Catalytic Application of Gold-Supported Ferrocene-Containing Diblock Copolymer Thin Films in Ethanol Solution

DOE PAGES

Ghimire, Govinda; Coceancigh, Herman; Yi, Yi; ...

2017-01-25

This study reports the electrochemical behavior and catalytic property of electrode-supported thin films of polystyrene- block-poly(2-(acryloyloxy)ethyl ferrocenecarboxylate) (PS- b-PAEFc) in an ethanol (EtOH) solution. The electrochemical properties of PS- b-PAEFc films with different PAEFc volume fractions (f PAEFc = 0.47, 0.30, and 0.17) in 0.1 M ethanolic sodium hexafluorophosphate were compared with those in an acetonitrile (MeCN) solution of 0.1 M tetrabutylammonium hexafluorophosphate. Pristine PS- b-PAEFc films did not afford significant faradaic currents in the EtOH solution because EtOH is a nonsolvent for both PS and PAEFc. However, the films could be rendered redox-active in the EtOH solution by applyingmore » potentials in the MeCN solution to induce the redox-associated incorporation of the supporting electrolytes into the films. Atomic force microscopy images verified the stability of PAEFc microdomains upon electrochemical measurements in these solutions. Cyclic voltammograms measured in the EtOH solution for PS- b-PAEFc with the larger f PAEFc were diffusion-controlled regardless of ellipsometric film thickness (23 – 152 nm) at relatively slow scan rates, in contrast to those in the MeCN solution that were controlled by surface-confined redox species. The electron propagation efficiency in the EtOH solution was significantly lower than that in the MeCN solution due to the poorer swelling of the films, which limited the migration of counter ions and the collisional motions of the ferrocene moieties. PS- b-PAEFc films were applied as electrochemically-responsive heterogeneous catalysts based on the ferrocenium moieties for Michael addition reaction between methyl vinyl ketone and ethyl 2-oxocyclopentanecarboxylate (E2OC) in 0.1 M NaPF 6/EtOH. The catalytic activities of thin films were similar regardless of f PAEFc, suggesting that the catalytic reaction took place for the reactants that could penetrate through the film and reach PAEFc microdomains communicable with the underlying electrode. Interestingly, the permeability of PS-b-PAEFc films provided a means to control the reaction selectivity, as suggested by negligible reaction of E2OC with trans-4-phenyl-3-buten-2-one.« less

UV-Vis spectrophotometry of quinone flow battery electrolyte for in situ monitoring and improved electrochemical modeling of potential and quinhydrone formation.

PubMed

Tong, Liuchuan; Chen, Qing; Wong, Andrew A; Gómez-Bombarelli, Rafael; Aspuru-Guzik, Alán; Gordon, Roy G; Aziz, Michael J

2017-12-06

Quinone-based aqueous flow batteries provide a potential opportunity for large-scale, low-cost energy storage due to their composition from earth abundant elements, high aqueous solubility, reversible redox kinetics and their chemical tunability such as reduction potential. In an operating flow battery utilizing 9,10-anthraquinone-2,7-disulfonic acid, the aggregation of an oxidized quinone and a reduced hydroquinone to form a quinhydrone dimer causes significant variations from ideal solution behavior and of optical absorption from the Beer-Lambert law. We utilize in situ UV-Vis spectrophotometry to establish (a), quinone, hydroquinone and quinhydrone molar attenuation profiles and (b), an equilibrium constant for formation of the quinhydrone dimer (K QHQ ) ∼ 80 M -1 . We use the molar optical attenuation profiles to identify the total molecular concentration and state of charge at arbitrary mixtures of quinone and hydroquinone. We report density functional theory calculations to support the quinhydrone UV-Vis measurements and to provide insight into the dimerization conformations. We instrument a quinone-bromine flow battery with a Pd-H reference electrode in order to demonstrate how complexation in both the negative (quinone) and positive (bromine) electrolytes directly impacts measured half-cell and full-cell voltages. This work shows how accounting for electrolyte complexation improves the accuracy of electrochemical modeling of flow battery electrolytes.

Quantification of the effect of 4-tert-butylpyridine addition to I-/I3- redox electrolytes in dye-sensitized nanostructured TiO2 solar cells.

PubMed

Boschloo, Gerrit; Häggman, Leif; Hagfeldt, Anders

2006-07-06

Addition of 4-tert-butylpyridine (4TBP) to redox electrolytes used in dye-sensitized TiO2 solar cells has a large effect on their performance. In an electrolyte containing 0.7 M LiI and 0.05 M I2 in 3-methoxypropionitrile, addition of 0.5 M 4TBP gave an increase of the open-circuit potential of 260 mV. Using charge extraction and electron lifetime measurements, this increases could be attributed to a shift of the TiO2 band edge toward negative potentials (responsible for 60% of the voltage increase) and to an increase of the electron lifetime (40%). At a lower 4TBP concentration the shift of the band edge was similar, but the effect on the electron lifetime was less pronounced. The working mechanism of 4TBP can be summarized as follows: (1) 4TBP affects the surface charge of TiO2 by decreasing the amount of adsorbed protons and/or Li+ ions. (2) It decreases the recombination of electrons in TiO2 with triiodide in the electrolyte by preventing triiodide access to the TiO2 surface and/or by complexation with iodine in the electrolyte.

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Encapsulation of redox polysulphides via chemical interaction with nitrogen atoms in the organic linkers of metal-organic framework nanocrystals

PubMed Central

Park, Jung Hyo; Choi, Kyung Min; Lee, Dong Ki; Moon, Byeong Cheul; Shin, Sang Rim; Song, Min-Kyu; Kang, Jeung Ku

2016-01-01

Lithium polysulphides generated during discharge in the cathode of a lithium-sulphur redox cell are important, but their dissolution into the electrolyte from the cathode during each redox cycle leads to a shortened cycle life. Herein, we use in situ spectroelectrochemical measurements to demonstrate that sp2 nitrogen atoms in the organic linkers of nanocrystalline metal-organic framework-867 (nMOF-867) are able to encapsulate lithium polysulphides inside the microcages of nMOF-867, thus helping to prevent their dissolution into the electrolyte during discharge/charge cycles. This encapsulation mechanism of lithiated/delithiated polysulphides was further confirmed by observations of shifted FTIR spectra for the C = N and C-N bonds, the XPS spectra for the Li-N bonds from nMOF-867, and a visualization method, demonstrating that nMOF-867 prevents lithium polysulphides from being dissolved in the electrolyte. Indeed, a cathode fabricated using nMOF-867 exhibited excellent capacity retention over a long cycle life of 500 discharge/charge cycles, with a capacity loss of approximately 0.027% per cycle from a discharge capacity of 788 mAh/g at a high current rate of 835 mA/g. PMID:27149405

Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

PubMed

Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

2017-01-18

As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

Electrolyte for batteries with regenerative solid electrolyte interface

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

Xiao, Jie; Lu, Dongping; Shao, Yuyan

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

High conductivity electrolyte solutions and rechargeable cells incorporating such solutions

DOEpatents

Angell, C.A.; Zhang, S.S.; Xu, K.

1998-10-20

This invention relates generally to electrolyte solvents for use in liquid or rubbery polymer electrolyte solutions as are used, for example, in electrochemical devices. More specifically, this invention relates to sulfonyl/phospho-compound electrolyte solvents and sulfonyl/phospho-compound electrolyte solutions incorporating such solvents. 9 figs.

Wide electrochemical window solvents for use in electrochemical devices and electrolyte solutions incorporating such solvents

DOEpatents

Angell, Charles Austen; Zhang, Sheng-Shui; Xu, Kang

1998-01-01

The present invention relates to electrolyte solvents for use in liquid or rubbery electrolyte solutions. Specifically, this invention is directed to boron-containing electrolyte solvents and boron-containing electrolyte solutions.

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

PubMed

Sepehr, Fatemeh; Paddison, Stephen J

2015-06-04

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

Redox active polymers and colloidal particles for flow batteries

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

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

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

Electrochemical incineration of wastes

NASA Technical Reports Server (NTRS)

Bhardwaj, R. C.; Sharma, D. K.; Bockris, J. OM.

1990-01-01

The novel technology of waste removal in space vehicles by electrochemical methods is presented to convert wastes into chemicals that can be eventually recycled. The important consideration for waste oxidation is to select a right kind of electrode (anode) material that should be stable under anodic conditions and also a poor electrocatalyst for oxygen and chlorine evolution. On the basis of long term electrolysis experiments on seven different electrodes and on the basis of total organic carbon reduced, two best electrodes were identified. The effect of redox ions on the electrolyte was studied. Though most of the experiments were done in mixtures of urine and waste, the experiments with redox couples involved 2.5 M sulfuric acid in order to avoid the precipitation of redox ions by urea. Two methods for long term electrolysis of waste were investigated: (1) the oxidation on Pt and lead dioxide electrodes using the galvanostatic methods; and (2) potentiostatic method on other electrodes. The advantage of the first method is the faster rate of oxidation. The chlorine evolution in the second method is ten times less then in the first. The accomplished research has shown that urine/feces mixtures can be oxidized to carbon dioxide and water, but current densities are low and must be improved. The perovskite and Ti4O7 coated with RuO2 are the best electrode materials found. Recent experiment with the redox agent improves the current density, however, sulphuric acid is required to keep the redox agent in solution to enhance oxidation effectively. It is desirable to reduce the use of acid and/or find substitutes.

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

PubMed

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

2016-01-20

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

Redox mediation and hydrogen-generation with bipyridinium reagents

DOEpatents

Wrighton, Mark S.; Bookbinder, Dana C.; Bruce, James A.; Dominey, Raymond N.; Lewis, Nathan S.

1984-03-27

A variety of redox mediating agents employing bipyridinium reagents and such reagents in conjunction with dispersed noble metals, such as platinium, are disclosed as coatings for substrates and electrodes. The agents may be charged by an applied voltage or by photoelectric effects or may be equilibrated with hydrogen. The agents are useful in reducing biological materials and electrolytic hydrogen production.

Polymer Electrolyte Fuel Cells Employing Heteropolyacids as Redox Mediators for Oxygen Reduction Reactions: Pt-Free Cathode Systems.

PubMed

Matsui, Toshiaki; Morikawa, Eri; Nakada, Shintaro; Okanishi, Takeou; Muroyama, Hiroki; Hirao, Yoshifumi; Takahashi, Tsuyoshi; Eguchi, Koichi

2016-07-20

In this study, the heteropolyacids of H3+xPVxMO12-xO40 (x = 0, 2, and 3) were applied as redox mediators for the oxygen reduction reaction in polymer electrolyte fuel cells, of which the cathode is free from the usage of noble metals such as Pt/C. In this system, the electrochemical reduction of heteropolyacid over the carbon cathode and the subsequent reoxidation of the partially reduced heteropolyacid by exposure to the dissolved oxygen in the regenerator are important processes for continuous power generation. Thus, the redox properties of catholytes containing these heteropolyacids were investigated in detail. The substitution quantity of V in the heteropolyacid affected the onset reduction potential as well as the reduction current density, resulting in a difference in cell performance. The chemical composition of heteropolyacid also had a significant impact on the reoxidation property. Among the three compounds, H6PV3Mo9O40 was the most suitable redox mediator. Furthermore, the pH of the catholyte was found to be the crucial factor in determining the reoxidation rate of partially reduced heteropolyacid as well as cell performance.

High Electrocatalytic Activity of Vertically Aligned Single-Walled Carbon Nanotubes towards Sulfide Redox Shuttles.

PubMed

Hao, Feng; Dong, Pei; Zhang, Jing; Zhang, Yongchang; Loya, Phillip E; Hauge, Robert H; Li, Jianbao; Lou, Jun; Lin, Hong

2012-01-01

Vertically aligned single-walled carbon nanotubes (VASWCNTs) have been successfully transferred onto transparent conducting oxide glass and implemented as efficient low-cost, platinum-free counter electrode in sulfide -mediated dye-sensitized solar cells (DSCs), featuring notably improved electrocatalytic activity toward thiolate/disulfide redox shuttle over conventional Pt counter electrodes. Impressively, device with VASWCNTs counter electrode demonstrates a high fill factor of 0.68 and power conversion efficiency up to 5.25%, which is significantly higher than 0.56 and 3.49% for that with a conventional Pt electrode. Moreover, VASWCNTs counter electrode produces a charge transfer resistance of only 21.22 Ω towards aqueous polysulfide electrolyte commonly applied in quantum dots-sensitized solar cells (QDSCs), which is several orders of magnitude lower than that of a typical Pt electrode. Therefore, VASWCNTs counter electrodes are believed to be a versatile candidate for further improvement of the power conversion efficiency of other iodine-free redox couple based DSCs and polysulfide electrolyte based QDSCs.

Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing

DOE PAGES

Prabhakaran, Venkateshkumar; Mehdi, B. Layla; Ditto, Jeffrey J.; ...

2016-04-21

Here, the rational design of improved electrode-electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly-dispersed discrete redox-active cluster anions (50 ng of pure ~0.7 nm size molybdenum polyoxometalate anions (POM) anions on 25 mg (≈ 0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft-landingmore » (SL). For the first time, electron microscopy provides atomically-resolved images of individual POM species directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.« less

Material design and engineering of next-generation flow-battery technologies

NASA Astrophysics Data System (ADS)

Park, Minjoon; Ryu, Jaechan; Wang, Wei; Cho, Jaephil

2017-01-01

Spatial separation of the electrolyte and electrode is the main characteristic of flow-battery technologies, which liberates them from the constraints of overall energy content and the energy/power ratio. The concept of a flowing electrolyte not only presents a cost-effective approach for large-scale energy storage, but has also recently been used to develop a wide range of new hybrid energy storage and conversion systems. The advent of flow-based lithium-ion, organic redox-active materials, metal-air cells and photoelectrochemical batteries promises new opportunities for advanced electrical energy-storage technologies. In this Review, we present a critical overview of recent progress in conventional aqueous redox-flow batteries and next-generation flow batteries, highlighting the latest innovative alternative materials. We outline their technical feasibility for use in long-term and large-scale electrical energy-storage devices, as well as the limitations that need to be overcome, providing our view of promising future research directions in the field of redox-flow batteries.

Towards High-Energy-Density Pseudocapacitive Flowable Electrodes by the Incorporation of Hydroquinone

DOE PAGES

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

2015-01-29

Our study reports an investigation of hydroquinone (HQ) as a multielectron organic redox molecule to enhance the performance of flowable electrodes. Moreover, two different methods to produce high-performance pseudocapacitive flowable electrodes were investigated for electrochemical flow capacitors. First, HQ molecules were deposited on carbon spheres (CSs) by a self-assembly approach using various HQ loadings. In the second approach, HQ was used as a redox-mediating agent in the electrolyte. Flowable electrodes composed of HQ showed a capacitance of 342 Fg 1, which is >200% higher than that of flowable electrodes based on nontreated CSs (160 Fg 1), and outperformed (in gravimetricmore » performance) many reported film electrodes. A similar trend in capacitance was observed if HQ was used as a redox agent in the electrolyte; however, its poor cycle life restricted further consideration. Additionally, a twofold increase in capacitance was observed under flow conditions compared to that of previous studies.« less

Dual field effects in electrolyte-gated spinel ferrite: electrostatic carrier doping and redox reactions.

PubMed

Ichimura, Takashi; Fujiwara, Kohei; Tanaka, Hidekazu

2014-07-24

Controlling the electronic properties of functional oxide materials via external electric fields has attracted increasing attention as a key technology for next-generation electronics. For transition-metal oxides with metallic carrier densities, the electric-field effect with ionic liquid electrolytes has been widely used because of the enormous carrier doping capabilities. The gate-induced redox reactions revealed by recent investigations have, however, highlighted the complex nature of the electric-field effect. Here, we use the gate-induced conductance modulation of spinel ZnxFe₃₋xO₄ to demonstrate the dual contributions of volatile and non-volatile field effects arising from electronic carrier doping and redox reactions. These two contributions are found to change in opposite senses depending on the Zn content x; virtual electronic and chemical field effects are observed at appropriate Zn compositions. The tuning of field-effect characteristics via composition engineering should be extremely useful for fabricating high-performance oxide field-effect devices.

Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries

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

Firouzi, Ali; Qiao, Ruimin; Motallebi, Shahrokh

The demand of sustainable power supply requires high-performance cost-effective energy storage technologies. Here in this paperwe report a high-rate long-life low-cost sodium-ion battery full-cell system by innovating both the anode and the electrolyte. The redox couple of manganese(I/II) in Prussian blue analogs enables a high-rate and stable anode. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering provide direct evidence suggesting the existence of monovalent manganese in the charged anode. There is a strong hybridization between cyano ligands and manganese-3d states, which benefits the electronic property for improving rate performance. Additionally, we employ an organic-aqueous cosolvent electrolyte to solve themore » long-standing solubility issue of Prussian blue analogs. A full-cell sodium-ion battery with low-cost Prussian blue analogs in both electrodes and co-solvent electrolyte retains 95% of its initial discharge capacity after 1000 cycles at 1C and 9 5% depth of discharge. The revealed manganese(I/II) redox couple inspires conceptual innovations of batteries based on atypical oxidation states.« less

Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries

DOE PAGES

Firouzi, Ali; Qiao, Ruimin; Motallebi, Shahrokh; ...

2018-02-28

The demand of sustainable power supply requires high-performance cost-effective energy storage technologies. Here in this paperwe report a high-rate long-life low-cost sodium-ion battery full-cell system by innovating both the anode and the electrolyte. The redox couple of manganese(I/II) in Prussian blue analogs enables a high-rate and stable anode. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering provide direct evidence suggesting the existence of monovalent manganese in the charged anode. There is a strong hybridization between cyano ligands and manganese-3d states, which benefits the electronic property for improving rate performance. Additionally, we employ an organic-aqueous cosolvent electrolyte to solve themore » long-standing solubility issue of Prussian blue analogs. A full-cell sodium-ion battery with low-cost Prussian blue analogs in both electrodes and co-solvent electrolyte retains 95% of its initial discharge capacity after 1000 cycles at 1C and 9 5% depth of discharge. The revealed manganese(I/II) redox couple inspires conceptual innovations of batteries based on atypical oxidation states.« less

Critical safety features of the vanadium redox flow battery

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Dye-sensitized solar cells using ionic liquids as redox mediator

NASA Astrophysics Data System (ADS)

Denizalti, Serpil; Ali, Abdulrahman Khalaf; Ela, Çağatay; Ekmekci, Mesut; Erten-Ela, Sule

2018-01-01

In this research, the influence of ionic liquid on the conversion efficiency, incident photons to converted electrons (IPCE) and performance of fabricated solar cell was investigated using various ionic liquids. Ionic liquids with different substituents and ions were prepared and used as redox mediators in dye-sensitized solar cells (DSSCs). Ionic liquids were characterized 1H and 13C NMR spectra. We practically investigated the performance of ionic liquid salts were used as the mobile ions and found that the efficiencies of DSSCs were increased up to 40% comparing commercial electrolyte system. The ionic liquid compounds were incorporated in DSSCs to obtain an efficient charge transfer, solving the corrosion problem of platinum layer in counter electrode compared to commercial electrolyte.

Optically transparent FTO-free cathode for dye-sensitized solar cells.

PubMed

Kavan, Ladislav; Liska, Paul; Zakeeruddin, Shaik M; Grätzel, Michael

2014-12-24

The woven fabric containing electrochemically platinized tungsten wire is an affordable flexible cathode for liquid-junction dye-sensitized solar cells with the I3(-)/I(-) redox mediator and electrolyte solution consisting of ionic liquids and propionitrile. The fabric-based electrode outperforms the thermally platinized FTO in serial ohmic resistance and charge-transfer resistance for triiodide reduction, and it offers comparable or better optical transparency in the visible and particularly in the near-IR spectral region. The electrode exhibits good stability during electrochemical loading and storage at open circuit. The dye-sensitized solar cells with a C101-sensitized titania photoanode and either Pt-W/PEN or Pt-FTO cathodes show a comparable performance.

Textile Organic Electrochemical Transistors as a Platform for Wearable Biosensors

NASA Astrophysics Data System (ADS)

Gualandi, I.; Marzocchi, M.; Achilli, A.; Cavedale, D.; Bonfiglio, A.; Fraboni, B.

2016-09-01

The development of wearable chemical sensors is receiving a great deal of attention in view of non-invasive and continuous monitoring of physiological parameters in healthcare applications. This paper describes the development of a fully textile, wearable chemical sensor based on an organic electrochemical transistor (OECT) entirely made of conductive polymer (PEDOT:PSS). The active polymer patterns are deposited into the fabric by screen printing processes, thus allowing the device to actually “disappear” into it. We demonstrate the reliability of the proposed textile OECTs as a platform for developing chemical sensors capable to detect in real-time various redox active molecules (adrenaline, dopamine and ascorbic acid), by assessing their performance in two different experimental contexts: i) ideal operation conditions (i.e. totally dipped in an electrolyte solution); ii) real-life operation conditions (i.e. by sequentially adding few drops of electrolyte solution onto only one side of the textile sensor). The OECTs response has also been measured in artificial sweat, assessing how these sensors can be reliably used for the detection of biomarkers in body fluids. Finally, the very low operating potentials (<1 V) and absorbed power (~10-4 W) make the here described textile OECTs very appealing for portable and wearable applications.

Tin, Bismuth, and Tin–Bismuth Alloy Electrodeposition from Chlorometalate Salts in Deep Eutectic Solvents

PubMed Central

Vieira, Luciana; Burt, Jennifer; Richardson, Peter W.; Schloffer, Daniel; Fuchs, David; Moser, Alwin; Bartlett, Philip N.; Reid, Gillian

2017-01-01

Abstract The electrodeposition of tin, bismuth, and tin–bismuth alloys from SnII and BiIII chlorometalate salts in the choline chloride/ethylene glycol (1:2 molar ratio) deep eutectic solvent was studied on glassy carbon and gold by cyclic voltammetry, rotating disc voltammetry, and chronoamperometry. The SnII‐containing electrolyte showed one voltammetric redox process corresponding to SnII/Sn0. The diffusion coefficient of [SnCl3]−, detected as the dominating species by Raman spectroscopy, was determined from Levich and Cottrell analyses. The BiIII‐containing electrolyte showed two voltammetric reduction processes, both attributed to BiIII/Bi0. Dimensionless current/time transients revealed that the electrodeposition of both Sn and Bi on glassy carbon proceeded by 3D‐progressive nucleation at a low overpotential and changed to instantaneous at higher overpotentials. The nucleation rate of Bi on glassy carbon was considerably smaller than that of Sn. Elemental Sn and Bi were electrodeposited on Au‐coated glass slides from their respective salt solutions, as were Sn–Bi alloys from a 2:1 SnII/BiIII solution. The biphasic Sn–Bi alloys changed from a Bi‐rich composition to a Sn‐rich composition by making the deposition potential more negative. PMID:28638772

Textile Organic Electrochemical Transistors as a Platform for Wearable Biosensors

PubMed Central

Gualandi, I.; Marzocchi, M.; Achilli, A.; Cavedale, D.; Bonfiglio, A.; Fraboni, B.

2016-01-01

The development of wearable chemical sensors is receiving a great deal of attention in view of non-invasive and continuous monitoring of physiological parameters in healthcare applications. This paper describes the development of a fully textile, wearable chemical sensor based on an organic electrochemical transistor (OECT) entirely made of conductive polymer (PEDOT:PSS). The active polymer patterns are deposited into the fabric by screen printing processes, thus allowing the device to actually “disappear” into it. We demonstrate the reliability of the proposed textile OECTs as a platform for developing chemical sensors capable to detect in real-time various redox active molecules (adrenaline, dopamine and ascorbic acid), by assessing their performance in two different experimental contexts: i) ideal operation conditions (i.e. totally dipped in an electrolyte solution); ii) real-life operation conditions (i.e. by sequentially adding few drops of electrolyte solution onto only one side of the textile sensor). The OECTs response has also been measured in artificial sweat, assessing how these sensors can be reliably used for the detection of biomarkers in body fluids. Finally, the very low operating potentials (<1 V) and absorbed power (~10−4 W) make the here described textile OECTs very appealing for portable and wearable applications. PMID:27667396

Electrolyte salts for nonaqueous electrolytes

DOEpatents

Amine, Khalil; Zhang, Zhengcheng; Chen, Zonghai

2012-10-09

Metal complex salts may be used in lithium ion batteries. Such metal complex salts not only perform as an electrolyte salt in a lithium ion batteries with high solubility and conductivity, but also can act as redox shuttles that provide overcharge protection of individual cells in a battery pack and/or as electrolyte additives to provide other mechanisms to provide overcharge protection to lithium ion batteries. The metal complex salts have at least one aromatic ring. The aromatic moiety may be reversibly oxidized/reduced at a potential slightly higher than the working potential of the positive electrode in the lithium ion battery. The metal complex salts may also be known as overcharge protection salts.

Operating a redox flow battery with a negative electrolyte imbalance

DOEpatents

Pham, Quoc; Chang, On; Durairaj, Sumitha

2015-03-31

Loss of flow battery electrode catalyst layers during self-discharge or charge reversal may be prevented by establishing and maintaining a negative electrolyte imbalance during at least parts of a flow battery's operation. Negative imbalance may be established and/or maintained actively, passively or both. Actively establishing a negative imbalance may involve detecting an imbalance that is less negative than a desired threshold, and processing one or both electrolytes until the imbalance reaches a desired negative level. Negative imbalance may be effectively established and maintained passively within a cell by constructing a cell with a negative electrode chamber that is larger than the cell's positive electrode chamber, thereby providing a larger quantity of negative electrolyte for reaction with positive electrolyte.

High-performance dye-sensitized solar cells based on solvent-free electrolytes produced from eutectic melts.

PubMed

Bai, Yu; Cao, Yiming; Zhang, Jing; Wang, Mingkui; Li, Renzhi; Wang, Peng; Zakeeruddin, Shaik M; Grätzel, Michael

2008-08-01

Low-cost excitonic solar cells based on organic optoelectronic materials are receiving an ever-increasing amount of attention as potential alternatives to traditional inorganic photovoltaic devices. In this rapidly developing field, the dye-sensitized solar cell (DSC) has achieved so far the highest validated efficiency of 11.1% (ref. 2) and remarkable stability. However, the cells with the best performance use volatile solvents in their electrolytes, which may be prohibitive for outdoor solar panels in view of the need for robust encapsulation. Solvent-free room-temperature ionic liquids have been pursued as an attractive solution to this dilemma, and device efficiencies of over 7% were achieved by using some low-viscosity formulations containing 1-ethyl-3-methylimidazolium thiocyanate, selenocyanate, tricyanomethide or tetracyanoborate. Unfortunately, apart from tetracyanoborate, all of these low-viscosity melts proved to be unstable under prolonged thermal stress and light soaking. Here, we introduce the concept of using eutectic melts to produce solvent-free liquid redox electrolytes. Using a ternary melt in conjunction with a nanocrystalline titania film and the amphiphilic heteroleptic ruthenium complex Z907Na (ref. 10) as a sensitizer, we reach excellent stability and an unprecedented efficiency of 8.2% under air-mass 1.5 global illumination. Our results are of importance to realize large-scale outdoor applications of mesoscopic DSCs.

A solid ceramic electrolyte system for measuring redox conditions in high temperature gas mixing studies

NASA Technical Reports Server (NTRS)

Williams, R. J.

1972-01-01

The details of the construction and operation of a gas mixing furnace are presented. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a standard vertical-quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the highinput impedance electronics necessary for measurements and a simplified version of standard gas mixing apparatus. The calibration and maintenance of the system are discussed.

Swiss roll nanomembranes with controlled proton diffusion as redox micro-supercapacitors.

PubMed

Ji, Hengxing; Mei, Yongfeng; Schmidt, Oliver G

2010-06-14

We demonstrate a redox Swiss roll micro-supercapacitor by rolling up a multilayered nanomembrane with an electrochemical active layer at either the outer or inner surface for different proton diffusion behaviors. The Swiss roll micro-supercapacitor could achieve high performance (e.g. capacity and life time) in a microscale power source and is helpful for studying charge transfer at the electrolyte/electrode interface.

A review of electrolyte materials and compositions for electrochemical supercapacitors.

PubMed

Zhong, Cheng; Deng, Yida; Hu, Wenbin; Qiao, Jinli; Zhang, Lei; Zhang, Jiujun

2015-11-07

Electrolytes have been identified as some of the most influential components in the performance of electrochemical supercapacitors (ESs), which include: electrical double-layer capacitors, pseudocapacitors and hybrid supercapacitors. This paper reviews recent progress in the research and development of ES electrolytes. The electrolytes are classified into several categories, including: aqueous, organic, ionic liquids, solid-state or quasi-solid-state, as well as redox-active electrolytes. Effects of electrolyte properties on ES performance are discussed in detail. The principles and methods of designing and optimizing electrolytes for ES performance and application are highlighted through a comprehensive analysis of the literature. Interaction among the electrolytes, electro-active materials and inactive components (current collectors, binders, and separators) is discussed. The challenges in producing high-performing electrolytes are analyzed. Several possible research directions to overcome these challenges are proposed for future efforts, with the main aim of improving ESs' energy density without sacrificing existing advantages (e.g., a high power density and a long cycle-life) (507 references).

Electrochemical measurements and thermodynamic calculations of redox equilibria in pallasite meteorites - Implications for the eucrite parent body

NASA Technical Reports Server (NTRS)

Righter, Kevin; Arculus, Richard J.; Paslick, Cassi; Delano, John W.

1990-01-01

The intrinsic oxygen fugacity (IOF) of olivine separates from the Salta, Springwater, and Eagle Station pallasites was measured between 850 and 1150 C using oxygen-specific solid zirconia electrolytes at 100,000 Pa. Thermodynamic calculations of redox equilibria involving equalibrium pallasite assemblages are in good agreement with the experimental results and provide a lower limit to pallasite redox stability; others involving disequilibrium assemblages, suggest that pallasites experienced localized, late-stage oxidation and reduction effects. Consideration of the redox buffer metal-olivine-orthopyroxene utilizing calculated Eucrite Parent Body (EPB) mantle phase compositions indicates that small redox gradients may have existed in the EPB. Such gradients may have produced strong compositional variation within the EPB. In addition, there is apparently significant redox heterogeneity in the source area of Eagle Station Trio pallasites and Bocaiuva iron meteorites.

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Redox-Active Hydrogel Polymer Electrolytes with Different pH Values for Enhancing the Energy Density of the Hybrid Solid-State Supercapacitor.

PubMed

Tang, Xiaohui; Lui, Yu Hui; Merhi, Abdul Rahman; Chen, Bolin; Ding, Shaowei; Zhang, Bowei; Hu, Shan

2017-12-27

To enhance the energy density of solid-state supercapacitors, a novel solid-state cell, made of redox-active poly(vinyl alcohol) (PVA) hydrogel electrolytes and functionalized carbon nanotube-coated cellulose paper electrodes, was investigated in this work. Briefly, acidic PVA-[BMIM]Cl-lactic acid-LiBr and neutral PVA-[BMIM]Cl-sodium acetate-LiBr hydrogel polymer electrolytes are used as catholyte and anolyte, respectively. The acidic condition of the catholyte contributes to suppression of the undesired irreversible reaction of Br - and extension of the oxygen evolution reaction potential to a higher value than that of the redox potential of Br - /Br 3 - reaction. The observed Br - /Br 3 - redox activity at the cathode contributes to enhance the cathode capacitance. The neutral condition of the anolyte helps extend the operating voltage window of the supercapacitor by introducing hydrogen evolution reaction overpotential to the anode. The electrosorption of nascent H on the negative electrode also increases the anode capacitance. As a result, the prepared solid-state hybrid supercapacitor shows a broad voltage window of 1.6 V, with a high Coulombic efficiency of 97.6% and the highest energy density of 16.3 Wh/kg with power density of 932.6 W/kg at 2 A/g obtained. After 10 000 cycles of galvanostatic charge and discharge tests at the current density of 10 A/g, it exhibits great cyclic stability with 93.4% retention of the initial capacitance. In addition, a robust capacitive performance can also be observed from the solid-state supercapacitor at different bending angles, indicating its great potential as a flexible energy storage device.

In Situ Real-Time Mechanical and Morphological Characterization of Electrodes for Electrochemical Energy Storage and Conversion by Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring.

PubMed

Shpigel, Netanel; Levi, Mikhael D; Sigalov, Sergey; Daikhin, Leonid; Aurbach, Doron

2018-01-16

Quartz crystal microbalance with dissipation monitoring (QCM-D) generates surface-acoustic waves in quartz crystal plates that can effectively probe the structure of films, particulate composite electrodes of complex geometry rigidly attached to quartz crystal surface on one side and contacting a gas or liquid phase on the other side. The output QCM-D characteristics consist of the resonance frequency (MHz frequency range) and resonance bandwidth measured with extra-ordinary precision of a few tenths of Hz. Depending on the electrodes stiffness/softness, QCM-D operates either as a gravimetric or complex mechanical probe of their intrinsic structure. For at least 20 years, QCM-D has been successfully used in biochemical and environmental science and technology for its ability to probe the structure of soft solvated interfaces. Practical battery and supercapacitor electrodes appear frequently as porous solids with their stiffness changing due to interactions with electrolyte solutions or as a result of ion intercalation/adsorption and long-term electrode cycling. Unfortunately, most QCM measurements with electrochemical systems are carried out based on a single (fundamental) frequency and, as such, provided that the resonance bandwidth remains constant, are suitable for only gravimetric sensing. The multiharmonic measurements have been carried out mainly on conducting/redox polymer films rather than on typical composite battery/supercapacitor electrodes. Here, we summarize the most recent publications devoted to the development of electrochemical QCM-D (EQCM-D)-based methodology for systematic characterization of mechanical properties of operating battery/supercapacitor electrodes. By varying the electrodes' composition and structure (thin/thick layers, small/large particles, binders with different mechanical properties, etc.), nature of the electrolyte solutions and charging/cycling conditions, the method is shown to be operated in different application modes. A variety of useful electrode-material properties are assessed noninvasively, in situ, and in real time frames of ion intercalation into the electrodes of interest. A detailed algorithm for the mechanical characterization of battery electrodes kept in the gas phase and immersed into the electrolyte solutions has been developed for fast recognition of stiff and viscoelastic materials in terms of EQCM-D signatures treated by the hydrodynamic and viscoelastic models. Working examples of the use of in situ hydrodynamic spectroscopy to characterize stiff rough/porous solids of complex geometry and viscoelastic characterization of soft electrodes are presented. The most demonstrative example relates to the formation of solid electrolyte interphase on Li 4 Ti 5 O 12 electrodes in the presence of different electrolyte solutions and additives: only a few cycles (an experiment during ∼30 min) were required for screening the electrolyte systems for their ability to form high-quality surface films in experimental EQCM-D cells as compared to 100 cycles (200 h cycling) in conventional coin cells. Thin/small-mass electrodes required for the EQCM-D analysis enable accelerated cycling tests for ultrafast mechanical characterization of these electrodes in different electrolyte solutions. Hence, this methodology can be easily implemented as a highly effective in situ analytical tool in the field of energy storage and conversion.

An induced current method for measuring zeta potential of electrolyte solution-air interface.

PubMed

Song, Yongxin; Zhao, Kai; Wang, Junsheng; Wu, Xudong; Pan, Xinxiang; Sun, Yeqing; Li, Dongqing

2014-02-15

This paper reports a novel and very simple method for measuring the zeta potential of electrolyte solution-air interface. When a measuring electrode contacts the electrolyte solution-air interface, an electrical current will be generated due to the potential difference between the electrode-air surface and the electrolyte solution-air interface. The amplitude of the measured electric signal is linearly proportional to this potential difference; and depends only on the zeta potential at the electrolyte solution-air interface, regardless of the types and concentrations of the electrolyte. A correlation between the zeta potential and the measured voltage signal is obtained based on the experimental data. Using this equation, the zeta potential of any electrolyte solution-air interface can be evaluated quickly and easily by inserting an electrode through the electrolyte solution-air interface and measuring the electrical signal amplitude. This method was verified by comparing the obtained results of NaCl, MgCl2 and CaCl2 solutions of different pH values and concentrations with the zeta potential data reported in the published journal papers. Copyright © 2013 Elsevier Inc. All rights reserved.

Specific Interaction between Redox Phospholipid Polymers and Plastoquinone in Photosynthetic Electron Transport Chain.

PubMed

Tanaka, Kenya; Kaneko, Masahiro; Ishikawa, Masahito; Kato, Souichiro; Ito, Hidehiro; Kamachi, Toshiaki; Kamiya, Kazuhide; Nakanishi, Shuji

2017-04-19

Redox phospholipid polymers added in culture media are known to be capable of extracting electrons from living photosynthetic cells across bacterial cell membranes with high cytocompatibility. In the present study, we identify the intracellular redox species that transfers electrons to the polymers. The open-circuit electrochemical potential of an electrolyte containing the redox polymer and extracted thylakoid membranes shift to positive (or negative) under light irradiation, when an electron transport inhibitor specific to plastoquinone is added upstream (or downstream) in the photosynthetic electron transport chain. The same trend is also observed for a medium containing living photosynthetic cells of Synechococcus elongatus PCC7942. These results clearly indicate that the phospholipid redox polymers extract photosynthetic electrons mainly from plastoquinone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries

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

Weinrich, Henning; Come, Jérémy; Tempel, Hermann

Iron-air cells provide a promising and resource-efficient alternative battery concept with superior area specific power density characteristics compared to state-of-the-art Li-air batteries and potentially superior energy density characteristics compared to present Li-ion batteries. Understanding charge-transfer reactions at the anode-electrolyte interface is the key to develop high-performance cells. By employing in-situ electrochemical atomic force microscopy (in-situ EC-AFM), in-depth insight into the electrochemically induced surface reaction processes on iron in concentrated alkaline electrolyte is obtained. The results highlight the formation and growth of the redox-layer on iron over the course of several oxidation/reduction cycles. By this means, a direct correlation between topographymore » changes and the corresponding electrochemical reactions at the nanoscale could unambiguously be established. Here in this paper, the twofold character of the nanoparticulate redox-layer in terms of its passivating character and its contribution to the electrochemical reactions is elucidated. Furthermore, the evolution of single nanoparticles on the iron electrode surface is evaluated in unprecedented and artifact-free detail. Based on the dedicated topography analysis, a detailed structural model for the evolution of the redox-layer which is likewise elementary for corrosion science and battery research is derived.« less

Interfacial interactions and their impact on redox-based resistive switching memories (ReRAMs)

NASA Astrophysics Data System (ADS)

Valov, Ilia

2017-09-01

Redox-based resistive switching memories are nowadays one of the most studied systems in both academia and industrial communities. These devices are scalable down to an almost atomic level and are supposed to be applicable not only for next-generation nonvolatile memories, but also for neuromorphic computing, alternative logic operations and selector devices. The main characteristic feature of these cells is their nano- to sub-nano dimension. This makes the control and especially prediction of their properties very challenging. One of the ways to achieve better understanding and to improve the control of these systems is to study and modify their interfaces. In this review, first the fundamentals will be discussed, as these are essential for understanding which factors control the nanoscale interface properties. Further, different types of interactions at the electrode/solid electrolyte interface reported for ECM- and VCM-type cells will be exemplarily shown. Finally, the strategies and different solutions used to modify the interfaces and overcome the existing problems on the way to more stable and reliable devices will be highlighted.

A Polymer Electrolyte for Dye-Sensitized Solar Cells Based on a Poly(Polyvinylidenefluoride-Co-Hexafluoropropylene)/Hydroxypropyl Methyl Cellulose Blend

NASA Astrophysics Data System (ADS)

Won, Lee Ji; Kim, Jae Hong; Thogiti, Suresh

2018-05-01

A novel polymer blend electrolyte for dye-sensitized solar cells (DSSCs) was synthesized by quasi-solidifying a liquid-based electrolyte containing an iodide/triiodide redox couple and supporting salts with a mixture of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and indigenous hydroxypropyl methyl cellulose (HPMC). A high ionic conductivity of 8.8 × 10-4 S cm-1 was achieved after introducing 5 wt% of HPMC with respect to the weight of PVDH-HFP. DSSCs were fabricated using gel polymer blend electrolytes, and the J-V characteristics of the fabricated devices were analyzed. Under optimal conditions, the photovoltaic conversion efficiency of cells with the novel HPMC-blended gel electrolyte (5.34%) was significantly greater than that of cells without HPMC (3.97%).

A search map for organic additives and solvents applicable in high-voltage rechargeable batteries.

PubMed

Park, Min Sik; Park, Insun; Kang, Yoon-Sok; Im, Dongmin; Doo, Seok-Gwang

2016-09-29

Chemical databases store information such as molecular formulas, chemical structures, and the physical and chemical properties of compounds. Although the massive databases of organic compounds exist, the search of target materials is constrained by a lack of physical and chemical properties necessary for specific applications. With increasing interest in the development of energy storage systems such as high-voltage rechargeable batteries, it is critical to find new electrolytes efficiently. Here we build a search map to screen organic additives and solvents with novel core and functional groups, and thus establish a database of electrolytes to identify the most promising electrolyte for high-voltage rechargeable batteries. This search map is generated from MAssive Molecular Map BUilder (MAMMBU) by combining a high-throughput quantum chemical simulation with an artificial neural network algorithm. MAMMBU is designed for predicting the oxidation and reduction potentials of organic compounds existing in the massive organic compound database, PubChem. We develop a search map composed of ∼1 000 000 redox potentials and elucidate the quantitative relationship between the redox potentials and functional groups. Finally, we screen a quinoxaline compound for an anode additive and apply it to electrolytes and improve the capacity retention from 64.3% to 80.8% near 200 cycles for a lithium ion battery in experiments.

Kinetic and energetic paradigms for dye-sensitized solar cells: moving from the ideal to the real.

PubMed

O'Regan, Brian C; Durrant, James R

2009-11-17

Dye-sensitized solar cells (DSSCs) are photoelectrochemical solar cells. Their function is based on photoinduced charge separation at a dye-sensitized interface between a nanocrystalline, mesoporous metal oxide electrode and a redox electrolyte. They have been the subject of substantial academic and commercial research over the last 20 years, motivated by their potential as a low-cost solar energy conversion technology. Substantial progress has been made in enhancing the efficiency, stability, and processability of this technology and, in particular, the interplay between these technology drivers. However, despite intense research efforts, our ability to identify predictive materials and structure/device function relationships and, thus, achieve the rational optimization of materials and device design, remains relatively limited. A key challenge in developing such predictive design tools is the chemical complexity of the device. DSSCs comprise distinct materials components, including metal oxide nanoparticles, a molecular sensitizer dye, and a redox electrolyte, all of which exhibit complex interactions with each other. In particular, the electrolyte alone is chemically complex, including not only a redox couple (almost always iodide/iodine) but also a range of additional additives found empirically to enhance device performance. These molecular solutes make up typically 20% of the electrolyte by volume. As with most molecular systems, they exhibit complex interactions with both themselves and the other device components (e.g., the sensitizer dye and the metal oxide). Moreover, these interactions can be modulated by solar irradiation and device operation. As such, understanding the function of these photoelectrochemical solar cells requires careful consideration of the chemical complexity and its impact upon device operation. In this Account, we focus on the process by which electrons injected into the nanocrystalline electrode are collected by the external electrical circuit in real devices under operating conditions. We first of all summarize device function, including the energetics and kinetics of the key processes, using an "idealized" description, which does not fully account for much of the chemical complexity of the system. We then go on to consider recent advances in our understanding of the impact of these complexities upon the efficiency of electron collection. These include "catalysis" of interfacial recombination losses by surface adsorption processes and the influence of device operating conditions upon the recombination rate constant and conduction band energy, both attributed to changes in the chemical composition of the interface. We go on to discuss appropriate methodologies for quantifying the efficiency of electron collection in devices under operation. Finally, we show that, by taking into account these advances in our understanding of the DSSC function, we are able to recreate the current/voltage curves of both efficient and degraded devices without any fitting parameters and, thus, gain significant insight into the determinants of DSSC performance.

Influence of electrical double-layer interaction on coal flotation.

PubMed

Harvey, Paul A; Nguyen, Anh V; Evans, Geoffrey M

2002-06-15

In the early 1930s it was first reported that inorganic electrolytes enhance the floatability of coal and naturally hydrophobic minerals. To date, explanations of coal flotation in electrolytes have not been entirely clear. This research investigated the floatability of coal in NaCl and MgCl2 solutions using a modified Hallimond tube to examine the role of the electrical double-layer interaction between bubbles and particles. Flotation of coal was highly dependent on changes in solution pH, type of electrolyte, and electrolyte concentration. Floatability of coal in electrolyte solutions was seen not to be entirely controlled by the electrical double-layer interaction. Coal flotation in low electrolyte concentration solutions decreases with increase in concentration, not expected from the theory since the electrical double layer is compressed, resulting in diminishing the (electrical double layer) repulsion between the bubble and the coal particles. Unlike in low electrolyte concentration solutions, coal flotation in high electrolyte concentration solutions increases with increase in electrolyte concentration. Again, this behavior of coal flotation in high electrolyte concentration solutions cannot be quantitatively explained using the electrical double-layer interaction. Possible mechanisms are discussed in terms of the bubston (i.e., bubble stabilized by ions) phenomenon, which explains the existence of the submicron gas bubbles on the hydrophobic coal surface.

Symposium on High Power, Ambient Temperature Lithium Batteries, 180th Meeting of the Electrochemical Society, Phoenix, AZ, Oct. 13-17, 1991, Proceedings

NASA Technical Reports Server (NTRS)

Clark, W. D. K. (Editor); Halpert, Gerald (Editor)

1992-01-01

Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.

Materials for suspension (semi-solid) electrodes for energy and water technologies

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

Hatzell, Kelsey B.; Boota, Muhammad; Gogotsi, Yury

2015-01-01

Suspension or semi-solid electrodes have recently gained increased attention for large-scale applications such as grid energy storage, capacitive water deionization, and wastewater treatment. A suspension electrode is a multiphase material system comprised of an active (charge storing) material suspended in ionic solution (electrolyte). Gravimetrically, the electrolyte is the majority component and aids in physical transport of the active material. For the first time, this principle enables, scalability of electrochemical energy storage devices (supercapacitors and batteries) previously limited to small and medium scale applications. This critical review describes the ongoing material challenges encompassing suspension-based systems. The research described here combines classicalmore » aspects of electrochemistry, colloidal science, material science, fluid mechanics, and rheology to describe ion and charge percolation, adsorption of ions, and redox charge storage processes in suspension electrodes. Our review summarizes the growing inventory of material systems, methods and practices used to characterize suspension electrodes, and describes universal material system properties (rheological, electrical, and electrochemical) that are pivotal in the design of high performing systems. We include a discussion of the primary challenges and future research directions.« less

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

PubMed

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

2015-11-21

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

Liquid Quinones for Solvent-Free Redox Flow Batteries.

PubMed

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

2017-11-01

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

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

PubMed

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

2016-11-23

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

Dual overcharge protection and solid electrolyte interphase-improving action in Li-ion cells containing a bis-annulated dialkoxyarene electrolyte additive

NASA Astrophysics Data System (ADS)

Zhang, Jingjing; Shkrob, Ilya A.; Assary, Rajeev S.; Zhang, Shuo; Hu, Bin; Liao, Chen; Zhang, Zhengcheng; Zhang, Lu

2018-02-01

1,4-Dialkoxybenzene additives are commonly used as redox active shuttles in lithium-ion batteries in order to prevent runaway oxidation of electrolyte when overcharge conditions set in. During this action the shuttle molecule goes through a futile cycle, becoming oxidized at the cathode and reduced at the anode. Minimizing parasitic reactions in all states of charge is paramount for sustained protective action. Here we demonstrate that recently developed bis-annulated 9,10-bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethano-anthracene shuttle molecule (that yields exceptionally stable radical cations) survives over 120 cycles of overcharge abuse with 100% overcharge ratio at C/5 rate. Equally remarkably, in the presence of this additive the cell impedance becomes significantly lower compared to the control cells without the additive; this decrease is observed during the formation, normal cycling, and even under overcharge conditions. This unusual dual action has not been observed in other redox shuttle systems, and it presents considerable practical interest.

Ultrathin Hierarchical Porous Carbon Nanosheets for High-Performance Supercapacitors and Redox Electrolyte Energy Storage.

PubMed

Jayaramulu, Kolleboyina; Dubal, Deepak P; Nagar, Bhawna; Ranc, Vaclav; Tomanec, Ondrej; Petr, Martin; Datta, Kasibhatta Kumara Ramanatha; Zboril, Radek; Gómez-Romero, Pedro; Fischer, Roland A

2018-04-01

The design of advanced high-energy-density supercapacitors requires the design of unique materials that combine hierarchical nanoporous structures with high surface area to facilitate ion transport and excellent electrolyte permeability. Here, shape-controlled 2D nanoporous carbon sheets (NPSs) with graphitic wall structure through the pyrolysis of metal-organic frameworks (MOFs) are developed. As a proof-of-concept application, the obtained NPSs are used as the electrode material for a supercapacitor. The carbon-sheet-based symmetric cell shows an ultrahigh Brunauer-Emmett-Teller (BET)-area-normalized capacitance of 21.4 µF cm -2 (233 F g -1 ), exceeding other carbon-based supercapacitors. The addition of potassium iodide as redox-active species in a sulfuric acid (supporting electrolyte) leads to the ground-breaking enhancement in the energy density up to 90 Wh kg -1 , which is higher than commercial aqueous rechargeable batteries, maintaining its superior power density. Thus, the new material provides a double profits strategy such as battery-level energy and capacitor-level power density. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved electrochemical performances of binder-free CoMoO4 nanoplate arrays@Ni foam electrode using redox additive electrolyte

NASA Astrophysics Data System (ADS)

Veerasubramani, Ganesh Kumar; Krishnamoorthy, Karthikeyan; Kim, Sang Jae

2016-02-01

Herein, we are successfully prepared cobalt molybdate (CoMoO4) grown on nickel foam as a binder free electrode by hydrothermal approach for supercapacitors and improved their electrochemical performances using potassium ferricyanide (K3Fe(CN)6) as redox additive. The formation of CoMoO4 on Ni foam with high crystallinity is confirmed using XRD, Raman, and XPS measurements. The nanoplate arrays (NPAs) of CoMoO4 are uniformly grown on Ni foam which is confirmed by FE-SEM analysis. The prepared binder-free CoMoO4 NPAs achieved maximum areal capacity of 227 μAh cm-2 with KOH electrolyte at 2.5 mA cm-2. This achieved areal capacity is further improved about three times using the addition of K3Fe(CN)6 as redox additive. The increased electrochemical performances of CoMoO4 NPAs on Ni foam electrode via redox additive are discussed in detail and the mechanism has been explored. Moreover, the assembled CoMoO4 NPAs on Ni foam//activated carbon asymmetric supercapacitor device with an extended operating voltage window of 1.5 V exhibits an excellent performances such as high energy density and cyclic stability. The overall performances of binder-free CoMoO4 NPAs on Ni foam with redox additives suggesting their potential use as positive electrode material for high performance supercapacitors.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance.

PubMed

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-02-12

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance

PubMed Central

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-01-01

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization. PMID:29439514

Current status of solid-state lithium batteries employing solid redox polymerization cathodes

NASA Astrophysics Data System (ADS)

Visco, S. J.; Doeff, M. M.; Dejonghe, L. C.

1991-03-01

The rapidly growing demand for secondary batteries having high specific energy and power has naturally led to increased efforts in lithium battery technology. Still, the increased safety risks associated with high energy density systems has tempered the enthusiasm of proponents of such systems for use in the consumer marketplace. The inherent advantages of all-solid-state batteries in regards to safety and reliability are strong factors in advocating their introduction to the marketplace. However, the low ionic conductivity of solid electrolytes relative to nonaqueous liquid electrolytes implies low power densities for solid state systems operating at ambient temperatures. Recent advances in polymer electrolytes have led to the introduction of solid electrolytes having conductivities in the range of 10(exp -4)/ohm cm at room temperature; this is still two orders of magnitude lower than liquid electrolytes. Although these improved ambient conductivities put solid state batteries in the realm of practical devices, it is clear that solid state batteries using such polymeric separators will be thin film devices. Fortunately, thin film fabrication techniques are well established in the plastics and paper industry, and present the possibility of continuous web-form manufacturing. This style of battery manufacture should make solid polymer batteries very cost-competitive with conventional secondary cells. In addition, the greater geometric flexibility of thin film solid state cells should provide benefits in terms of the end-use form factor in device design. This work discusses the status of solid redox polymerization cathodes.

High voltage AC/AC electrochemical capacitor operating at low temperature in salt aqueous electrolyte

NASA Astrophysics Data System (ADS)

Abbas, Qamar; Béguin, François

2016-06-01

We demonstrate that an activated carbon (AC)-based electrochemical capacitor implementing aqueous lithium sulfate electrolyte in 7:3 vol:vol water/methanol mixture can operate down to -40 °C with good electrochemical performance. Three-electrode cell investigations show that the faradaic contributions related with hydrogen chemisorption in the negative AC electrode are thermodynamically unfavored at -40 °C, enabling the system to work as a typical electrical double-layer (EDL) capacitor. After prolonged floating of the AC/AC capacitor at 1.6 V and -40°C, the capacitance, equivalent series resistance and efficiency remain constant, demonstrating the absence of ageing related with side redox reactions at this temperature. Interestingly, when temperature is increased back to 24 °C, the redox behavior due to hydrogen storage reappears and the system behaves as a freshly prepared one.

A Hybrid Redox-Supercapacitor System with Anionic Catholyte and Cationic Anolyte

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

Wang, B; Macia-Agullo, JA; Prendiville, DG

A significant challenge for energy storage technologies is to realize battery-level energy density and capacitor-level durability and power density in one device. By introducing an electrolyte composed of an anionic catholyte and a cationic anolyte into a symmetric carbon-based supercapacitor configuration, a hybrid electrochemical battery-supercapacitor system using soluble redox species delivers significantly improved energy density from 20 to 42 W.h/kg (based on the electrode mass) and stable capacities for > 10(4) cycles. The ionic species formed in the electrolyte are studied by UV-Vis, Raman and mass spectroscopy to probe the energy storage mechanism. The strategy is general and may providemore » a route to critically-needed fast-charging devices with both high energy density and power. (C) 2014 The Electrochemical Society. All rights reserved.« less

Thermodynamic Studies of Levitated Microdroplets of Highly Supersaturated Electrolyte Solutions

NASA Technical Reports Server (NTRS)

Myerson, Allan S.; Izmailov, Alexander F.; Na, Han-Soo

1996-01-01

Highly supersaturated electrolyte solutions are studied by employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. A correspondence of 96-99% between the theory and experiment for the all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin) and its calculation for various electrolyte solutions at 298 K.

A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

NASA Astrophysics Data System (ADS)

Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

2005-05-01

The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

Study of Early Transition Metal Carbides for Energy Storage Applications

NASA Astrophysics Data System (ADS)

Dall'Agnese, Yohan

An increase in energy and power density is needed to match the growing energy storage demands linked with the development of renewable energy production, and portable electronics. Several energy storage technologies exist including lithium-ion batteries, sodium-ion batteries, fuel cells and supercapacitors. These systems are mutually complementary. For example, supercapacitors can deliver high power densities whereas batteries can be used for high energy density applications. The first objective of this work was to investigate the electrochemical performances of a new family of 2-D materials called MXenes by cyclic voltammetry and galvanostatic charge-discharge measurements and to propose new solutions to tackle the energy storage concern. To achieve this goal, several directions have been explored. The first part of the research focused on Ti3C 2-based MXenes behavior as electrode materials for supercapacitors in aqueous electrolytes. The charge storage mechanisms in basic and neutral aqueous electrolytes, investigated by X-ray diffraction, were demonstrated to be attributed to cations intercalation between Ti3C2 layers. X-ray photoelectron spectroscopy highlighted the contribution of oxygenated functional groups on surface redox reactions in sulfuric acid. High capacitances were achieved, up to 520 F/cm3 and 325 F/g. Then the electrochemical behaviors of MXenes in sodium-based organic electrolytes were explored. A new hybrid system of sodium-ion capacitor was proposed. It was demonstrated that V2C-based MXene electrodes were suitable to be used as positive electrodes with an operating potential from 1 V to 3.5 V vs. Na+/Na. Continuous intercalation and de-intercalation of sodium ions between the V2C layers during sodiation and desodiation were showed by X-ray diffraction. An asymmetric sodium-ion capacitor full cell was assembled using hard carbon as negative electrode and showed promising results, with a capacity of 50 mAh/g. The last part was focused on the study of MXene electrodes for supercapacitors in an organic electrolyte; 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI) in acetonitrile. High volumetric capacitances, up to 245 F/cm 3, were achieved by using carbon nanotubes as an additive to improve ion accessibility to Ti3C2 layers. The redox intercalation of large EMI+ cations between Ti3C2 layers at -0.4 V vs. Ag was observed by X-ray diffraction.

Redox shuttles for lithium ion batteries

DOEpatents

Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

2014-11-04

Compounds may have general Formula IVA or IVB. ##STR00001## where, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 are each independently selected from H, F, Cl, Br, CN, NO.sub.2, alkyl, haloalkyl, and alkoxy groups; X and Y are each independently O, S, N, or P; and Z' is a linkage between X and Y. Such compounds may be used as redox shuttles in electrolytes for use in electrochemical cells, batteries and electronic devices.

Neuromorphic transistor achieved by redox reaction of WO3 thin film

NASA Astrophysics Data System (ADS)

Tsuchiya, Takashi; Jayabalan, Manikandan; Kawamura, Kinya; Takayanagi, Makoto; Higuchi, Tohru; Jayavel, Ramasamy; Terabe, Kazuya

2018-04-01

An all-solid-state neuromorphic transistor composed of a WO3 thin film and a proton-conducting electrolyte was fabricated for application to next-generation information and communication technology including artificial neural networks. The drain current exhibited a 4-order-of-magnitude increment by redox reaction of the WO3 thin film owing to proton migration. Learning and forgetting characteristics were well tuned by the gate control of WO3 redox reactions owing to the separation of the current reading path and pulse application path in the transistor structure. This technique should lead to the development of versatile and low-power-consumption neuromorphic devices.

The Chemistry of Redox-Flow Batteries.

PubMed

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

2015-08-17

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

Technical Update: Johnson Space Center system using a solid electrolytic cell in a remote location to measure oxygen fugacities in CO/CO2 controlled-atmosphere furnaces

NASA Technical Reports Server (NTRS)

Jurewicz, A. J. G.; Williams, R. J.; Le, L.; Wagstaff, J.; Lofgren, G.; Lanier, A.; Carter, W.; Roshko, A.

1993-01-01

Details are given for the design and application of a (one atmosphere) redox-control system. This system differs from that given in NASA Technical Memorandum 58234 in that it uses a single solid-electrolytic cell in a remote location to measure the oxygen fugacities of multiple CO/CO2 controlled-atmosphere furnaces. This remote measurement extends the range of sample-furnace conditions that can be measured using a solid-electrolytic cell, and cuts costs by extending the life of the sensors and by minimizing the number of sensors in use. The system consists of a reference furnace and an exhaust-gas manifold. The reference furnace is designed according to the redox control system of NASA Technical Memorandum 58234, and any number of CO/CO2 controlled-atmosphere furnaces can be attached to the exhaust-gas manifold. Using the manifold, the exhaust gas from individual CO/CO2 controlled atmosphere furnaces can be diverted through the reference furnace, where a solid-electrolyte cell is used to read the ambient oxygen fugacity. The oxygen fugacity measured in the reference furnace can then be used to calculate the oxygen fugacity in the individual CO/CO2 controlled-atmosphere furnace. A BASIC computer program was developed to expedite this calculation.

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

PubMed

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

2014-10-22

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

Black-to-Transmissive Electrochromism with Visible-to-Near-Infrared Switching of a Co(II)-Based Metallo-Supramolecular Polymer for Smart Window and Digital Signage Applications.

PubMed

Hsu, Chih-Yu; Zhang, Jian; Sato, Takashi; Moriyama, Satoshi; Higuchi, Masayoshi

2015-08-26

Black-to-transmissive electrochromism has been obtained with a Co(II)-based metallo-supramolecular polymer (polyCo). Thin films of polyCo, based on bisterpyridine ligand assembled with Co(II) metal ion, were constructed by spray casting the polymer onto ITO glass. With such simple fabricating means to form good-quality films, polyCo films show stable switching at the central metal ion of the Co(II)/Co(I) redox reaction when immersed in aqueous solution. With an increase in the pH of the aqueous electrolyte solution from neutral, the film exhibits a color response due to the interaction between the d-orbital electron and hydroxide ions affecting the d-d* transition. As a result, a nearly transparent-to-black electrochromic performance can be achieved with a transmittance difference at 550 nm of 74.3% (81.9-7.6%) in pH 13 solution. The light absorption of the film can be tuned over light regions from visible to near-infrared with a large attenuation.

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2015-11-01

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

Modifications in structure and interaction of nanoparticle-protein-surfactant complexes in electrolyte solution

NASA Astrophysics Data System (ADS)

Mehan, Sumit; Kumar, S.; Aswal, V. K.; Schweins, R.

2016-05-01

SANS experiments of three-component system of anionic silica nanoparticles, anionic BSA protein and anionic SDS surfactants have been carried out without and with electrolyte in aqueous solution. In both the cases, the interaction of surfactant with protein results in formation of bead-necklace structure of protein-surfactant complexes in solution. These protein-surfactant complexes interact very differently with nanoparticles in absence and presence of electrolyte. In absence of electrolyte, nanoparticles remain in dispersed phase in solution, whereas with the addition of electrolyte the nanoparticles fractal aggregates are formed. SANS describes the phase behavior to be governed by competition of electrostatic and depletion interactions among the components solution.

A molecular Debye-Hückel theory and its applications to electrolyte solutions: The size asymmetric case

DOE PAGES

Xiao, Tiejun; Song, Xueyu

2017-03-28

We developed a molecular Debye-Hückel theory for electrolyte solutions with size asymmetry, where the dielectric response of an electrolyte solution is described by a linear combination of Debye-Hückel-like response modes. Furthermore, as the size asymmetry of an electrolyte solution leads to a charge imbalanced border zone around a solute, the dielectric response to the solute is characterized by two types of charge sources, namely, a bare solute charge and a charge distribution due to size asymmetry. These two kinds of charge sources are screened by the solvent differently, our theory presents a method to calculate the mean electric potential asmore » well as the electrostatic contributions to thermodynamic properties. Finally, the theory was successfully applied to binary as well as multi-component primitive models of electrolyte solutions.« less

Electrochromic devices

DOEpatents

Allemand, Pierre M.; Grimes, Randall F.; Ingle, Andrew R.; Cronin, John P.; Kennedy, Steve R.; Agrawal, Anoop; Boulton, Jonathan M.

2001-01-01

An electrochromic device is disclosed having a selective ion transport layer which separates an electrochemically active material from an electrolyte containing a redox active material. The devices are particularly useful as large area architectural and automotive glazings due to there reduced back reaction.

Redox reactions with empirical potentials: atomistic battery discharge simulations.

PubMed

Dapp, Wolf B; Müser, Martin H

2013-08-14

Batteries are pivotal components in overcoming some of today's greatest technological challenges. Yet to date there is no self-consistent atomistic description of a complete battery. We take first steps toward modeling of a battery as a whole microscopically. Our focus lies on phenomena occurring at the electrode-electrolyte interface which are not easily studied with other methods. We use the redox split-charge equilibration (redoxSQE) method that assigns a discrete ionization state to each atom. Along with exchanging partial charges across bonds, atoms can swap integer charges. With redoxSQE we study the discharge behavior of a nano-battery, and demonstrate that this reproduces the generic properties of a macroscopic battery qualitatively. Examples are the dependence of the battery's capacity on temperature and discharge rate, as well as performance degradation upon recharge.

Mitigation of chemical membrane degradation in fuel cells: understanding the effect of cell voltage and iron ion redox cycle.

PubMed

Wong, Ka Hung; Kjeang, Erik

2015-03-01

Chemical membrane degradation through the Fenton's reaction is one of the main lifetime-limiting factors for polymer-electrolyte fuel cells. In this work, a comprehensive, transient membrane degradation model is developed to capture and elucidate the complex in situ degradation mechanism. A redox cycle of iron ions is discovered within the membrane electrolyte assembly, which sustains the Fe(II) concentration and results in the most severe chemical degradation at open circuit voltage. The cycle strength is critically reduced at lower cell voltages, which leads to an exponential decrease in Fe(II) concentration and associated membrane degradation rate. When the cell voltage is held below 0.7 V, a tenfold reduction in cumulative fluoride release is achieved, which suggests that intermediate cell voltage operation would efficiently mitigate chemical membrane degradation and extend the fuel cell lifetime. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

Minke, Christine; Kunz, Ulrich; Turek, Thomas

2017-09-01

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

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

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

NASA Astrophysics Data System (ADS)

Kumar, S.; Jayanti, S.

2016-03-01

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

A Key concept in Magnesium Secondary Battery Electrolytes.

PubMed

Bertasi, Federico; Hettige, Chaminda; Sepehr, Fatemeh; Bogle, Xavier; Pagot, Gioele; Vezzù, Keti; Negro, Enrico; Paddison, Stephen J; Greenbaum, Steve G; Vittadello, Michele; Di Noto, Vito

2015-09-21

A critical roadblock toward practical Mg-based energy storage technologies is the lack of reversible electrolytes that are safe and electrochemically stable. Here, we report on high-performance electrolytes based on 1-ethyl-3-methylimidazolium chloride (EMImCl) doped with AlCl3 and highly amorphous δ-MgCl2 . The phase diagram of the electrolytes reveals the presence of four thermal transitions that strongly depend on salt content. High-level density functional theory (DFT)-based electronic structure calculations substantiate the structural and vibrational assignment of the coordination complexes. A 3D chloride-concatenated dynamic network model accounts for the outstanding redox behaviour and the electric and magnetic properties, providing insight into the conduction mechanism of the electrolytes. Mg anode cells assembled using the electrolytes were cyclically discharged at a high rate (35 mA g(-1) ), exhibiting an initial capacity of 80 mA h g(-1) and a steady-state voltage of 2.3 V. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical Shuttle Additives in Lithium Ion Batteries

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

Patterson, Mary

2013-03-31

The goals of this program were to discover and implement a redox shuttle that is compatible with large format lithium ion cells utilizing LiNi{sub 1/3}Mn{sub 1/3}Co{sub 1/3}O{sub 2} (NMC) cathode material and to understand the mechanism of redox shuttle action. Many redox shuttles, both commercially available and experimental, were tested and much fundamental information regarding the mechanism of redox shuttle action was discovered. In particular, studies surrounding the mechanism of the reduction of the oxidized redox shuttle at the carbon anode surface were particularly revealing. The initial redox shuttle candidate, namely 2-(pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole (BDB) supplied by Argonne National Laboratory (ANL, Lemont,more » Illinois), did not effectively protect cells containing NMC cathodes from overcharge. The ANL-RS2 redox shuttle molecule, namely 1,4-bis(2-methoxyethoxy)-2,5-di-tert-butyl-benzene, which is a derivative of the commercially successful redox shuttle 2,5-di-tert-butyl-1,4-dimethoxybenzene (DDB, 3M, St. Paul, Minnesota), is an effective redox shuttle for cells employing LiFePO{sub 4} (LFP) cathode material. The main advantage of ANL-RS2 over DDB is its larger solubility in electrolyte; however, ANL-RS2 is not as stable as DDB. This shuttle also may be effectively used to rebalance cells in strings that utilize LFP cathodes. The shuttle is compatible with both LTO and graphite anode materials although the cell with graphite degrades faster than the cell with LTO, possibly because of a reaction with the SEI layer. The degradation products of redox shuttle ANL-RS2 were positively identified. Commercially available redox shuttles Li{sub 2}B{sub 12}F{sub 12} (Air Products, Allentown, Pennsylvania and Showa Denko, Japan) and DDB were evaluated and were found to be stable and effective redox shuttles at low C-rates. The Li{sub 2}B{sub 12}F{sub 12} is suitable for lithium ion cells utilizing a high voltage cathode (potential that is higher than NMC) and the DDB is useful for lithium ion cells with LFP cathodes (potential that is lower than NMC). A 4.5 V class redox shuttle provided by Argonne National Laboratory was evaluated which provides a few cycles of overcharge protection for lithium ion cells containing NMC cathodes but it is not stable enough for consideration. Thus, a redox shuttle with an appropriate redox potential and sufficient chemical and electrochemical stability for commercial use in larger format lithium ion cells with NMC cathodes was not found. Molecular imprinting of the redox shuttle molecule during solid electrolyte interphase (SEI) layer formation likely contributes to the successful reduction of oxidized redox shuttle species at carbon anodes. This helps to understand how a carbon anode covered with an SEI layer, that is supposed to be electrically insulating, can reduce the oxidized form of a redox shuttle.« less

Vertically aligned ZnO nanorod core-polypyrrole conducting polymer sheath and nanotube arrays for electrochemical supercapacitor energy storage

PubMed Central

2014-01-01

Nanocomposite electrodes having three-dimensional (3-D) nanoscale architecture comprising of vertically aligned ZnO nanorod array core-polypyrrole (PPy) conducting polymer sheath and the vertical PPy nanotube arrays have been investigated for supercapacitor energy storage. The electrodes in the ZnO nanorod core-PPy sheath structure are formed by preferential nucleation and deposition of PPy layer over hydrothermally synthesized vertical ZnO nanorod array by controlled pulsed current electropolymerization of pyrrole monomer under surfactant action. The vertical PPy nanotube arrays of different tube diameter are created by selective etching of the ZnO nanorod core in ammonia solution for different periods. Cyclic voltammetry studies show high areal-specific capacitance approximately 240 mF.cm-2 for open pore and approximately 180 mF.cm-2 for narrow 30-to-36-nm diameter PPy nanotube arrays attributed to intensive faradic processes arising from enhanced access of electrolyte ions through nanotube interior and exterior. Impedance spectroscopy studies show that capacitive response extends over larger frequency domain in electrodes with PPy nanotube structure. Simulation of Nyquist plots by electrical equivalent circuit modeling establishes that 3-D nanostructure is better represented by constant phase element which accounts for the inhomogeneous electrochemical redox processes. Charge-discharge studies at different current densities establish that kinetics of the redox process in PPy nanotube electrode is due to the limitation on electron transport rather than the diffusive process of electrolyte ions. The PPy nanotube electrodes show deep discharge capability with high coulomb efficiency and long-term charge-discharge cyclic studies show nondegrading performance of the specific areal capacitance tested for 5,000 cycles. PMID:25246867

Membranes for redox flow battery applications.

PubMed

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-06-19

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

Membranes for Redox Flow Battery Applications

PubMed Central

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-01-01

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention. PMID:24958177

Photo-electrochemical communication between cyanobacteria (Leptolyngbia sp.) and osmium redox polymer modified electrodes.

PubMed

Hasan, Kamrul; Bekir Yildiz, Huseyin; Sperling, Eva; Conghaile, Peter Ó; Packer, Michael A; Leech, Dónal; Hägerhäll, Cecilia; Gorton, Lo

2014-12-07

Photosynthetic microbial fuel cells (PMFCs) are an emerging technology for renewable solar energy conversion. Major efforts have been made to explore the electrogenic activity of cyanobacteria, mostly using practically unsustainable reagents. Here we report on photocurrent generation (≈8.64 μA cm(-2)) from cyanobacteria immobilized on electrodes modified with an efficient electron mediator, an Os(2+/3+) redox polymer. Upon addition of ferricyanide to the electrolyte, cyanobacteria generate the maximum current density of ≈48.2 μA cm(-2).

Electrical Microengineering of Redox Enzymes

DTIC Science & Technology

1994-03-31

coating applied to the electrode 41 to prevent lose of mediator graphite foil potassium -~0.02a 0.03  electrolyte wus dioxane with 15% 42...hexacyanoferrats(ll)d aqueous buffer carbon fiber’ none h 40-5000 biotin/avidin complex used to obtain a 43 surface layer of HRP Pt organic metal, potassium ...OFFICE OF NAVAL RESEARCH AD-A279 015 FINAL REPORT FOR CONTRACT NOOO 14-91 -J- 1656 R&T CODE 413h007---05 ELECTRICAL MICROENGINEERING OF REDOX ENZYMES

Microfluidic redox battery.

PubMed

Lee, Jin Wook; Goulet, Marc-Antoni; Kjeang, Erik

2013-07-07

A miniaturized microfluidic battery is proposed, which is the first membraneless redox battery demonstrated to date. This unique concept capitalizes on dual-pass flow-through porous electrodes combined with stratified, co-laminar flow to generate electrical power on-chip. The fluidic design is symmetric to allow for both charging and discharging operations in forward, reverse, and recirculation modes. The proof-of-concept device fabricated using low-cost materials integrated in a microfluidic chip is shown to produce competitive power levels when operated on a vanadium redox electrolyte. A complete charge/discharge cycle is performed to demonstrate its operation as a rechargeable battery, which is an important step towards providing sustainable power to lab-on-a-chip and microelectronic applications.

Thiourea incorporated poly(ethylene oxide) as transparent gel polymer electrolyte for dye sensitized solar cell applications

NASA Astrophysics Data System (ADS)

Pavithra, Nagaraj; Velayutham, David; Sorrentino, Andrea; Anandan, Sambandam

2017-06-01

A new series of transparent gel polymer electrolytes are prepared by adding various weight percent of thiourea coupled with poly(ethylene oxide) for the application of dye-sensitized solar cells. Coupling of thiourea in the presence of iodine undergoes dimerization reaction to produce formamidine disulfide. Fourier Transform Infrared spectroscopy shows that the interactions of thiourea and formamidine disulfide with electronegative ether linkage of poly(ethylene oxide) results in conformational changes of gel polymer electrolytes. Electrochemical impedance spectroscopy and linear sweep voltammetry experiments reveal an increment in ionic conductivity and tri-iodide diffusion coefficient, for thiourea modified gel polymer electrolytes. Finally, the prepared electrolytes are used as a redox mediator in dye-sensitized solar cells and the photovoltaic properties were studied. Apart from transparency, the gel polymer electrolytes with thiorurea show higher photovoltaic properties compared to bare gel polymer electrolyte and a maximum photocurrent efficiency of 7.17% is achieved for gel polymer electrolyte containing 1 wt% of thiourea with a short circuit current of 11.79 mA cm-2 and open circuit voltage of 834 mV. Finally, under rear illumination, almost 90% efficiency is retained upon compared to front illumination.

Silicon nanowire field-effect transistors for the detection of proteins

NASA Astrophysics Data System (ADS)

Madler, Carsten

In this dissertation I present results on our efforts to increase the sensitivity and selectivity of silicon nanowire ion-sensitive field-effect transistors for the detection of biomarkers, as well as a novel method for wireless power transfer based on metamaterial rectennas for their potential use as implantable sensors. The sensing scheme is based on changes in the conductance of the semiconducting nanowires upon binding of charged entities to the surface, which induces a field-effect. Monitoring the differential conductance thus provides information of the selective binding of biological molecules of interest to previously covalently linked counterparts on the nanowire surface. In order to improve on the performance of the nanowire sensing, we devised and fabricated a nanowire Wheatstone bridge, which allows canceling out of signal drift due to thermal fluctuations and dynamics of fluid flow. We showed that balancing the bridge significantly improves the signal-to-noise ratio. Further, we demonstrated the sensing of novel melanoma biomarker TROY at clinically relevant concentrations and distinguished it from nonspecific binding by comparing the reaction kinetics. For increased sensitivity, an amplification method was employed using an enzyme which catalyzes a signal-generating reaction by changing the redox potential of a redox pair. In addition, we investigated the electric double layer, which forms around charges in an electrolytic solution. It causes electrostatic screening of the proteins of interest, which puts a fundamental limitation on the biomarker detection in solutions with high salt concentrations, such as blood. We solved the coupled Nernst-Planck and Poisson equations for the electrolyte under influence of an oscillating electric field and discovered oscillations of the counterion concentration at a characteristic frequency. In addition to exploring different methods for improved sensing capabilities, we studied an innovative method to supply power to implantable biosensors wirelessly, eliminating the need for batteries. A metamaterial split ring resonator is integrated with a rectifying circuit for efficient conversion of microwave radiation to direct electrical power. We studied the near-field behavior of this rectenna with respect to distance, polarization, power, and frequency. Using a 100 mW microwave power source, we demonstrated operating a simple silicon nanowire pH sensor with light indicator.

Enhancing the Performance of Vanadium Redox Flow Batteries using Quinones

NASA Astrophysics Data System (ADS)

Mulcahy, James W., III

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

Semi-empirical equation of limiting current for cobalt electrodeposition in the presence of magnetic field and additive electrolyte

NASA Astrophysics Data System (ADS)

Sudibyo, Aziz, N.

2016-02-01

One of the available methods to solve a roughening in cobalt electrodeposition is magneto electrodeposition (MED) in the presence of additive electrolyte. Semi-empirical equation of limiting current under a magnetic field for cobalt MED in the presence of boric acid as an additive electrolyte was successfully developed. This semi empirical equation shows the effects of the electrode area (A), the concentration of the electro active species (C), the diffusion coefficient of the electro active species (D), the kinematic viscosity of the electrolyte (v), magnetic strength (B) and the number of electrons involved in the redox process (n). The presence of boric acid led to decrease in the limiting current, but the acid was found useful as a buffer to avoid the local pH rise caused by parallel hydrogen evolution reaction (HER).

Conducting polymer actuator based on chemically deposited polypyrrole and polyurethane-based solid polymer electrolyte working in air

NASA Astrophysics Data System (ADS)

Choi, Hwa-Jeong; Song, Young-Min; Chung, Ildoo; Ryu, Kwang-Sun; Jo, Nam-Ju

2009-02-01

Conducting polymers (CPs), such as polypyrrole, polythiophene, and polyaniline, are unique in that they have switchable properties due to their two or more mechanically stable oxidation states. Thus, their films or coatings can be easily switched by the application of a small voltage and current to change their volume during electrochemical redox processes. In particular, polypyrrole (PPy) has been studied most extensively because of its high electrical conductivity and good environmental stability under ambient conditions. In this work, we have studied a new CP actuator, fully polymeric, assembled with two PPy film electrodes and a solid polymer electrolyte (SPE), polyurethane/Mg(ClO4)2. Polyurethanes (PUs) were synthesized from 4,4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (1,4-BD) and three types of polyol: poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and PPG-block-PEG-block-PPG (PPG-co-PEG). The chemical polymerization of PPy by immersion in Py monomer aqueous solution and oxidant aqueous solution is an adequate method to prepare PU/PPy composite film as an actuator. To find the proper thickness of the PPy coating layer for actuation, we measured the displacements of the actuators according to the thickness of the PPy coating layer. The displacement of all actuators is discussed in connection with the properties of the SPE and PPy. All the results obtained in this work show the feasibility of electrochemomechanical devices based on PPy and SPE film being able to work in air.

Evaluating Transport Properties and Ionic Dissociation of LiPF 6 in Concentrated Electrolyte

DOE PAGES

Feng, Zhange; Higa, Kenneth; Han, Kee Sung; ...

2017-08-17

The presence of lithium hexafluorophosphate (LiPF 6) ion pairs in carbonate-based electrolyte solutions is widely accepted in the field of battery electrolyte research and is expected to affect solution transport properties. No existing techniques are capable of directly quantifying salt dissociation in these solutions. Previous publications by others have provided estimates of dissociation degrees using dilute solution theory and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR) measurements of self-diffusivity. However, the behavior of a concentrated electrolyte solution can deviate significantly from dilute solution theory predictions. This paper, for the first time, instead uses Onsager–Stefan–Maxwell concentrated solution theory and themore » generalized Darken relation with PFG-NMR measurements to quantify the degrees of dissociation in electrolyte solutions (LiPF 6 in ethylene carbonate/diethyl carbonate, 1:1 by weight). At LiPF 6 concentrations ranging from 0.1 M to 1.5 M, the salt dissociation degree is found to range from 61% to 37%. Finally, transport properties are then calculated through concentrated solution theory with corrections for these significant levels of ion pairing.« less

Evaluating Transport Properties and Ionic Dissociation of LiPF 6 in Concentrated Electrolyte

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

Feng, Zhange; Higa, Kenneth; Han, Kee Sung

2017-01-01

The presence of lithium hexafluorophosphate (LiPF6) ion pairs in carbonate-based electrolyte solutions is widely accepted in the field of battery electrolyte research and is expected to affect solution transport properties. No existing techniques are capable of directly quantifying salt dissociation in these solutions. Previous publications by others have provided estimates of dissociation degrees using dilute solution theory and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR) measurements of self-diffusivity. However, the behavior of a concentrated electrolyte solution can deviate significantly from dilute solution theory predictions. This work, for the first time, instead uses Onsager–Stefan–Maxwell concentrated solution theory and the generalized.more » Darken relation with PFG-NMR measurements to quantify the degrees of dissociation in electrolyte solutions (LiPF6 in ethylene carbonate/diethyl carbonate, 1:1 by weight). At LiPF6 concentrations ranging from 0.1 M to 1.5 M, the salt dissociation degree is found to range from 61% to 37%. Transport properties are then calculated through concentrated solution theory with corrections for these significant levels of ion pairing.« less

Experimental determination of activities in FeTiO3-MnTiO3 ilmenite solid solution by redox reversals

NASA Astrophysics Data System (ADS)

Feenstra, A.; Peters, Tjerk

1996-12-01

Solid solutions of (Fe,Mn)TiO3 were synthesized, mostly at 0.10 XMn intervals, at 1 bar, 900°C and log f O 2 = 17.50. Analysis by EMP indicate an ideal stoichiometry for the Fe-Mn ilmenites with (Fe+Mn) = Ti = 1.000 when normalized to 3 oxygens. Their unit cell volume increases linearly with XMn. The composition of Fe-Mn ilmenite coexisting with metallic Fe and rutile was reversed at 1 bar, 700 900°C and fixed f O 2 in a gas-mixing furnace. Oxygen fugacity was controlled by mixing CO2 and H2 gas and was continuously monitored with an yttrium-stabilized zirconia electrolyte. Solution properties of Fe-Mn ilmenite were derived from the experimental data by mathematical programming (Engi and Feenstra, in preparation) including notably the results of Fe-Mn exchange experiments between ilmenite and garnet (Feenstra and Engi, submitted) and anchoring the standard state properties to the updated thermodynamic dataset of Berman and Aranovich (1996). The thermodynamic analysis resulted in positive deviations from ideality for (Fe,Mn)TiO3 ilmenite, which is well described by an asymmetric Margules model with WH FeFeMn = 9.703 and WH FeMnMn = 23.234 kJ/mol, WS FeFeMn = 19.65 and WS FeMnMn = 22.06 J/(K·mol). The excess free energy for Fe-Mn ilmenite derived from the redox reversals is larger than in the symmetric ilmenite model (WG FeMn = +2.2 kJ/mol) determined by O'Neill et al. from emf measurements on the assemblage iron-rutile-(Fe,Mn)ilmenite.

Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

DOEpatents

Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

2011-12-13

Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

Redox shuttles for high voltage cathodes

DOEpatents

Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil; Chen, Zonghai

2015-03-03

A compound has general Formula I, II, III, or IV: ##STR00001## where X and Y are independently a group of Formula (A): ##STR00002## and Z a group of Formula (B): ##STR00003## The compounds may be used in electrolytes and electrochemical devices.

The Effects of Phosphonic Acids in Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

James, Keith Edward

Novel methods for the construction of dye-sensitized solar cells (DSSCs) were developed. A thin dense underlayer of TiO2 was applied on fluorine-doped tin oxide (FTO) glass using as a precursor Tyzor AA-105. Subsequently a mesoporous film of P-25 TiO2 was applied by spreading a suspension uniformly over the surface of the underlayer and allowing the plate to slowly dry while resting on a level surface. After sintering at 500° C slides were treated with TCPP as a sensitizing dye and assembled into DSSCs. A novel method was used to seal the cells; strips of ParafilmRTM were used as spacers between the electrodes and to secure the electrodes together. The cells were filled with a redox electrolyte and sealed by dipping into molten paraffin. A series of phosphonic acids and one arsonic acid were employed as coadsorbates in DSSCs. The coadsorbates were found to compete for binding sites, resulting in lower levels of dye adsorption. The resulting loss of photocurrent was not linear with the reduction of dye loading, and in some cases photocurrent and efficiency were higher for cells with lower levels of dye loading. Electrodes were treated with coadsorbates by procedures including pre-adsorption, simultaneous (sim-adsorption), and post-adsorption, using a range of concentrations and treatment times and a variety of solvents. Most cells were tested using an iodide-triiodide based electrolyte (I3I-1) but some cells were tested using electrolytes based on a Co(II)/Co(III) redox couple (CoBpy electrolytes). Phosphonic acid post-adsorbates increased the Voc of cells using CoBpy electrolytes but caused a decrease in the Voc of cells using I3I-1 electrolyte. Phosphonic acids as sim-adsorbates resulted in a significant increase in efficiency and Jsc, and they show promise as a treatment for TCPP DSSCs.

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1991-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1988-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1989-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Efficient quasisolid dye- and quantum-dot-sensitized solar cells using thiolate/disulfide redox couple and CoS counter electrode.

PubMed

Meng, Ke; Thampi, K Ravindranathan

2014-12-10

For the first time, a quasisolid thiolate/disulfide-based electrolyte was prepared using succinonitrile as a matrix. An optimized configuration of the quasisolid electrolyte contains 5-mercapto-1-methyltetrazole N-tetramethylammonium/disulfide/LiClO4/N-methylbenzimidazole in the molar ratio of 0.8:0.8:0.1:0.1. Dye-sensitized solar cells fabricated using this quasisolid electrolyte, together with N719 dye-sensitized photoelectrode and CoS counter electrode, attained power conversion efficiencies of 4.25% at 1 sun and 6.19% at 0.1 sun illumination intensities. The optimized quasisolid electrolyte, when introduced to quasisolid CdS quantum-dot-sensitized solar cells, exhibited a power conversion efficiency of 0.94%, despite the fact that CdS absorbs only a small fraction of the visible light, unlike dyes. The encouraging results show the potential for the utilization of the quasisolid thiolate/disulfide-based electrolyte in sensitized solar cells.

Battery technologies for large-scale stationary energy storage.

PubMed

Soloveichik, Grigorii L

2011-01-01

In recent years, with the deployment of renewable energy sources, advances in electrified transportation, and development in smart grids, the markets for large-scale stationary energy storage have grown rapidly. Electrochemical energy storage methods are strong candidate solutions due to their high energy density, flexibility, and scalability. This review provides an overview of mature and emerging technologies for secondary and redox flow batteries. New developments in the chemistry of secondary and flow batteries as well as regenerative fuel cells are also considered. Advantages and disadvantages of current and prospective electrochemical energy storage options are discussed. The most promising technologies in the short term are high-temperature sodium batteries with β″-alumina electrolyte, lithium-ion batteries, and flow batteries. Regenerative fuel cells and lithium metal batteries with high energy density require further research to become practical.

Stack developments in a kW class all vanadium mixed acid redox flow battery at the Pacific Northwest National Laboratory

DOE PAGES

Reed, David M.; Thomsen, Edwin C.; Li, Bin; ...

2015-11-21

Over the past several years, efforts have been focused on improving the performance of kW class stacks with increasing current density. The influence of the Nafion membrane resistance, an interdigitated design to reduce the pressure drop in the electrolyte circuit, the temperature of the electrolyte, and the electrode structure will be discussed and correlated to the electrical performance. Furthermore, improvements to the stack energy efficiency and how those translate to the overall system efficiency will also be discussed.

Superlattice photoelectrodes for photoelectrochemical cells

DOEpatents

Nozik, A.J.

1985-07-03

The application of superlattice semiconductors as photoelectrodes in photoelectrochemical energy conversion processes is described. The invention is comprised of a multiple quantum well, or superlattice, semiconductor positioned on a plate and encapsulated in an insulation material, except the top surface, which is left exposed. An opening in insulation exposes a portion of the plate. When the photoelectrochemical cell is immersed in a liquid electrolyte and exposed to solar radiation, a redox reaction occurs, producing gases such as hydrogen and oxygen from a water electrolyte, which bubble off the cathode and anode portions of the cell. (LEW)

A prospective randomized trial of two solutions for intrapartum amnioinfusion: effects on fetal electrolytes, osmolality, and acid-base status.

PubMed

Pressman, E K; Blakemore, K J

1996-10-01

Our purpose was to compare the effects of intrapartum amnioinfusion with normal saline solution versus lactated Ringer's solution plus physiologic glucose on neonatal electrolytes and acid-base balance. Patients undergoing amnioinfusion for obstetric indications were randomized to receive normal saline solution or lactated Ringer's solution plus physiologic glucose at standardized amnioinfusion rates. Data were collected prospectively on maternal demographics, course of labor, and maternal and neonatal outcome. Arterial cord blood was obtained for analysis of electrolytes, glucose, osmolality, lactic acid, and blood gases. Control subjects with normal fetal heart rate patterns, and clear amniotic fluid not receiving amnioinfusion were studied concurrently. Data were collected on 59 patients (21 normal saline solution, 18 lactated Ringer's solution plus physiologic glucose, and 20 controls). Maternal demographics, course of labor, and neonatal outcome were similar in all three groups. Cesarean sections were performed more often in the amnioinfusion groups (33.3% for normal saline solution, 38.9% for lactated Ringer's solution plus physiologic glucose) than in the control group (5.0%), p < 0.05. Cord arterial electrolytes, glucose, osmolality, lactic acid, and blood gases were not altered by amnioinfusion with either solution. Intrapartum amnioinfusion with normal saline solution or lactated Ringer's solution plus physiologic glucose has no effect on neonatal electrolytes or acid-base balance.

Separation and/or sequestration apparatus and methods

DOEpatents

Rieke, Peter C; Towne, Silas A; Coffey, Greg W; Appel, Aaron M

2015-02-03

Apparatus for separating CO.sub.2 from an electrolyte solution are provided. Example apparatus can include: a vessel defining an interior volume and configured to house an electrolyte solution; an input conduit in fluid communication with the interior volume; an output conduit in fluid communication with the interior volume; an exhaust conduit in fluid communication with the interior volume; and an anode located within the interior volume. Other example apparatus can include: an elongated vessel having two regions; an input conduit extending outwardly from the one region; an output conduit extending outwardly from the other region; an exhaust conduit in fluid communication with the one region; and an anode located within the one region. Methods for separating CO.sub.2 from an electrolyte solution are provided. Example methods can include: providing a CO.sub.2 rich electrolyte solution to a vessel containing an anode; and distributing hydrogen from the anode to acidify the electrolyte solution.

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

PubMed

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

2013-03-13

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

Hybrid energy storage systems utilizing redox active organic compounds

DOEpatents

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.

The chemical behavior of acidified chromium (3) solutions. B.S. Thesis

NASA Technical Reports Server (NTRS)

Terman, D. K.

1981-01-01

A unique energy-storage system has been developed at NASA's Lewis Research Center called REDOX. This NASA-REDOX system is an electrochemical storage device that utilized the oxidation and reduction of two fully soluble redox couples for charging and discharging. The redox couples now being investigated are acidified chloride solutions of chromium (Cr(+2)/Cr(+3)) and iron (Fe(+2)/Fe(+3)).

Sodium Sulfur Battery Cell Experiment (NaSBE)

NASA Technical Reports Server (NTRS)

Garner, J. Christopher

1997-01-01

The Ford Motor Company published papers describing new types of secondary battery comprised of: solid, sodium ion conducting electrolyte; liquid metal electrode; redox electrode; operating temperature between 300 and 400 deg. C; specific energy of 150 Wh/kg; and a nominal voltage of 2.0 V.

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

PubMed

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

2017-07-10

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

Photoelectrochemical processes in organic semiconductor: Ambipolar perylene diimide thin film

NASA Astrophysics Data System (ADS)

Kim, Jung Yong; Chung, In Jae

2018-03-01

A thin film of N,N‧-dioctadecyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C18) is spin-coated on indium tin oxide (ITO) glass. Using the PTCDI-C18/ITO electrode, we fabricate a photoelectrochemical cell with the ITO/PTCDI-C18/Redox Electrolyte/Pt configuration. The electrochemical properties of this device are investigated as a function of hydroquinone (HQ) concentration, bias voltage, and wavelength of light. Anodic photocurrent is observed at V ≥ -0.2 V vs. Ag/AgCl, indicating that the PTCDI-C18 film acts as an n-type semiconductor as usual. However, when benzoquinone (BQ) is inserted into the electrolyte system instead of HQ, cathodic photocurrent is observed at V ≤ 0.0 V, displaying that PTCDI-C18 abnormally serves as a p-type semiconductor. Hence the overall results reveal that the PTCDI-C18 film can be an ambipolar functional semiconductor depending on the redox couple in the appropriate voltage.

Facile electrodeposition of reduced graphene oxide hydrogels for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Pham, Viet Hung; Gebre, Tesfaye; Dickerson, James H.

2015-03-01

We report both a facile, scalable method to prepare reduced graphene oxide hydrogels through the electrodeposition of graphene oxide and its use as an electrode for high-performance supercapacitors. Such systems exhibited specific capacitances of 147 and 223 F g-1 at a current density of 10 A g-1 when using H2SO4 and H2SO4 + hydroquinone redox electrolytes, respectively.We report both a facile, scalable method to prepare reduced graphene oxide hydrogels through the electrodeposition of graphene oxide and its use as an electrode for high-performance supercapacitors. Such systems exhibited specific capacitances of 147 and 223 F g-1 at a current density of 10 A g-1 when using H2SO4 and H2SO4 + hydroquinone redox electrolytes, respectively. Electronic supplementary information (ESI) available: GO synthesis, characterization, fabrication of ERGO supercapacitor and electrochemical measurement, elemental composition, TGA and XRD of GO and ERGO. See DOI: 10.1039/c4nr07508k

Optimization of Pore Structure of Cathodic Carbon Supports for Solvate Ionic Liquid Electrolytes Based Lithium-Sulfur Batteries.

PubMed

Zhang, Shiguo; Ikoma, Ai; Li, Zhe; Ueno, Kazuhide; Ma, Xiaofeng; Dokko, Kaoru; Watanabe, Masayoshi

2016-10-04

Lithium-sulfur (Li-S) batteries are a promising energy-storage technology owing to their high theoretical capacity and energy density. However, their practical application remains a challenge because of the serve shuttle effect caused by the dissolution of polysulfides in common organic electrolytes. Polysulfide-insoluble electrolytes, such as solvate ionic liquids (ILs), have recently emerged as alternative candidates and shown great potential in suppressing the shuttle effect and improving the cycle stability of Li-S batteries. Redox electrochemical reactions in polysulfide-insoluble electrolytes occur via a solid-state process at the interphase between the electrolyte and the composite cathode; therefore, creating an appropriate interface between sulfur and a carbon support is of great importance. Nevertheless, the porous carbon supports established for conventional organic electrolytes may not be suitable for polysulfide-insoluble electrolytes. In this work, we investigated the effect of the porous structure of carbon materials on the Li-S battery performance in polysulfide-insoluble electrolytes using solvate ILs as a model electrolyte. We determined that the pore volume (rather than the surface area) exerts a major influence on the discharge capacity of S composite cathodes. In particular, inverse opal carbons with three-dimensionally ordered interconnected macropores and a large pore volume deliver the highest discharge capacity. The battery performance in both polysulfide-soluble electrolytes and solvate ILs was used to study the effect of electrolytes. We propose a plausible mechanism to explain the different porous structure requirements in polysulfide-soluble and polysulfide-insoluble electrolytes.

Evaluation of the antimicrobial effect of super-oxidized water (Sterilox®) and sodium hypochlorite against Enterococcus faecalis in a bovine root canal model

PubMed Central

ROSSI-FEDELE, Giampiero; de FIGUEIREDO, José Antonio Poli; STEIER, Liviu; CANULLO, Luigi; STEIER, Gabriela; ROBERTS, Adam P.

2010-01-01

Ideally root canal irrigants should have, amongst other properties, antimicrobial action associated with a lack of toxicity against periapical tissues. Sodium hypochlorite (NaOCl) is a widely used root canal irrigant, however it has been shown to have a cytotoxic effect on vital tissue and therefore it is prudent to investigate alternative irrigants. Sterilox's Aquatine Alpha Electrolyte® belongs to the group of the super-oxidized waters; it consists of a mixture of oxidizing substances, and has been suggested to be used as root canal irrigant. Super-oxidized waters have been shown to provide efficient cleaning of root canal walls, and have been proposed to be used for the disinfection of medical equipment. Objective To compare the antimicrobial action against Enterococcus faecalis of NaOCl, Optident Sterilox Electrolyte Solution® and Sterilox's Aquatine Alpha Electrolyte® when used as irrigating solutions in a bovine root canal model. Methodology Root sections were prepared and inoculated with E. faecalis JH2-2. After 10 days of incubation the root canals were irrigated using one of three solutions (NaOCl, Optident Sterilox Electrolyte Solution® and Sterilox's Aquatine Alpha Electrolyte®) and subsequently sampled by grinding dentin using drills. The debris was placed in BHI broth and dilutions were plated onto fresh agar plates to quantify growth. Results Sodium hypochlorite was the only irrigant to eliminate all bacteria. When the dilutions were made, although NaOCl was still statistically superior, Sterilox's Aquatine Alpha Electrolyte® solution was superior to Optident Sterilox Electrolyte Solution®. Conclusion Under the conditions of this study Sterilox's Aquatine Alpha Electrolyte® appeared to have significantly more antimicrobial action compared to the Optident Sterilox Electrolyte Solution® alone, however NaOCl was the only solution able to consistently eradicate E. faecalis in the model. PMID:21085808

Non-electrolytic synthesis of copper oxide/carbon nanocomposite by surface plasma in super-dehydrated ethanol

NASA Astrophysics Data System (ADS)

Kozak, Dmytro S.; Sergiienko, Ruslan A.; Shibata, Etsuro; Iizuka, Atsushi; Nakamura, Takashi

2016-02-01

Electrolytic processes are widely used to synthesize different nanomaterials and it does not depend on what kind of the method has been applied (wet-chemistry, sonochemistry, plasma chemistry, electrolysis and so on). Generally, the reactions in the electrolyte are considered to be reduction/oxidation (REDOX) reactions between chemical reagents or the deposition of matter on the electrodes, in line with Faraday’s law. Due to the presence of electroconductive additives in any electrolyte, the polarization effect of polar molecules conducting an electrical current disappears, when external high-strength electric field is induced. Because initially of the charge transfer always belongs of electroconductive additive and it does not depend on applied voltage. The polarization of ethanol molecules has been applied to conduct an electric current by surface plasma interaction for the synthesis of a copper oxide/carbon nanocomposite material.

Charge regulation at semiconductor-electrolyte interfaces.

PubMed

Fleharty, Mark E; van Swol, Frank; Petsev, Dimiter N

2015-07-01

The interface between a semiconductor material and an electrolyte solution has interesting and complex electrostatic properties. Its behavior will depend on the density of mobile charge carriers that are present in both phases as well as on the surface chemistry at the interface through local charge regulation. The latter is driven by chemical equilibria involving the immobile surface groups and the potential determining ions in the electrolyte solution. All these lead to an electrostatic potential distribution that propagate such that the electrolyte and the semiconductor are dependent on each other. Hence, any variation in the charge density in one phase will lead to a response in the other. This has significant implications on the physical properties of single semiconductor-electrolyte interfaces and on the electrostatic interactions between semiconductor particles suspended in electrolyte solutions. The present paper expands on our previous publication (Fleharty et al., 2014) and offers new results on the electrostatics of single semiconductor interfaces as well as on the interaction of charged semiconductor colloids suspended in electrolyte solution. Copyright © 2014 Elsevier Inc. All rights reserved.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, M.W.; George, W.A.

1991-06-18

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg[sub 2]Cl[sub 2] employing as the electrolyte solution a mixture of HCl and H[sub 2]O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H[sub 2]O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds. 3 figures.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, M.W.; George, W.A.

1989-11-07

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg[sub 2]Cl[sub 2] employing as the electrolyte solution a mixture of HCl and H[sub 2]O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H[sub 2]O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds. 3 figs.

Electrolyte Chemistry for Simultaneous Stabilization of Potassium Metal and Superoxide in K-O₂ Batteries.

PubMed

Xiao, Neng; Gourdin, Gerald; Wu, Yiying

2018-05-22

In the superoxide batteries based on O2/O2- redox chemistry, identifying an electrolyte to stabilize both alkali metal and superoxide remains challenging due to their reactivity towards electrolyte components. Bis(fluorosulfonyl)imide (FSI-) has been recognized as a "magical anion" for passivating alkali metals. Herein, we illustrate the chemical reactions between FSI- and superoxide, and the resultant dilemma when considering an anode-compatible electrolyte vs. a cathode-compatible one in K-O2 batteries. On one side, the KFSI-dimethoxyethane (DME) electrolyte passivates the potassium metal anode via the cleavage of S-F bond and formation of a KF-rich solid electrolyte interface (SEI). Nevertheless, the KFSI salt is chemically unstable due to the nucleophilic attack by superoxide and/or hydroxide species. On the other hand, potassium bis(trifluorosulfonyl)imide (KTFSI) is stable for KO2, but results in mossy deposition and irreversible plating and stripping. In order to circumvent this dilemma, we develop an artificial SEI for K metal anode to achieve long cycle-life K-O2 batteries. This work contributes to the understanding of electrolyte chemistry and guides the development of stable electrolytes and artificial SEI in metal-O2 batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water-based thixotropic polymer gel electrolyte for dye-sensitized solar cells.

PubMed

Park, Se Jeong; Yoo, Kichoen; Kim, Jae-Yup; Kim, Jin Young; Lee, Doh-Kwon; Kim, Bongsoo; Kim, Honggon; Kim, Jong Hak; Cho, Jinhan; Ko, Min Jae

2013-05-28

For the practical application of dye-sensitized solar cells (DSSCs), it is important to replace the conventional organic solvents based electrolyte with environmentally friendly and stable ones, due to the toxicity and leakage problems. Here we report a noble water-based thixotropic polymer gel electrolyte containing xanthan gum, which satisfies both the environmentally friendliness and stability against leakage and water intrusion. For application in DSSCs, it was possible to infiltrate the prepared electrolyte into the mesoporous TiO2 electrode at the fluidic state, resulting in sufficient penetration. As a result, this electrolyte exhibited similar conversion efficiency (4.78% at 100 mW cm(-2)) and an enhanced long-term stability compared to a water-based liquid electrolyte. The effects of water on the photovoltaic properties were examined elaborately from the cyclic voltammetry curves and impedance spectra. Despite the positive shift in the conduction band potential of the TiO2 electrode, the open-circuit voltage was enhanced by addition of water in the electrolyte due to the greater positive shift in the I(-)/I3(-) redox potential. However, due to the dye desorption and decreased diffusion coefficient caused by the water content, the short-circuit photocurrent density was reduced. These results will provide great insight into the development of efficient and stable water-based electrolytes.

Electrochemical storage cell containing a substituted anisole or di-anisole redox shuttle additive for overcharge protection and suitable for use in liquid organic and solid polymer electrolytes

DOEpatents

Kerr, John B.; Tian, Minmin

2000-01-01

A electrochemical cell is described comprising an anode, a cathode, a solid polymer electrolyte, and a redox shuttle additive to protect the cell against overcharging and a redox shuttle additive to protect the cell against overcharging selected from the group consisting of: (a) a substituted anisole having the general formula (in an uncharged state): ##STR1## where R.sub.1 is selected from the group consisting of H, OCH.sub.3, OCH.sub.2 CH.sub.3, and OCH.sub.2 phenyl, and R.sub.2 is selected from the group consisting of OCH.sub.3, OCH.sub.2 CH.sub.3, OCH.sub.2 phenyl, and O.sup.- Li.sup.+ ; and (b) a di-anisole compound having the general formula (in an uncharged state): ##STR2## where R is selected from the group consisting of -OCH.sub.3 and -CH.sub.3, m is either 1 or 0, n is either 1 or 0, and X is selected from the group consisting of -OCH.sub.3 (methoxy) or its lithium salt --O.sup.- Li.sup.+. The lithium salt of the di-anisole is the preferred form of the redox shuttle additive because the shuttle anion will then initially have a single negative charge, it loses two electrons when it is oxidized at the cathode, and then moves toward the anode as a single positively charged species where it is then reduced to a single negatively charged species by gaining back two electrons.

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

Wei, Xiaoliang; Nie, Zimin; Luo, Qingtao

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

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

PubMed

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

2017-01-25

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

Interfacial Electron Transfer at Sensitized Nanocrystalline TiO2 Electrolyte Interfaces: Influence of Surface Electric Fields and Lewis-Acidic Cations

NASA Astrophysics Data System (ADS)

Barr, Timothy J.

Interfacial electron transfer reactions facilitate charge separation and recombination in dye-sensitized solar cells (DSSCs). Understanding what controls these electron transfer reactions is necessary to develop efficient DSSCs. Gerischer proposed a theory for interfacial electron transfer where the rate constant was related to the energetic overlap between the donor and acceptor states. The present work focuses on understanding how the composition of the CH3CN electrolyte influenced this overlap. It was found that the identity of the electrolyte cation tuned the energetic position of TiO2 electron acceptor states, similar to how pH influences the flatband potential of bulk semiconductors in aqueous electrolytes. For example, the onset for absorption changes, that were attributed to electrons in the TiO2 thin film, were 0.5 V more positive in Mg2+ containing electrolyte than TBA+, where TBA+ is tetrabutylammonium. Similar studies performed on mesoporous, nanocrystalline SnO2 thin films reported a similar cation dependence, but also found evidence for electrons that did not absorb in the visible region that were termed ‘phantom electrons.’. Electron injection is known to generate surface electric fields on the order of 2 MV/cm. The rearrangement of cations in response to surface electric fields, termed screening, was investigated. It was found that magnitude of the electric field and the screening dynamics were dependent on the identity of the electrolyte cation. The rate of charge recombination to the anionic iodide/triiodide redox mediator correlated with the screening ability of the cation, and was initially thought to control charge recombination. However, it was difficult to determine whether electron diffusion or driving force were also cation dependent. Therefore, a in-lab built apparatus, termed STRiVE, was constructed that could disentangle the influence electron diffusion, driving force, and electric fields had on charge recombination. It was found that electron diffusion was independent of the electrolyte cation. Furthermore, charge recombination displayed the same cation-sensitivity using both anionic and cationic redox mediators, indicating electric fields did not cause the cation-dependence of charge recombination. Instead, it was found that the electrolyte cation tuned the energetic position of the TiO2 acceptor states and modulated the driving force for charge recombination.

Supersaturated Electrolyte Solutions: Theory and Experiment

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.; Na, Han-Soo

1995-01-01

Highly supersaturated electrolyte solutions can be prepared and studied employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. In the approach suggested the metastable state for electrolyte solutions is described in terms of the conserved order parameter omega(r,t) associated with fluctuations of the mean solute concentration n(sub 0). Parameters of the corresponding Ginzburg-Landau free energy functional which defines the dynamics of metastable state relaxation are determined and expressed through the experimentally measured quantities. A correspondence of 96-99 % between theory and experiment for all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin), and its calculation for various electrolyte solutions at 298 K. The assumption that subcritical solute clusters consist of the electrically neutral Bjerrum pairs has allowed both analytical and numerical investigation of the number-size N(sub c) of nucleation monomers (aggregates of the Bjerrum pairs) which are elementary units of the solute critical clusters. This has also allowed estimations for the surface tension Alpha, and equilibrium bulk energy Beta per solute molecule in the nucleation monomers. The dependence of these properties on the temperature T and on the solute concentration n(sub 0) through the entire metastable zone (from saturation concentration n(sub sat) to spinodal n(sub spin) is examined. It has been demonstrated that there are the following asymptotics: N(sub c), = I at spinodal concentration and N(sub c) = infinity at saturation.

Vanadium proton exchange membrane water electrolyser

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Synthesis, optical and electrochemical properties of Zn-porphyrin for dye sensitized solar cell applications

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

Kotteswaran, S.; Pandian, M. Senthil; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in

2016-05-23

Zn-Porphyrin dye has been synthesized by the reaction between aldehydes and pyrrole. The dye structure was confirmed by {sup 1}H NMR, {sup 13}C NMR spectrum. The functional group of the dye molecule was confirmed by FTIR spectrum. The UV-Vis-NIR absorption spectrum of Zn-Porphyrin in DMF solution was recorded in spectrophotometer. The UV-Vis NIR spectrum of dye exhibits a strong Soret band and Q-band. Cyclic Voltammograms were obtained with three electrode systems: Pt as counter electrode, saturated calomel used as a reference electrode and glassy carbon as working electrode at a scan rate of 100 mV/s. The curves recorded the oxidation ofmore » 0.5 mM compound Zn-Porphyrin in a dichloromethane solution containing 0.1M TBAP as supporting electrolyte, reveal two successive quasi reversible redox couples with the first anodic and cathodic peak potentials of -0.2 V and -1 V. The second anodic and cathodic peak potentials are 0.82 V and 0.01 V respectively.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

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

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.; ...

2015-08-13

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

ELECTROCHEMICAL DECONTAMINATION AND RECOVERY OF URANIUM VALUES

DOEpatents

McLaren, J.A.; Goode, J.H.

1958-05-13

An electrochemical process is described for separating uranium from fission products. The method comprises subjecting the mass of uranium to anodic dissolution in an electrolytic cell containing aqueous alkali bicarbonate solution as its electrolyte, thereby promoting a settling from the solution of a solid sludge from about the electrodes and separating the resulting electrolyte solution containing the anodically dissolved uranium from the sludge which contains the rare earth fission products.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

Wei, Xiaoliang; Pan, Wenxiao; Duan, Wentao

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 familiesmore » 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.« less

Methods and electrolytes for electrodeposition of smooth films

DOEpatents

Zhang, Jiguang; Xu, Wu; Graff, Gordon L; Chen, Xilin; Ding, Fei; Shao, Yuyan

2015-03-17

Electrodeposition involving an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and/or film surface. For electrodeposition of a first conductive material (C1) on a substrate from one or more reactants in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential in the solution lower than that of the reactants.

Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts.

PubMed

Yuan, Zhe; Peng, Hong-Jie; Hou, Ting-Zheng; Huang, Jia-Qi; Chen, Cheng-Meng; Wang, Dai-Wei; Cheng, Xin-Bing; Wei, Fei; Zhang, Qiang

2016-01-13

Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

Chemical overcharge protection of lithium and lithium-ion secondary batteries

DOEpatents

Abraham, Kuzhikalail M.; Rohan, James F.; Foo, Conrad C.; Pasquariello, David M.

1999-01-01

This invention features the use of redox reagents, dissolved in non-aqueous electrolytes, to provide overcharge protection for cells having lithium metal or lithium-ion negative electrodes (anodes). In particular, the invention features the use of a class of compounds consisting of thianthrene and its derivatives as redox shuttle reagents to provide overcharge protection. Specific examples of this invention are thianthrene and 2,7-diacetyl thianthrene. One example of a rechargeable battery in which 2,7-diacetyl thianthrene is used has carbon negative electrode (anode) and spinet LiMn.sub.2 O.sub.4 positive electrode (cathode).

Chemical overcharge protection of lithium and lithium-ion secondary batteries

DOEpatents

Abraham, K.M.; Rohan, J.F.; Foo, C.C.; Pasquariello, D.M.

1999-01-12

This invention features the use of redox reagents, dissolved in non-aqueous electrolytes, to provide overcharge protection for cells having lithium metal or lithium-ion negative electrodes (anodes). In particular, the invention features the use of a class of compounds consisting of thianthrene and its derivatives as redox shuttle reagents to provide overcharge protection. Specific examples of this invention are thianthrene and 2,7-diacetyl thianthrene. One example of a rechargeable battery in which 2,7-diacetyl thianthrene is used has carbon negative electrode (anode) and spinet LiMn{sub 2}O{sub 4} positive electrode (cathode). 8 figs.

Anion selective membrane. [ion exchange resins and ion exchange membrane electrolytes for electrolytic cells

NASA Technical Reports Server (NTRS)

Alexander, S. S.; Geoffroy, R. R.; Hodgdon, R. B.

1975-01-01

Experimental anion permselective membranes were prepared and tested for their suitability as cell separators in a chemical redox power storage system being developed at NASA-Lewis Research Center. The goals of long-term (1000 hr) oxidative and thermal stability at 80 C in FeCl3 and CrCl3 electrolytes were met by most of the weak base and strong base amino exchange groups considered in the program. Good stability is exhibited by several of the membrane substrate resins. These are 'styrene' divinylbenzene copolymer and PVC film. At least four membrane systems produce strong flexible films with electrochemical properties (resistivity, cation transfer) superior to those of the 103QZL, the most promising commercial membrane. The physical and chemical properties of the resins are listed.

Electrolyte Solutions and Specific Ion Effects on Interfaces

ERIC Educational Resources Information Center

Friedman, Ran

2013-01-01

Introductory general and physical chemistry courses often deal with colligative properties of solutions and do not discuss nonideal solutions in detail. Yet, a growing body of evidence reveals that even at physiological concentrations electrolyte solutions cannot be treated as ideal when a charged or partially charged solute (such as a protein) is…

Charge-discharge characteristics of nickel/zinc battery with polymer hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Iwakura, Chiaki; Murakami, Hiroki; Nohara, Shinji; Furukawa, Naoji; Inoue, Hiroshi

A new nickel/zinc (Ni/Zn) battery was assembled by using polymer hydrogel electrolyte prepared from cross-linked potassium poly(acrylate) and KOH aqueous solution, and its charge-discharge characteristics were investigated. The experimental Ni/Zn cell with the polymer hydrogel electrolyte exhibited well-defined charge-discharge curves and remarkably improved charge-discharge cycle performance, compared to that with a KOH aqueous solution. Moreover, it was found that dendritic growth hardly occurred on the zinc electrode surface during charge-discharge cycles in the polymer hydrogel electrolyte. These results indicate that the polymer hydrogel electrolyte can successfully be used in Ni/Zn batteries as an electrolyte with excellent performance.

Design of a miniature flow cell for in situ x-ray imaging of redox flow batteries

NASA Astrophysics Data System (ADS)

Jervis, Rhodri; Brown, Leon D.; Neville, Tobias P.; Millichamp, Jason; Finegan, Donal P.; Heenan, Thomas M. M.; Brett, Dan J. L.; Shearing, Paul R.

2016-11-01

Flow batteries represent a possible grid-scale energy storage solution, having many advantages such as scalability, separation of power and energy capabilities, and simple operation. However, they can suffer from degradation during operation and the characteristics of the felt electrodes are little understood in terms of wetting, compression and pressure drops. Presented here is the design of a miniature flow cell that allows the use of x-ray computed tomography (CT) to study carbon felt materials in situ and operando, in both lab-based and synchrotron CT. Through application of the bespoke cell it is possible to observe felt fibres, electrolyte and pore phases and therefore enables non-destructive characterisation of an array of microstructural parameters during the operation of flow batteries. Furthermore, we expect this design can be readily adapted to the study of other electrochemical systems.

Efficient and Stable Photovoltaic Characteristics of Quasi-Solid State DSSC using Polymer Gel Electrolyte Based on Ionic Liquid in Organosiloxane Polymer Gels

NASA Astrophysics Data System (ADS)

Pujiarti, H.; Arsyad, W. S.; Shobih; Muliani, L.; Hidayat, R.

2018-04-01

Dye-Sensitized Solar Cell (DSSC) is still one of the promising solar cell types among the third generation of solar cells because of easiness of fabrication and variety of available materials. In this type of solar cell, the electrolyte is one of the important components for regenerating excited dyes and transporting electric charge carriers to the counter electrode. Indeed, the power conversion efficiency of DSSC can be then significantly affected by the chemical and physical properties of the electrolyte. The simplest electrolyte system of an I-/I3 - redox couple in an organic solvent, however, has some drawbacks due to corrosive properties, volatile and leakage problem. Use of solid phase or gel phase electrolyte may overcome those problems, but it is often considered to suppress the efficiency due to low ion diffusion. Here, we report the photovoltaic characteristics of DSSC using polymer gel electrolyte (PGE), which is composed of ionic liquid and an organosiloxane polymer gel. The better cell performance with power conversion efficiency of about 6% has been obtained by optimizing the mesoporous size of the TiO2 layer and the PGE viscosity.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-11-01

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

A Shell-Shaped Carbon Architecture with High-Loading Capability for Lithium Sulfide Cathodes

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

Chung, Sheng-Heng; Han, Pauline; Chang, Chi-Hao

We present that lithium sulfide (Li 2S) is considered a highly attractive cathode for establishing high-energy-density rechargeable batteries, especially due to its high charge-storage capacity and compatibility with lithium-metal-free anodes. Although various approaches have recently been pursued with Li 2S to obtain high performance, formidable challenges still remain with cell design (e.g., low Li 2S loading, insufficient Li 2S content, and an excess electrolyte) to realize high areal, gravimetric, and volumetric capacities. This study demonstrates a shell-shaped carbon architecture for holding pure Li 2S, offering innovation in cell-design parameters and gains in electrochemical characteristics. The Li 2S core–carbon shell electrodemore » encapsulates the redox products within the conductive shell so as to facilitate facile accessibility to electrons and ions. The fast redox-reaction kinetics enables the cells to attain the highest Li 2S loading of 8 mg cm -2 and the lowest electrolyte/Li 2S ratio of 9/1, which is the best cell-design specifications ever reported with Li 2S cathodes so far. Lastly, benefiting from the excellent cell-design criterion, the core–shell cathodes exhibit stable cyclability from slow to fast cycle rates and, for the first time, simultaneously achieve superior performance metrics with areal, gravimetric, and volumetric capacities.« less

A Shell-Shaped Carbon Architecture with High-Loading Capability for Lithium Sulfide Cathodes

DOE PAGES

Chung, Sheng-Heng; Han, Pauline; Chang, Chi-Hao; ...

2017-05-11

We present that lithium sulfide (Li 2S) is considered a highly attractive cathode for establishing high-energy-density rechargeable batteries, especially due to its high charge-storage capacity and compatibility with lithium-metal-free anodes. Although various approaches have recently been pursued with Li 2S to obtain high performance, formidable challenges still remain with cell design (e.g., low Li 2S loading, insufficient Li 2S content, and an excess electrolyte) to realize high areal, gravimetric, and volumetric capacities. This study demonstrates a shell-shaped carbon architecture for holding pure Li 2S, offering innovation in cell-design parameters and gains in electrochemical characteristics. The Li 2S core–carbon shell electrodemore » encapsulates the redox products within the conductive shell so as to facilitate facile accessibility to electrons and ions. The fast redox-reaction kinetics enables the cells to attain the highest Li 2S loading of 8 mg cm -2 and the lowest electrolyte/Li 2S ratio of 9/1, which is the best cell-design specifications ever reported with Li 2S cathodes so far. Lastly, benefiting from the excellent cell-design criterion, the core–shell cathodes exhibit stable cyclability from slow to fast cycle rates and, for the first time, simultaneously achieve superior performance metrics with areal, gravimetric, and volumetric capacities.« less

Numerical investigation and thermodynamic analysis of the effect of electrolyte flow rate on performance of all vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Khazaeli, Ali; Vatani, Ali; Tahouni, Nassim; Panjeshahi, Mohammad Hassan

2015-10-01

In flow batteries, electrolyte flow rate plays a crucial role on the minimizing mass transfer polarization which is at the compensation of higher pressure drop. In this work, a two-dimensional numerical method is applied to investigate the effect of electrolyte flow rate on cell voltage, maximum depth of discharge and pressure drop a six-cell stack of VRFB. The results show that during the discharge process, increasing electrolyte flow rate can raise the voltage of each cell up to 50 mV on average. Moreover, the maximum depth of discharge dramatically increases with electrolyte flow rate. On the other hand, the pressure drop also positively correlates with electrolyte flow rate. In order to investigate all these effects simultaneously, average energy and exergy efficiencies are introduced in this study for the transient process of VRFB. These efficiencies give insight into choosing an appropriate strategy for the electrolyte flow rate. Finally, the energy efficiency of electricity storage using VRFB is investigated and compared with other energy storage systems. The results illustrate that this kind of battery has at least 61% storage efficiency based on the second law of thermodynamics, which is considerably higher than that of their counterparts.

Two-Dimensional Phosphorene-Derived Protective Layers on a Lithium Metal Anode for Lithium-Oxygen Batteries.

PubMed

Kim, Youngjin; Koo, Dongho; Ha, Seongmin; Jung, Sung Chul; Yim, Taeeun; Kim, Hanseul; Oh, Seung Kyo; Kim, Dong-Min; Choi, Aram; Kang, Yongku; Ryu, Kyoung Han; Jang, Minchul; Han, Young-Kyu; Oh, Seung M; Lee, Kyu Tae

2018-05-04

Lithium-oxygen (Li-O 2 ) batteries are desirable for electric vehicles because of their high energy density. Li dendrite growth and severe electrolyte decomposition on Li metal are, however, challenging issues for the practical application of these batteries. In this connection, an electrochemically active two-dimensional phosphorene-derived lithium phosphide is introduced as a Li metal protective layer, where the nanosized protective layer on Li metal suppresses electrolyte decomposition and Li dendrite growth. This suppression is attributed to thermodynamic properties of the electrochemically active lithium phosphide protective layer. The electrolyte decomposition is suppressed on the protective layer because the redox potential of lithium phosphide layer is higher than that of electrolyte decomposition. Li plating is thermodynamically unfavorable on lithium phosphide layers, which hinders Li dendrite growth during cycling. As a result, the nanosized lithium phosphide protective layer improves the cycle performance of Li symmetric cells and Li-O 2 batteries with various electrolytes including lithium bis(trifluoromethanesulfonyl)imide in N,N-dimethylacetamide. A variety of ex situ analyses and theoretical calculations support these behaviors of the phosphorene-derived lithium phosphide protective layer.

Electrolytic Polishing and Etching Techniques for Preparing Specimens of Bismuth and Antimony and Their Alloys: Materials and Structures.

DTIC Science & Technology

Electrolytic polishing was performed in a solution of methyl alcohol, sulphuric acid , hydrocloric acid and ethylene glycol. Etching was done...electrolytically in a 5 percent chromic acid solution. Use of these techniques has permitted detailed studies of the microstructures of bismuth-antimony single

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

Feng, Zhange; Higa, Kenneth; Han, Kee Sung

The presence of lithium hexafluorophosphate (LiPF 6) ion pairs in carbonate-based electrolyte solutions is widely accepted in the field of battery electrolyte research and is expected to affect solution transport properties. No existing techniques are capable of directly quantifying salt dissociation in these solutions. Previous publications by others have provided estimates of dissociation degrees using dilute solution theory and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR) measurements of self-diffusivity. However, the behavior of a concentrated electrolyte solution can deviate significantly from dilute solution theory predictions. This paper, for the first time, instead uses Onsager–Stefan–Maxwell concentrated solution theory and themore » generalized Darken relation with PFG-NMR measurements to quantify the degrees of dissociation in electrolyte solutions (LiPF 6 in ethylene carbonate/diethyl carbonate, 1:1 by weight). At LiPF 6 concentrations ranging from 0.1 M to 1.5 M, the salt dissociation degree is found to range from 61% to 37%. Finally, transport properties are then calculated through concentrated solution theory with corrections for these significant levels of ion pairing.« less

Nanoclay gelation approach toward improved dye-sensitized solar cell efficiencies: an investigation of charge transport and shift in the TiO2 conduction band.

PubMed

Wang, Xiu; Kulkarni, Sneha A; Ito, Bruno Ieiri; Batabyal, Sudip K; Nonomura, Kazuteru; Wong, Chee Cheong; Grätzel, Michael; Mhaisalkar, Subodh G; Uchida, Satoshi

2013-01-23

Nanoclay minerals play a promising role as additives in the liquid electrolyte to form a gel electrolyte for quasi-solid-state dye-sensitized solar cells, because of the high chemical stability, unique swelling capability, ion exchange capacity, and rheological properties of nanoclays. Here, we report the improved performance of a quasi-solid-state gel electrolyte that is made from a liquid electrolyte and synthetic nitrate-hydrotalcite nanoclay. Charge transport mechanisms in the gel electrolyte and nanoclay interactions with TiO(2)/electrolyte interface are discussed in detail. The electrochemical analysis reveals that the charge transport is solely based on physical diffusion at the ratio of [PMII]:[I(2)] = 10:1 (where PMII is 1-propyl-3-methylimidazolium iodide). The calculated physical diffusion coefficient shows that the diffusion of redox ions is not affected much by the viscosity of nanoclay gel. The addition of nitrate-hydrotalcite clay in the electrolyte has the effect of buffering the protonation process at the TiO(2)/electrolyte interface, resulting in an upward shift in the conduction band and a boost in open-circuit voltage (V(OC)). Higher V(OC) values with undiminished photocurrent is achieved with nitrate-hydrotalcite nanoclay gel electrolyte for organic as well as for inorganic dye (D35 and N719) systems. The efficiency for hydrotalcite clay gel electrolyte solar cells is increased by 10%, compared to that of the liquid electrolyte. The power conversion efficiency can reach 10.1% under 0.25 sun and 9.6% under full sun. This study demonstrates that nitrate-hydrotalcite nanoclay in the electrolyte not only solidifies the liquid electrolyte to prevent solvent leakage, but also facilitates the improvement in cell efficiency.

Methods and energy storage devices utilizing electrolytes having surface-smoothing additives

DOEpatents

Xu, Wu; Zhang, Jiguang; Graff, Gordon L; Chen, Xilin; Ding, Fei

2015-11-12

Electrodeposition and energy storage devices utilizing an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and anode surface. For electrodeposition of a first metal (M1) on a substrate or anode from one or more cations of M1 in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second metal (M2), wherein cations of M2 have an effective electrochemical reduction potential in the solution lower than that of the cations of M1.

Understanding performance limitation and suppression of leakage current or self-discharge in electrochemical capacitors: a review.

PubMed

Ike, Innocent S; Sigalas, Iakovos; Iyuke, Sunny

2016-01-14

Self-discharge is known to have considerable adverse effects on the performance and application of electrochemical capacitors (ECs). Thus, obtaining an understanding of EC self-discharge mechanism(s) and subsequent derivation and solution of EC models, subject to a particular mechanism or combination of mechanisms during charging, discharging and storage of the device, is the only way to solve problems associated with EC self-discharge. In this review, we summarize recent progress with respect to EC self-discharge by considering the two basic types, electric double-layer capacitors (EDLC) and pseudocapacitors, and their hybrids with their respective charge storage mechanisms, distinguishable self-discharge mechanisms, charge redistribution and charge/energy loss during self-discharge. It was clearly observed that most of the voltage reduction is not purely due to the self-discharge effect but is basically due to redistribution of charge carriers deep inside pores and can therefore be retrieved from a capacitor during long-time discharging. Tuning the self-discharge rate is therefore feasible for single-walled carbon nanotube (SWNT) ECs and can be achieved by simply adjusting the surface chemistry of the nanotubes. The effects of surface chemistry modification on EC self-discharge are very important in studying and suppressing the self-discharge process and will benefit potential applications of ECs with respect to energy retention. Self-discharge can be averted by the use of redox couples that are transformed to insoluble species via electrolysis and adsorbed onto the activated carbon electrode in redox-couple EDLCs, thus transforming the EDLC electrolyte into a material that can store charge. Self-discharge in ECs can also be successfully suppressed by utilizing an ion-interchange layer (ion-exchange membrane), separator or CuSO4 mobile electrolyte that can be converted into an insoluble species by electrolysis during the charge/discharge process. This will help in producing a modern-day blueprint for ECs with high capacitance and improved energy sustainability.

Low-spin manganese(II) and high-spin manganese(III) complexes derived from disalicylaldehyde oxaloyldihydrazone: Synthesis, spectral characterization and electrochemical studies

NASA Astrophysics Data System (ADS)

Syiemlieh, Ibanphylla; Kumar, Arvind; Kurbah, Sunshine D.; De, Arjune K.; Lal, Ram A.

2018-01-01

Low-spin manganese(II) complexes [MnII(H2slox)].H2O (1), [MnII(H2slox)(SL)] (where SL (secondary ligand) = pyridine (py, 2), 2-picoline (2-pic, 3), 3-picoline (3-pic, 4), and 4-picoline (4-pic, 5) and high-spin manganese(III) complex Na(H2O)4[MnIII(slox)(H2O)2].2.5H2O have been synthesized from disalicyaldehyde oxaloyldihydrazone in methanolic - water medium. The composition of complexes has been established by elemental analyses and thermoanalytical data. The structures of the complexes have been discussed on the basis of data obtained from molar conductance, UV visible, 1H NMR, infrared spectra, magnetic moment and electron paramagnetic resonance spectroscopic studies. Conductivity measurements in DMF suggest that the complexes (1-5) are non-electrolyte while the complex (6) is 1:1 electrolyte. The electronic spectral studies and magnetic moment data suggest five - coordinate square pyramidal structure for the complexes (2-5) and square planar geometry for manganese(II) in complex (1). In complex (6), both sodium and manganese(III) have six coordinate octahedral geometry. IR spectral studies reveal that the dihydrazone coordinates to the manganese centre in keto form in complexes (1-5) and in enol form in complex (6). In all complexes, the ligand is present in anti-cis configuration. Magnetic moment and EPR studies indicate manganese in +2 oxidation state in complexes (1-5), with low-spin square planar complex (1) and square pyramidal stereochemistries complexes (2-5) while in +3 oxidation state in high-spin distorted octahedral stereochemistry in complex (6). The complex (1) involves significant metal - metal interaction in the solid state. All of the complexes show only one metal centred electron transfer reaction in DMF solution in cyclic voltammetric studies. The complexes (1-5) involve MnII→MnI redox reaction while the complex (6) involves MnIII→MnII redox reaction, respectively.

Redox Additive-Improved Electrochemically and Structurally Robust Binder-Free Nickel Pyrophosphate Nanorods as Superior Cathode for Hybrid Supercapacitors.

PubMed

Sankar, Kalimuthu Vijaya; Seo, Youngho; Lee, Su Chan; Chan Jun, Seong

2018-03-07

For several decades, one of the great challenges for constructing a high-energy supercapacitor has been designing electrode materials with high performance. Herein, we report for the first time to our knowledge a novel hybrid supercapacitor composed of battery-type nickel pyrophosphate one-dimensional (1D) nanorods and capacitive-type N-doped reduced graphene oxide as the cathode and anode, respectively, in an aqueous redox-added electrolyte. More importantly, ex situ microscopic images of the nickel pyrophosphate 1D nanorods revealed that the presence of the battery-type redox additive enhanced the charge storage capacity and cycling life as a result of the microstructure stability. The nickel pyrophosphate 1D nanorods exhibited their maximum specific capacitance (8120 mF cm -2 at 5 mV s -1 ) and energy density (0.22 mWh cm -2 at a power density of 1.375 mW cm -2 ) in 1 M KOH + 75 mg K 3 [Fe(CN) 6 ] electrolyte. On the other side, the N-doped reduced graphene oxide delivered an excellent electrochemical performance, demonstrating that it was an appropriate anode. A hybrid supercapacitor showed a high specific capacitance (224 F g -1 at a current density of 1 A g -1 ) and high energy density (70 Wh kg -1 at a power density of 750 W kg -1 ), as well as a long cycle life (a Coulombic efficiency of 96% over 5000 cycles), which was a higher performance than most of those in recent reports. Our results suggested that the materials and redox additive in this novel design hold great promise for potential applications in a next-generation hybrid supercapacitor.

Electrochemical energy storage devices comprising self-compensating polymers

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

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

The disclosed technology relates generally to devices comprising conductive polymers and more particularly to electrochemical devices comprising self-compensating conductive polymers. In one aspect, electrochemical energy storage device comprises a negative electrode comprising an active material including a redox-active polymer. The device additionally comprises a positive electrode comprising an active material including a redox-active polymer. The device further comprises an electrolyte material interposed between the negative electrode and positive electrode and configured to conduct mobile counterions therethrough between the negative electrode and positive electrode. At least one of the negative electrode redox-active polymer and the positive electrode redox-active polymer comprises amore » zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has first and second charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the first and second charge centers whose charge state is compensated by mobile counterions.« less

Integrating a redox-coupled dye-sensitized photoelectrode into a lithium-oxygen battery for photoassisted charging.

PubMed

Yu, Mingzhe; Ren, Xiaodi; Ma, Lu; Wu, Yiying

2014-10-03

With a high theoretical specific energy, the non-aqueous rechargeable lithium-oxygen battery is a promising next-generation energy storage technique. However, the large charging overpotential remains a challenge due to the difficulty in electrochemically oxidizing the insulating lithium peroxide. Recently, a redox shuttle has been introduced into the electrolyte to chemically oxidize lithium peroxide. Here, we report the use of a triiodide/iodide redox shuttle to couple a built-in dye-sensitized titanium dioxide photoelectrode with the oxygen electrode for the photoassisted charging of a lithium-oxygen battery. On charging under illumination, triiodide ions are generated on the photoelectrode, and subsequently oxidize lithium peroxide. Due to the contribution of the photovoltage, the charging overpotential is greatly reduced. The use of a redox shuttle to couple a photoelectrode and an oxygen electrode offers a unique strategy to address the overpotential issue of non-aqueous lithium-oxygen batteries and also a distinct approach for integrating solar cells and batteries.

A compartmentalized solute transport model for redox zones in contaminated aquifers: 1. Theory and development

USGS Publications Warehouse

Abrams , Robert H.; Loague, Keith

2000-01-01

This paper, the first of two parts [see Abrams and Loague, this issue], takes the compartmentalized approach for the geochemical evolution of redox zones presented by Abrams et al. [1998] and embeds it within a solute transport framework. In this paper the compartmentalized approach is generalized to facilitate the description of its incorporation into a solute transport simulator. An equivalent formulation is developed which removes any discontinuities that may occur when switching compartments. Rate‐limited redox reactions are modeled with a modified Monod relationship that allows either the organic substrate or the electron acceptor to be the rate‐limiting reactant. Thermodynamic constraints are used to inhibit lower‐energy redox reactions from occurring under infeasible geochemical conditions without imposing equilibrium on the lower‐energy reactions. The procedure used allows any redox reaction to be simulated as being kinetically limited or thermodynamically limited, depending on local geochemical conditions. Empirical reaction inhibition methods are not needed. The sequential iteration approach (SIA), a technique which allows the number of solute transport equations to be reduced, is adopted to solve the coupled geochemical/solute transport problem. When the compartmentalized approach is embedded within the SIA, with the total analytical concentration of each component as the dependent variable in the transport equation, it is possible to reduce the number of transport equations even further than with the unmodified SIA. A one‐dimensional, coupled geochemical/solute transport simulation is presented in which redox zones evolve dynamically in time and space. The compartmentalized solute transport (COMPTRAN) model described in this paper enables the development of redox zones to be simulated under both kinetic and thermodynamic constraints. The modular design of COMPTRAN facilitates the use of many different, preexisting solute transport and geochemical codes. The companion paper [Abrams and Loague, this issue] presents examples of the application of COMPTRAN to field‐scale problems.

ZnCl 2- and NH 4Cl-hydroponics gel electrolytes for zinc-carbon batteries

NASA Astrophysics Data System (ADS)

Khalid, N. H.; Ismail, Y. M. Baba; Mohamad, A. A.

Absorbency testing is used to determine the percentage of ZnCl 2 or NH 4Cl solution absorbed by a hydroponics gel (HPG). It is found that the absorbency of ZnCl 2 or NH 4Cl solution decreases with increasing solution concentration. The conductivity of ZnCl 2- and NH 4Cl-HPG electrolytes is dependent on the solution concentration. A mixture of salt solution with HPG yields excellent gel polymer electrolytes with conductivities of 0.026 and 0.104 S cm -1 at 3 M ZnCl 2 and 7 M NH 4Cl, respectively. These gel electrolytes are then used to produce zinc-carbon cells. The fabricated cells give capacities of 8.8 and 10.0 mAh, have an internal resistance of 25.4 and 19.8 Ω, a maximum power density of 12.7 and 12.2 mW cm -2, and a short-circuit current density of 29.1 and 33.9 mA cm -2 for ZnCl 2- and NH 4Cl-HPG electrolytes, respectively.

Redox flow batteries based on supporting solutions containing chloride

DOEpatents

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

2014-01-14

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

Redox flow batteries based on supporting solutions containing chloride

DOEpatents

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

2015-07-07

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

Redox flow batteries based on supporting solutions containing chloride

DOEpatents

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

2015-09-01

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

Redox flow batteries based on supporting solutions containing chloride

DOEpatents

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

2017-11-14

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

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Direct Observations of the Formation and Redox-Mediator-Assisted Decomposition of Li2 O2 in a Liquid-Cell Li-O2 Microbattery by Scanning Transmission Electron Microscopy.

PubMed

Yang, Chuchu; Han, Jiuhui; Liu, Pan; Hou, Chen; Huang, Gang; Fujita, Takeshi; Hirata, Akihiko; Chen, Mingwei

2017-11-01

Operando scanning transmission electron microscopy observations of cathodic reactions in a liquid-cell Li-O 2 microbattery in the presence of the redox mediator tetrathiafulvalene (TTF) in 1.0 m LiClO 4 dissolved dimethyl sulfoxide electrolyte are reported. It is found that the TTF addition does not obviously affect the discharge reaction for the formation of a solid Li 2 O 2 phase. The coarsening of Li 2 O 2 nanoparticles occurs via both conventional Ostwald ripening and nonclassical crystallization by particle attachment. During charging, the oxidation reaction at significantly reduced charge potentials mainly takes place at Li 2 O 2 /electrolyte interfaces and has obvious correspondence with the oxidized TTF + distributions in the electric fields of the charged electrode. This study provides direct evidence that TTF truly plays a role in promoting the decomposition of Li 2 O 2 as a soluble charge-transfer agent between the electrode and the Li 2 O 2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multi-electrolyte-step anodic aluminum oxide method for the fabrication of self-organized nanochannel arrays

PubMed Central

2012-01-01

Nanochannel arrays were fabricated by the self-organized multi-electrolyte-step anodic aluminum oxide [AAO] method in this study. The anodization conditions used in the multi-electrolyte-step AAO method included a phosphoric acid solution as the electrolyte and an applied high voltage. There was a change in the phosphoric acid by the oxalic acid solution as the electrolyte and the applied low voltage. This method was used to produce self-organized nanochannel arrays with good regularity and circularity, meaning less power loss and processing time than with the multi-step AAO method. PMID:22333268

Molecularly Engineered Ru(II) Sensitizers Compatible with Cobalt(II/III) Redox Mediators for Dye-Sensitized Solar Cells.

PubMed

Wu, Kuan-Lin; Huckaba, Aron J; Clifford, John N; Yang, Ya-Wen; Yella, Aswani; Palomares, Emilio; Grätzel, Michael; Chi, Yun; Nazeeruddin, Mohammad Khaja

2016-08-01

Thiocyanate-free isoquinazolylpyrazolate Ru(II) complexes were synthesized and applied as sensitizers in dye-sensitized solar cells (DSCs). Unlike most other successful Ru sensitizers, Co-based electrolytes were used, and resulting record efficiency of 9.53% was obtained under simulated sunlight with an intensity of 100 mW cm(-2). Specifically, dye 51-57dht.1 and an electrolyte based on Co(phen)3 led to measurement of a JSC of 13.89 mA cm(-2), VOC of 900 mV, and FF of 0.762 to yield 9.53% efficiency. The improved device performances were achieved by the inclusion of 2-hexylthiophene units onto the isoquinoline subunits, in addition to lengthening the perfluoroalkyl chain on the pyrazolate chelating group, which worked to increase light absorption and decrease recombination effects when using the Co-based electrolyte. As this study shows, Ru(II) sensitizers bearing sterically demanding ligands can allow successful utilization of important Co electrolytes and high performance.

Newly Elaborated Multipurpose Polymer Electrolyte Encompassing RTILs for Smart Energy-Efficient Devices.

PubMed

Nair, Jijeesh R; Porcarelli, Luca; Bella, Federico; Gerbaldi, Claudio

2015-06-17

Profoundly ion-conducting, self-standing, and tack-free ethylene oxide-based polymer electrolytes encompassing a room-temperature ionic liquid (RTIL) with specific amounts of lithium salt are successfully prepared via a rapid and easily upscalable process including a UV irradiation step. All prepared materials are thoroughly characterized in terms of their physical, chemical, and morphological properties and eventually galvanostatically cycled in lab-scale lithium batteries (LIBs) exploiting a novel direct polymerization procedure to get intimate electrode/electrolyte interfacial characteristics. The promising multipurpose characteristics of the newly elaborated materials are demonstrated by testing them in dye-sensitized solar cells (DSSCs), where the introduction of the iodine/iodide-based redox mediator in the polymer matrix assured the functioning of a lab-scale test cell with conversion efficiency exceeding 6% at 1 sun. The reported results enlighten the promising prospects of the material to be successfully implemented as stable, durable, and efficient electrolyte in next-generation energy conversion and storage devices.

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

Kim, Soowhan; Thomsen, Edwin; Xia, Guanguang

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

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

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

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Redox buffered hydrofluoric acid etchant for the reduction of galvanic attack during release etching of MEMS devices having noble material films

DOEpatents

Hankins, Matthew G [Albuquerque, NM

2009-10-06

Etchant solutions comprising a redox buffer can be used during the release etch step to reduce damage to the structural layers of a MEMS device that has noble material films. A preferred redox buffer comprises a soluble thiophosphoric acid, ester, or salt that maintains the electrochemical potential of the etchant solution at a level that prevents oxidation of the structural material. Therefore, the redox buffer preferentially oxidizes in place of the structural material. The sacrificial redox buffer thereby protects the exposed structural layers while permitting the dissolution of sacrificial oxide layers during the release etch.

Halogen-free boron based electrolyte solution for rechargeable magnesium batteries

NASA Astrophysics Data System (ADS)

Zhu, Jinjie; Guo, Yongsheng; Yang, Jun; Nuli, Yanna; Zhang, Fan; Wang, Jiulin; Hirano, Shin-ichi

2014-02-01

All halogen containing electrolytes for Mg battery are apt to corrode conventional metal current collectors. In this paper, a new type of halogen-free boron based electrolyte (Mg[Mes3BPh]2/THF) is designed and prepared. Electrochemical tests show that this electrolyte system possesses high ion conductivity (1.5 × 10-3 S cm-1) and good Mg deposition-dissolution reversibility. More importantly, the same electrochemical window (2.6 V vs. Mg RE) of the electrolyte on Pt and stainless steel electrodes indicates that halogen-free electrolyte indeed lessens the corrosion to conventional metal current collectors. The surface morphologies of stainless steel, aluminum and copper are further observed after their anodic potentiostatic polarization in 0.25 mol L-1 Mg[Mes3BPh]2/THF electrolyte solution for 2 days. A comparison with halogen containing electrolytes proves that the presence of halogen in electrolyte is the reason for corrosion. This work provides a stepping stone for developing new halogen-free electrolyte systems for rechargeable Mg batteries.

Oral salt supplements to compensate for jejunostomy losses: comparison of sodium chloride capsules, glucose electrolyte solution, and glucose polymer electrolyte solution.

PubMed

Nightingale, J M; Lennard-Jones, J E; Walker, E R; Farthing, M J

1992-06-01

Six patients with jejunostomies and residual jejunal lengths of 105 to 250 cm took the same food and water each day for eight study days. In random order, three methods of salt replacement were tested, each over 48 hours, against a period without added salt. During the three test periods the patients took 120 mmol of sodium chloride daily, as salt in gelatine capsules, as an isotonic glucose electrolyte (280 mOsmol/kg; 30 kcal) solution, and as a glucose polymer (Maxijul) solution (280 mOsmol/kg; 200 kcal). The daily stomal output remained constant for each patient during the four test periods but varied between patients from 0.60 to 2.84 kg (daily intestinal fluid balance 0.74-2.61 kg). Without a salt supplement, three patients lost more sodium from the stoma than they took in by mouth (-25, -94, and -101 mmol/day) and the mean sodium balance for all six subjects was -16 mmol (range -101 to 79) daily. Extra salt was absorbed with each form of supplement (p less than 0.05); no patient with the glucose electrolyte solution (mean 96, range 0 to 226 mmol), but one patient with the glucose-polymer solution (mean 96, range -25 to 164 mmol) and two with the salt capsules (mean 66, range -8 to 145 mmol) were in negative balance. Two patients vomited with the salt capsules. There was only a small increase in energy absorption (mean 115 kcal) with the glucose polymer solution compared with the glucose electrolyte solution. A sipped glucose electrolyte solution seems to be the optimal mode of sodium replacement in patients with a high output jejunostomy.

Oral salt supplements to compensate for jejunostomy losses: comparison of sodium chloride capsules, glucose electrolyte solution, and glucose polymer electrolyte solution.

PubMed Central

Nightingale, J M; Lennard-Jones, J E; Walker, E R; Farthing, M J

1992-01-01

Six patients with jejunostomies and residual jejunal lengths of 105 to 250 cm took the same food and water each day for eight study days. In random order, three methods of salt replacement were tested, each over 48 hours, against a period without added salt. During the three test periods the patients took 120 mmol of sodium chloride daily, as salt in gelatine capsules, as an isotonic glucose electrolyte (280 mOsmol/kg; 30 kcal) solution, and as a glucose polymer (Maxijul) solution (280 mOsmol/kg; 200 kcal). The daily stomal output remained constant for each patient during the four test periods but varied between patients from 0.60 to 2.84 kg (daily intestinal fluid balance 0.74-2.61 kg). Without a salt supplement, three patients lost more sodium from the stoma than they took in by mouth (-25, -94, and -101 mmol/day) and the mean sodium balance for all six subjects was -16 mmol (range -101 to 79) daily. Extra salt was absorbed with each form of supplement (p less than 0.05); no patient with the glucose electrolyte solution (mean 96, range 0 to 226 mmol), but one patient with the glucose-polymer solution (mean 96, range -25 to 164 mmol) and two with the salt capsules (mean 66, range -8 to 145 mmol) were in negative balance. Two patients vomited with the salt capsules. There was only a small increase in energy absorption (mean 115 kcal) with the glucose polymer solution compared with the glucose electrolyte solution. A sipped glucose electrolyte solution seems to be the optimal mode of sodium replacement in patients with a high output jejunostomy. PMID:1624155

Requirements for optimization of electrodes and electrolyte for the iron/chromium Redox flow cell

NASA Technical Reports Server (NTRS)

Jalan, V.; Stark, H.; Giner, J.

1981-01-01

Improved catalyzation techniques that included a pretreatment of carbon substrate and provided normalized carbon surface for uniform gold deposition were developed. This permits efficient use of different batches of carbon felt materials which initially vary significantly in their physical and surface chemical properties, as well as their electrochemical behavior. Further modification of gold impregnation technique gave the best performing electrodes. In addition to the linear sweep voltammetry, cyclic voltammetry was used to determine the effects of different activation procedures on the Cr(3)/Cr(2) Redox and H2 evolution reactions. The roles of carbon, gold and lead in the overall Redox cycle are identified. The behavior of the electrodes at both normal battery operating potentials and more extreme potentials is discussed preparing efficient and stable electrodes for the energy storage battery is implicated.

A mathematical model for the iron/chromium redox battery

NASA Technical Reports Server (NTRS)

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.

Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Whole-bowel irrigation for mechanical colon cleansing.

PubMed

Michael, K A; DiPiro, J T; Bowden, T A; Tedesco, F J

1985-01-01

The physiology, solution composition, indications, efficacy, and safety of whole-bowel irrigation (WBI) for mechanical bowel cleansing are reviewed. WBI with isotonic electrolyte solutions produces diarrhea when the infusion rate exceeds the capacity of the intestine to distend and absorb the solution. A number of solutions are used for WBI, including 0.9% sodium chloride, balanced electrolyte solutions, lactated Ringer's, mannitol, and electrolyte solutions containing polyethylene glycol 3350 (PEG). WBI solution administration rates vary from 15-90 mL/min, by oral ingestion or nasogastric tube, with total volumes ranging from 1 to 20 L. The onset of diarrhea occurs as soon as 20 minutes with clearing of the effluent as early as 90 minutes. Faster administration rates appear to shorten overall cleansing time. Two PEG-electrolyte lavage solutions (ELSs) have recently gained FDA approval. The recommended dosage rate is 1.2-1.8 L/hr orally or by nasogastric tube until rectal effluent is clear. In most patients, this requires a maximum of 4-6 L. Initial data indicate that PEG-ELSs are safe for elderly patients and for patients who have an increased risk of fluid overload, but these solutions have not been evaluated in children, pregnant women, or patients with inflammatory bowel disease. WBI is an effective alternative to other regimens for removing fecal material and reducing bowel lumen bacterial counts before colonoscopy and colorectal surgery. Retention of bacterial counts before colonoscopy and colorectal surgery. Retention of excess WBI solution may interfere with the quality of barium enema radiographs; this can be minimized by completing the irrigation the evening before the examination. Gastrointestinal side effects occur in about one third of the patients following WBI, but do not generally require discontinuing the irrigation. Solutions containing PEG with sodium sulfate as the primary electrolyte result in the least net water and electrolyte movement and are preferred over other solutions.

[Rice water with and without electrolytes in diarrhea with a high stool output].

PubMed

Mota-Hernández, F; Posadas-Tello, N M; Rodríguez-Leyva, G

1993-12-01

The objective of the study was to determine the efficacy and safety of two rice-based oral rehydration solutions, with and without added electrolyte in children presenting acute diarrheal dehydration with high stool output (> 10 mL/kg/h) during a two-hour rehydration period. Twenty-two patients of one to 18 months old were recruited and randomly distributed into two groups: group A received the rice-based solution without electrolytes, and group B received the rice-based solution with electrolytes. A stool output diminishing was observed in both groups and rehydration was achieved in 4.0 +/- 0.9 hours in 21 patients from group A and in 4.6 +/- 0.9 hours in 13 patients group group B. There was not a statistically significant difference between the groups regarding the laboratory results. The rice-based oral rehydration solution without added electrolytes was useful for rehydration of children presenting high stool output, after administering the WHO/ORS recommended formula during a two-hour period.

A sealed optical cell for the study of lithium-electrode|electrolyte interfaces

NASA Astrophysics Data System (ADS)

Howlett, P. C.; MacFarlane, D. R.; Hollenkamp, A. F.

A sealed, symmetrical, lithium optical cell, which enables optical images of lithium surface deposits and in situ Raman spectra to be obtained simply and conveniently during charge-discharge cycling of lithium metal electrodes, has been designed and tested. A conventional aprotic liquid, 1 M lithium hexafluorophosphate in propylene carbonate, and an experimental ionic liquid, 20 mol% lithium bis(trifluoromethanesulfonyl)amide in 1-ethyl 3-methyl imidazolium bis(trifluoromethanesulfonyl)amide, are investigated as electrolyte solutions. Images obtained from the cell with the former electrolyte solution demonstrate the problems associated with cycling lithium metal electrodes. Images obtained with the latter electrolyte solution provide clear evidence that continued investigation of ionic liquids for use with lithium metal electrodes is warranted. Operation of the cell with the conventional electrolyte yields Raman spectra of good quality. The spectra display vibrational modes which arise from the electrolyte, as well as several additional modes which are associated with the deposits formed during cycling.

MetILs 3: A Strategy for High Density Energy Storage Using Redox-Active Ionic Liquids

DOE PAGES

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

2017-07-26

We present a systematic approach for increasing the concentration of redox-active species in electrolytes for nonaqueous redox flow batteries (RFBs). Starting with an ionic liquid consisting of a metal coordination cation (MetIL), ferrocene-containing ligands and iodide anions are substituted incrementally into the structure. While chemical structures can be drawn for molecules with 10 m redox-active electrons (RAE), practical limitations such as melting point and phase stability constrain the structures to 4.2 m RAE, a 2.3× improvement over the original MetIL. Dubbed “MetILs 3,” these ionic liquids possess redox activity in the cation core, ligands, and anions. Throughout all compositions, infraredmore » spectroscopy shows the ethanolamine-based ligands primarily coordinate to the Fe 2+ core via hydroxyl groups. Calorimetry conveys a profound change in thermophysical properties, not only in melting temperature but also in suppression of a cold crystallization only observed in the original MetIL. Square wave voltammetry reveals redox processes characteristic of each molecular location. Testing a laboratory-scale RFB demonstrates Coulombic efficiencies >95% and increased voltage efficiencies due to more facile redox kinetics, effectively increasing capacity 4×. Application of this strategy to other chemistries, optimizing melting point and conductivity, can yield >10 m RAE, making nonaqueous RFB a viable technology for grid scale storage.« less

In Situ Raman Spectroscopic Studies on Concentration of Electrolyte Salt in Lithium-Ion Batteries by Using Ultrafine Multifiber Probes.

PubMed

Yamanaka, Toshiro; Nakagawa, Hiroe; Tsubouchi, Shigetaka; Domi, Yasuhiro; Doi, Takayuki; Abe, Takeshi; Ogumi, Zempachi

2017-03-09

Lithium-ion batteries have attracted considerable attention due to their high power density. The change in concentration of salt in the electrolyte solution in lithium-ion batteries during operation causes serious degradation of battery performance. Herein, a new method of in situ Raman spectroscopy with ultrafine multifiber probes was developed to simultaneously study the concentrations of ions at several different positions in the electrolyte solution in deep narrow spaces between the electrodes in batteries. The total amount of ions in the electrolyte solution clearly changed during operation due to the low permeability of the solid-electrolyte interphase (SEI) at the anode for Li + permeation. The permeability, which is a key factor to achieve high battery performance, was improved (enhanced) by adding film-forming additives to the electrolyte solution to modify the properties of the SEI. The results provide important information for understanding and predicting phenomena occurring in a battery and for designing a superior battery. The present method is useful for analysis in deep narrow spaces in other electrochemical devices, such as capacitors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iodide-free ionic liquid with dual redox couples for dye-sensitized solar cells with high open-circuit voltage.

PubMed

Li, Chun-Ting; Lee, Chuan-Pei; Lee, Chi-Ta; Li, Sie-Rong; Sun, Shih-Sheng; Ho, Kuo-Chuan

2015-04-13

A novel ionic-liquid mediator, 1-butyl-3-{2-oxo-2-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]ethyl}-1H-imidazol-3-ium selenocyanate (ITSeCN), has been successfully synthesized for dye-sensitized solar cells (DSSCs). ITSeCN possesses dual redox channels, imidazolium-functionalized 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) and selenocyanate, which can serve as the cationic redox mediator and the anionic redox mediator, respectively. Therefore, ITSeCN has a favorable redox nature, which results in a more positive standard potential, larger diffusivity, and better kinetic heterogeneous rate constant than those of iodide. The DSSC with the ITSeCN electrolyte shows an efficiency of 8.38 % with a high open-current voltage (VOC ) of 854.3 mV, and this VOC value is about 150 mV higher than that for the iodide-based DSSC. Moreover, different electrocatalytic materials were employed to trigger the redox reaction of ITSeCN. The ITSeCN-based DSSC with the CoSe counter electrode achieved the best performance of 9.01 %, which suggested that transition-metal compound-type materials would be suitable for our newly synthesized ITSeCN mediator. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

We present a systematic approach for increasing the concentration of redox-active species in electrolytes for nonaqueous redox flow batteries (RFBs). Starting with an ionic liquid consisting of a metal coordination cation (MetIL), ferrocene-containing ligands and iodide anions are substituted incrementally into the structure. While chemical structures can be drawn for molecules with 10 m redox-active electrons (RAE), practical limitations such as melting point and phase stability constrain the structures to 4.2 m RAE, a 2.3× improvement over the original MetIL. Dubbed “MetILs 3,” these ionic liquids possess redox activity in the cation core, ligands, and anions. Throughout all compositions, infraredmore » spectroscopy shows the ethanolamine-based ligands primarily coordinate to the Fe 2+ core via hydroxyl groups. Calorimetry conveys a profound change in thermophysical properties, not only in melting temperature but also in suppression of a cold crystallization only observed in the original MetIL. Square wave voltammetry reveals redox processes characteristic of each molecular location. Testing a laboratory-scale RFB demonstrates Coulombic efficiencies >95% and increased voltage efficiencies due to more facile redox kinetics, effectively increasing capacity 4×. Application of this strategy to other chemistries, optimizing melting point and conductivity, can yield >10 m RAE, making nonaqueous RFB a viable technology for grid scale storage.« less

Redox condition in molten salts and solute behavior: A first-principles molecular dynamics study

NASA Astrophysics Data System (ADS)

Nam, Hyo On; Morgan, Dane

2015-10-01

Molten salts technology is of significant interest for nuclear, solar, and other energy systems. In this work, first-principles molecular dynamics (FPMD) was used to model the solute behavior in eutectic LiCl-KCl and FLiBe (Li2BeF4) melts at 773 K and 973 K, respectively. The thermo-kinetic properties for solute systems such as the redox potential, solute diffusion coefficients and structural information surrounding the solute were predicted from FPMD modeling and the calculated properties are generally in agreement with the experiments. In particular, we formulate an approach to model redox energetics vs. chlorine (or fluorine) potential from first-principles approaches. This study develops approaches for, and demonstrates the capabilities of, FPMD to model solute properties in molten salts.

Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes-A Review.

PubMed

Rajput, Nav Nidhi; Seguin, Trevor J; Wood, Brandon M; Qu, Xiaohui; Persson, Kristin A

2018-04-26

Fundamental molecular-level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applications. In particular, exhaustive knowledge of solvation structure, stability, and transport properties is critical for developing stable electrolytes for fast-charging and high-energy-density next-generation energy storage systems. Accordingly, there is growing interest in the rational design of electrolytes for beyond lithium-ion systems by tuning the molecular-level interactions of solvate species present in the electrolytes. Here we present a review of the solvation structure of multivalent electrolytes and its impact on the electrochemical performance of these batteries. A direct correlation between solvate species present in the solution and macroscopic properties of electrolytes is sparse for multivalent electrolytes and contradictory results have been reported in the literature. This review aims to illustrate the current understanding, compare results, and highlight future needs and directions to enable the deep understanding needed for the rational design of improved multivalent electrolytes.

Semiconductor-Electrocatalyst Interfaces: Theory, Experiment, and Applications in Photoelectrochemical Water Splitting.

PubMed

Nellist, Michael R; Laskowski, Forrest A L; Lin, Fuding; Mills, Thomas J; Boettcher, Shannon W

2016-04-19

Light-absorbing semiconductor electrodes coated with electrocatalysts are key components of photoelectrochemical energy conversion and storage systems. Efforts to optimize these systems have been slowed by an inadequate understanding of the semiconductor-electrocatalyst (sem|cat) interface. The sem|cat interface is important because it separates and collects photoexcited charge carriers from the semiconductor. The photovoltage generated by the interface drives "uphill" photochemical reactions, such as water splitting to form hydrogen fuel. Here we describe efforts to understand the microscopic processes and materials parameters governing interfacial electron transfer between light-absorbing semiconductors, electrocatalysts, and solution. We highlight the properties of transition-metal oxyhydroxide electrocatalysts, such as Ni(Fe)OOH, because they are the fastest oxygen-evolution catalysts known in alkaline media and are (typically) permeable to electrolyte. We describe the physics that govern the charge-transfer kinetics for different interface types, and show how numerical simulations can explain the response of composite systems. Emphasis is placed on "limiting" behavior. Electrocatalysts that are permeable to electrolyte form "adaptive" junctions where the interface energetics change during operation as charge accumulates in the catalyst, but is screened locally by electrolyte ions. Electrocatalysts that are dense, and thus impermeable to electrolyte, form buried junctions where the interface physics are unchanged during operation. Experiments to directly measure the interface behavior and test the theory/simulations are challenging because conventional photoelectrochemical techniques do not measure the electrocatalyst potential during operation. We developed dual-working-electrode (DWE) photoelectrochemistry to address this limitation. A second electrode is attached to the catalyst layer to sense or control current/voltage independent from that of the semiconductor back ohmic contact. Consistent with simulations, electrolyte-permeable, redox-active catalysts such as Ni(Fe)OOH form "adaptive" junctions where the effective barrier height for electron exchange depends on the potential of the catalyst. This is in contrast to sem|cat interfaces with dense electrolyte-impermeable catalysts, such as nanocrystalline IrOx, that behave like solid-state buried (Schottky-like) junctions. These results elucidate a design principle for catalyzed photoelectrodes. The buried heterojunctions formed by dense catalysts are often limited by Fermi-level pinning and low photovoltages. Catalysts deposited by "soft" methods, such as electrodeposition, form adaptive junctions that tend to provide larger photovoltages and efficiencies. We also preview efforts to improve theory/simulations to account for the presence of surface states and discuss the prospect of carrier-selective catalyst contacts.

Solubility of non-polar gases in electrolyte solutions

NASA Technical Reports Server (NTRS)

Walker, R. L., Jr.

1970-01-01

Solubility theory describes the effects of both concentration and temperature on solute activity coefficients. It predicts the salting-out effect and the decrease in solubility of non-polar gases with increased electrolyte concentration, and can be used to calculate heats of solution, entropies, and partial molal volumes of dissolved gases

Multifunctional Sandwich‐Structured Electrolyte for High‐Performance Lithium–Sulfur Batteries

PubMed Central

Qu, Hongtao; Zhang, Jianjun; Du, Aobing; Chen, Bingbing; Chai, Jingchao; Xue, Nan; Wang, Longlong; Qiao, Lixin; Wang, Chen; Zang, Xiao; Yang, Jinfeng; Wang, Xiaogang

2018-01-01

Abstract Due to its high theoretical energy density (2600 Wh kg−1), low cost, and environmental benignity, the lithium–sulfur (Li‐S) battery is attracting strong interest among the various electrochemical energy storage systems. However, its practical application is seriously hampered by the so‐called shuttle effect of the highly soluble polysulfides. Herein, a novel design of multifunctional sandwich‐structured polymer electrolyte (polymer/cellulose nonwoven/nanocarbon) for high‐performance Li‐S batteries is demonstrated. It is verified that Li‐S battery with this sandwich‐structured polymer electrolyte delivers excellent cycling stability (only 0.039% capacity decay cycle−1 on average exceeding 1500 cycles at 0.5 C) and rate capability (with a reversible capacity of 594 mA h g−1 at 4 C). These electrochemical performances are attributed to the synergistic effect of each layer in this unique sandwich‐structured polymer electrolyte including steady lithium stripping/plating, strong polysulfide absorption ability, and increased redox reaction sites. More importantly, even with high sulfur loading of 4.9 mg cm−2, Li‐S battery with this sandwich‐structured polymer electrolyte can deliver high initial areal capacity of 5.1 mA h cm−2. This demonstrated strategy here may open up a new era of designing hierarchical structured polymer electrolytes for high‐performance Li‐S batteries. PMID:29593953

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

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

DOE PAGES

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

2016-03-10

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

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

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

Yang, Ping

The worldwide energy demand is increasing every day and it necessitates rational and efficient usage of renewable energy. Undoubtedly, utilization of renewable energy can address various environmental challenges. However, all current renewable energy resources (wind, solar, and hydroelectric power) are intermittent and fluctuating in their nature that raises an important question of introducing effective energy storage solutions. Utilization of redox flow cells (RFCs) has recently been recognized as a viable technology for large-scale energy storage and, hence, is well suited for integrating renewable energy and balancing electricity grids. In brief, RFC is an electrochemical storage device where energy is storedmore » 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.« less

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

PubMed

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.

Performance comparison of protonic and sodium phosphomolybdovanadate polyoxoanion catholytes within a chemically regenerative redox cathode polymer electrolyte fuel cell

NASA Astrophysics Data System (ADS)

Ward, David B.; Gunn, Natasha L. O.; Uwigena, Nadine; Davies, Trevor J.

2018-01-01

The direct reduction of oxygen in conventional polymer electrolyte fuel cells (PEFCs) is seen by many researchers as a key challenge in PEFC development. Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells offer an alternative approach via the indirect reduction of oxygen, improving durability and reducing cost. These systems substitute gaseous oxygen for a liquid catalyst that is reduced at the cathode then oxidised in a regeneration vessel via air bubbling. A key component of a CRRC system is the liquid catalyst or catholyte. To date, phosphomolybdovanadium polyoxometalates with empirical formula H3+nPVnMo12-nO40 have shown the most promise for CRRC PEFC systems. In this work, four catholyte formulations are studied and compared against each other. The catholytes vary in vanadium content, pH and counter ion, with empirical formulas H6PV3Mo9O40, H7PV4Mo8O40, Na3H3PV3Mo9O40 and Na4H3PV4Mo8O40. Thermodynamic properties, cell performance and regeneration rates are measured, generating new insights into how formulation chemistry affects the components of a CRRC system. The results include the best CRRC PEFC performance reported to date, with noticeable advantages over conventional PEFCs. The optimum catholyte formulation is then determined via steady state tests, the results of which will guide further optimization of the catholyte formulation.

NREL Establishes World Record for Solar Hydrogen Production | News | News |

Science.gov Websites

acid/water solution (electrolyte) where the water-splitting reaction occurs to form hydrogen and oxygen efficiency and to partially protect the critical underlying layers from the corrosive electrolyte solution

Drude-jellium model for the microwave conductivity of electrolyte solutions

NASA Astrophysics Data System (ADS)

Nhan, Tran Thi; Theu, Luong Thi; Tuan, Le; Viet, Nguyen Ai

2018-05-01

The microwave conductivity characteristics of electrolyte solutions have attracted much interest of researchers because a good understanding of their properties plays a key role to study fundamental processes in biology and chemistry. In this work, we consider the solution of sodium chloride as a plasma consisting of ions with water background. Its plasmon frequency is calculated by the jellium theory. The linear dependence of the microwave conductivity on the ion concentration of the electrolyte solutions is explained by a microscopic approach and described by a combination of this plasmon relationship and the simplified Drude formula for dielectric constant. Furthermore, the dependence of the microwave conductivity on the frequency of the salt solution is also examined. We suggest that it obeys the logistic distribution. We found a good agreement between theoretical calculations and experimental data. The values of the damping coefficient γ for the conductive solutions at low frequencies and the cutting frequency are estimated. The linear dependence of the diffusion coefficient on the temperature of the salt solution is also shown, in similarity with the result in the other model. The application of the Drude-jellium model could be done for the other electrolyte solutions in order to study theirs electro-dynamic properties.

Electrodeposition of magnesium and magnesium/aluminum alloys

DOEpatents

Mayer, Anton

1988-01-01

Electrolytes and plating solutions for use in processes for electroplating and electroforming pure magnesium and alloys of aluminum and magnesium and also electrodeposition processes. An electrolyte of this invention is comprised of an alkali metal fluoride or a quaternary ammonium halide, dimethyl magnesium and/or diethyl magnesium, and triethyl aluminum and/or triisobutyl aluminum. An electrolyte may be dissolved in an aromatic hydrocarbon solvent to form a plating solution. The proportions of the component compounds in the electrolyte are varied to produce essentially pure magnesium or magnesium/aluminum alloys having varying selected compositions.

Electrodeposition of magnesium and magnesium/aluminum alloys

DOEpatents

Mayer, A.

1988-01-21

Electrolytes and plating solutions for use in processes for electroplating and electroforming pure magnesium and alloys of aluminum and magnesium and also electrodeposition processes. An electrolyte of this invention is comprised of an alkali metal fluoride or a quaternary ammonium halide, dimethyl magnesium and/or diethyl magnesium, and triethyl aluminum and/or triisobutyl aluminum. An electrolyte may be dissolved in an aromatic hydrocarbon solvent to form a plating solution. The proportions of the component compounds in the electrolyte are varied to produce essentially pure magnesium or magnesium/aluminum alloys having varying selected compositions.

A Modified Robinson-Stokes equation for describing the thermodynamic properties of aqueous solutions of 1-1 electrolytes

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.

2008-05-01

Equations relating osmotic, mean ionic activity, and water activity coefficients to electrolyte concentrations in binary aqueous solutions were substantiated within the framework of cluster concepts. The model includes the contribution to solution nonideality of electrostatic interactions in terms of the Debye-Hückel theory along with hydration and association of salts via relations containing hydration and association numbers in the standard states. According to the description of data on 54 aqueous solutions of 1-1 electrolytes, this model should be given preference compared with the most extensively used NRTL, NRTL-NRF, Wilson, and Pitzer models.

Electrolyte solutions including a phosphoranimine compound, and energy storage devices including same

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

Klaehn, John R.; Dufek, Eric J.; Rollins, Harry W.

An electrolyte solution comprising at least one phosphoranimine compound and a metal salt. The at least one phosphoranimine compound comprises a compound of the chemical structure ##STR00001## where X is an organosilyl group or a tert-butyl group and each of R.sup.1, R.sup.2, and R.sup.3 is independently selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. An energy storage device including the electrolyte solution is also disclosed.

Exploratory studies on some electrochemical cell systems

NASA Astrophysics Data System (ADS)

Chaudhuri, Srikumar; Guha, D.

Exploratory studies were conducted on cell systems with different metal anodes, and iodine and sulphur mixed with graphite powder in a polymer matrix as cathodes, using different electrolytes in non-aqueous and aqueous media as ionic charge carriers. The electrical conductance of the electrolyte solutions in aqueous and non-aqueous solvents, the open circuit voltage (OCV) and short circuit current (SCC) for the different cell systems were measured. To date, the non-aqueous solvents used in our studies were dimethylformamide, formamide, dioxan, and nitrobenzene, and the electrolytes used were potassium iodide, caustic potash, cetyltrimethylammonium bromide (CTAB), sodium lauryl sulphate (SLS) and calcium chloride. These electrolytes were used in both non-aqueous and aqueous media. In general, aqueous electrolyte solutions gave a better performance than non-aqueous electrolyte solutions. Of the aqueous electrolytes, the highest conductance was shown by potassium chloride solution in water (conductance=0.0334 mho). However, the best OCV and SCC were shown by aluminium as anode and iodine as cathode with a saturated solution of caustic potash in water. The OCV was 1.85 V and the SCC was 290 mA cm -2. The highest conductance among the non-aqueous systems was shown by caustic potash in formamide. (Conductance=0.013 mho.) The best OCV and SCC, however, were shown by a zinc anode and iodine cathode with saturated potassium chloride in formamide, having an OCV of 1.55 V and an SCC of 150 mA cm -2. Further studies are in progress to obtain detailed performance data and recharging characteristics of some of the more promising systems reported here.

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

USGS Publications Warehouse

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.

Second harmonic generation study of malachite green adsorption at the interface between air and an electrolyte solution: observing the effect of excess electrical charge density at the interface.

PubMed

Song, Jinsuk; Kim, Mahn Won

2010-03-11

Understanding the differential adsorption of ions at the interface of an electrolyte solution is very important because it is closely related, not only to the fundamental aspects of biological systems, but also to many industrial applications. We have measured the excess interfacial negative charge density at air-electrolyte solution interfaces by using resonant second harmonic generation of oppositely charged probe molecules. The excess charge density increased with the square root of the bulk electrolyte concentration. A new adsorption model that includes the electrostatic interaction between adsorbed molecules is proposed to explain the measured adsorption isotherm, and it is in good agreement with the experimental results.

Isotonicity of liver and of kidney tissue in solutions of electrolytes.

PubMed

OPIE, E L

1959-07-01

Solutions of a wide variety of electrolytes, isotonic with liver or with kidney tissue, have approximately the same osmotic pressure as solutions of sodium chloride isotonic with tissues of the two organs respectively; that is, with solutions approximately twice as concentrated as the sodium chloride of mammalian blood plasma. The molar concentration of various electrolytes isotonic with liver or with kidney tissue immediately after its removal from the body is determined by the molecular weight, valency, and ion-dissociation of these electrolytes in accordance with the well known conditions of osmosis. The plasma membranes of liver and of kidney cells are imperfectly semipermeable to electrolytes, and those that enter the cell, though retarded in so doing, bring about injury which increases permeability to water. The osmotic activity of cells of mammalian liver and kidney immediately after their removal from the body resembles that of plant cells, egg cells of marine invertebrates, and mammalian red blood corpuscles and presumably represents a basic property of living cells by which osmotic pressure may be adjusted to functional need.

ISOTONICITY OF LIVER AND OF KIDNEY TISSUE IN SOLUTIONS OF ELECTROLYTES

PubMed Central

Opie, Eugene L.

1959-01-01

Solutions of a wide variety of electrolytes, isotonic with liver or with kidney tissue, have approximately the same osmotic pressure as solutions of sodium chloride isotonic with tissues of the two organs respectively; that is, with solutions approximately twice as concentrated as the sodium chloride of mammalian blood plasma. The molar concentration of various electrolytes isotonic with liver or with kidney tissue immediately after its removal from the body is determined by the molecular weight, valency, and ion-dissociation of these electrolytes in accordance with the well known conditions of osmosis. The plasma membranes of liver and of kidney cells are imperfectly semipermeable to electrolytes, and those that enter the cell, though retarded in so doing, bring about injury which increases permeability to water. The osmotic activity of cells of mammalian liver and kidney immediately after their removal from the body resembles that of plant cells, egg cells of marine invertebrates, and mammalian red blood corpuscles and presumably represents a basic property of living cells by which osmotic pressure may be adjusted to functional need. PMID:13664872

Sensitive bridge circuit measures conductance of low-conductivity electrolyte solutions

NASA Technical Reports Server (NTRS)

Schmidt, K.

1967-01-01

Compact bridge circuit measures sensitive and accurate conductance of low-conductivity electrolyte solutions. The bridge utilizes a phase sensitive detector to obtain a linear deflection of the null indicator relative to the measured conductance.

Carbon-Coated Honeycomb Ni-Mn-Co-O Inverse Opal: A High Capacity Ternary Transition Metal Oxide Anode for Li-ion Batteries

PubMed Central

McNulty, David; Geaney, Hugh; O’Dwyer, Colm

2017-01-01

We present the formation of a carbon-coated honeycomb ternary Ni-Mn-Co-O inverse opal as a conversion mode anode material for Li-ion battery applications. In order to obtain high capacity via conversion mode reactions, a single phase crystalline honeycombed IO structure of Ni-Mn-Co-O material was first formed. This Ni-Mn-Co-O IO converts via reversible redox reactions and Li2O formation to a 3D structured matrix assembly of nanoparticles of three (MnO, CoO and NiO) oxides, that facilitates efficient reactions with Li. A carbon coating maintains the structure without clogging the open-worked IO pore morphology for electrolyte penetration and mass transport of products during cycling. The highly porous IO was compared in a Li-ion half-cell to nanoparticles of the same material and showed significant improvement in specific capacity and capacity retention. Further optimization of the system was investigated by incorporating a vinylene carbonate additive into the electrolyte solution which boosted performance, offering promising high-rate performance and good capacity retention over extended cycling. The analysis confirms the possibility of creating a ternary transition metal oxide material with binder free accessible open-worked structure to allow three conversion mode oxides to efficiently cycle as an anode material for Li-ion battery applications. PMID:28186183

Calculation of DSSC parameters based on ZnO nanorod/TiO2 mesoporous photoanode

NASA Astrophysics Data System (ADS)

Safriani, L.; Nurrida, A.; Mulyana, C.; Susilawati, T.; Bahtiar, A.; Aprilia, A.

2017-07-01

Photoanode of dye sensitized solar cell (DSSC) plays an important role as electron transport media to accept photogenerated electron from excited state of dye. There are several physical properties that are required from photoanode of DSSC. It should be highly transparent, have large surface area, has a conduction band lower than LUMO of dye molecule, has high charge carrier mobility and finally has a good stability in redox electrolyte process. In this work, DSSC with structure FTO/ZnO nanorod/TiO2 mesoporous/Ru-dye/gel electrolyte/ Pt/FTO has been fabricated. In order to modified the structures of photoanode, ZnO nanorod was grown on aluminium doped ZnO seed layer by variation concentration of Al (0 wt%, 0.5 wt% and 1.0 wt%). Zinc nitrate hexahydrate and hexamethylenetetramine used as raw materials for ZnO nanorod growth solution and deposited by self-assembly methods on FTO/Al doped ZnO seed layer. It is then followed by deposition of titania (TiO2) paste by screen printing methods. DSSC parameters i.e. ideally factor (n), series resistance (RS ), and shunt resistance (RSH ) was derived from current density-voltage (I-V) curve using the simplify equation of ideal diode model. The influences of ZnO photoanode structures to the solar cell performance will be completely discussed.

Carbon-Coated Honeycomb Ni-Mn-Co-O Inverse Opal: A High Capacity Ternary Transition Metal Oxide Anode for Li-ion Batteries.

PubMed

McNulty, David; Geaney, Hugh; O'Dwyer, Colm

2017-02-10

We present the formation of a carbon-coated honeycomb ternary Ni-Mn-Co-O inverse opal as a conversion mode anode material for Li-ion battery applications. In order to obtain high capacity via conversion mode reactions, a single phase crystalline honeycombed IO structure of Ni-Mn-Co-O material was first formed. This Ni-Mn-Co-O IO converts via reversible redox reactions and Li 2 O formation to a 3D structured matrix assembly of nanoparticles of three (MnO, CoO and NiO) oxides, that facilitates efficient reactions with Li. A carbon coating maintains the structure without clogging the open-worked IO pore morphology for electrolyte penetration and mass transport of products during cycling. The highly porous IO was compared in a Li-ion half-cell to nanoparticles of the same material and showed significant improvement in specific capacity and capacity retention. Further optimization of the system was investigated by incorporating a vinylene carbonate additive into the electrolyte solution which boosted performance, offering promising high-rate performance and good capacity retention over extended cycling. The analysis confirms the possibility of creating a ternary transition metal oxide material with binder free accessible open-worked structure to allow three conversion mode oxides to efficiently cycle as an anode material for Li-ion battery applications.

Effects of ionic concentration gradient on electroosmotic flow mixing in a microchannel.

PubMed

Peng, Ran; Li, Dongqing

2015-02-15

Effects of ionic concentration gradient on electroosmotic flow (EOF) mixing of one stream of a high concentration electrolyte solution with a stream of a low concentration electrolyte solution in a microchannel are investigated numerically. The concentration field, flow field and electric field are strongly coupled via concentration dependent zeta potential, dielectric constant and electric conductivity. The results show that the electric field and the flow velocity are non-uniform when the concentration dependence of these parameters is taken into consideration. It is also found that when the ionic concentration of the electrolyte solution is higher than 1M, the electrolyte solution essentially cannot enter the channel due to the extremely low electroosmotic flow mobility. The effects of the concentration dependence of zeta potential, dielectric constant and electric conductivity on electroosmotic flow mixing are studied. Copyright © 2014 Elsevier Inc. All rights reserved.

Smart Multifunctional Fluids for Lithium Ion Batteries: Enhanced Rate Performance and Intrinsic Mechanical Protection

NASA Astrophysics Data System (ADS)

Ding, Jie; Tian, Tongfei; Meng, Qing; Guo, Zaiping; Li, Weihua; Zhang, Peng; Ciacchi, Fabio T.; Huang, Jewel; Yang, Wenrong

2013-08-01

Lithium ion batteries are attractive power sources for the consumer electronics market and are being aggressively developed for road transportation. Nevertheless, issues with safety and reliability need to be solved prior to the large-scale uptake of these batteries. There have recently been significant development and assessment of materials with resistance to mechanical abuse, with the aims of reinforcing the battery and preventing puncturing during a crash. Most of the work on battery mechanical safety has concentrated on the external packaging of batteries, with little attention being paid to the enclosed electrolyte. We report on smart multifunctional fluids that act as both highly conductive electrolytes and intrinsic mechanical protectors for lithium ion batteries. These fluids exhibit a shear thickening effect under pressure or impact and thus demonstrate excellent resistance to crushing. Also, the fluids show higher ionic conductivities and comparable redox stability windows to the commercial liquid electrolytes.

Electrochemical performance of solid oxide fuel cells having electrolytes made by suspension and solution precursor plasma spraying

NASA Astrophysics Data System (ADS)

Marr, M.; Kuhn, J.; Metcalfe, C.; Harris, J.; Kesler, O.

2014-01-01

Yttria-stabilized zirconia (YSZ) electrolytes were deposited by suspension plasma spraying (SPS) and solution precursor plasma spraying (SPPS). The electrolytes were evaluated for permeability, microstructure, and electrochemical performance. With SPS, three different suspensions were tested to explore the influence of powder size distribution and liquid properties. Electrolytes made from suspensions of a powder with d50 = 2.6 μm were more gas-tight than those made from suspensions of a powder with d50 = 0.6 μm. A peak open circuit voltage of 1.00 V was measured at 750 °C with a cell with an electrolyte made from a suspension of d50 = 2.6 μm powder. The use of a flammable suspension liquid was beneficial for improving electrolyte conductivity when using lower energy plasmas, but the choice of liquid was less important when using higher energy plasmas. With SPPS, peak electrolyte conductivities were comparable to the peak conductivities of the SPS electrolytes. However, leak rates through the SPPS electrolytes were higher than those through the electrolytes made from suspensions of d50 = 2.6 μm powder. The electrochemical test data on SPPS electrolytes are the first reported in the literature.

[On the influence of local molecular environment on the redox potential of electron transfer cofactors in bacterial photosynthetic reaction centers].

PubMed

Krasil'nikov, P M; Noks, P P; Rubin, A B

2011-01-01

The addition of cryosolvents (glycerol, dimethylsulfoxide) to a water solution containing bacterial photosynthetic reaction centers changes the redox potential of the bacteriochlorophyll dimer, but does not affect the redox potential of the quinone primary acceptor. It has been shown that the change in redox potential can be produced by changes of the electrostatic interactions between cofactors and the local molecular environment modified by additives entered into the solution. The degree of influence of a solvent on the redox potential of various cofactors is determined by degree of availability of these cofactors for molecules of solvent, which depends on the arrangement of cofactors in the structure of reaction centers.

A Review of RedOx Cycling of Solid Oxide Fuel Cells Anode

PubMed Central

Faes, Antonin; Hessler-Wyser, Aïcha; Zryd, Amédée; Van Herle, Jan

2012-01-01

Solid oxide fuel cells are able to convert fuels, including hydrocarbons, to electricity with an unbeatable efficiency even for small systems. One of the main limitations for long-term utilization is the reduction-oxidation cycling (RedOx cycles) of the nickel-based anodes. This paper will review the effects and parameters influencing RedOx cycles of the Ni-ceramic anode. Second, solutions for RedOx instability are reviewed in the patent and open scientific literature. The solutions are described from the point of view of the system, stack design, cell design, new materials and microstructure optimization. Finally, a brief synthesis on RedOx cycling of Ni-based anode supports for standard and optimized microstructures is depicted. PMID:24958298

Liquid electrode

DOEpatents

Ekechukwu, Amy A.

1994-01-01

A dropping electrolyte electrode for use in electrochemical analysis of non-polar sample solutions, such as benzene or cyclohexane. The liquid electrode, preferably an aqueous salt solution immiscible in the sample solution, is introduced into the solution in dropwise fashion from a capillary. The electrolyte is introduced at a known rate, thus, the droplets each have the same volume and surface area. The electrode is used in making standard electrochemical measurements in order to determine properties of non-polar sample solutions.

Ionic Effects on Supercritical CO2-Brine Interfacial Tensions: Molecular Dynamics Simulations and a Universal Correlation with Ionic Strength, Temperature, and Pressure.

PubMed

Zhao, Lingling; Ji, Jiayuan; Tao, Lu; Lin, Shangchao

2016-09-13

For geological CO2 storage in deep saline aquifers, the interfacial tension (IFT) between supercritical CO2 and brine is critical for the storage security and design of the storage capacitance. However, currently, no predictive model exists to determine the IFT of supercritical CO2 against complex electrolyte solutions involving various mixed salt species at different concentrations and compositions. In this paper, we use molecular dynamics (MD) simulations to investigate the effect of salt ions on the incremental IFT at the supercritical CO2-brine interface with respect to that at the reference supercritical CO2-water interface. Supercritical CO2-NaCl solution, CO2-CaCl2 solution and CO2-(NaCl+CaCl2) mixed solution systems are simulated at 343 K and 20 MPa under different salinities and salt compositions. We find that the valence of the cations is the primary contributor to the variation in IFT, while the Lennard-Jones potentials for the cations pose a smaller impact on the IFT. Interestingly, the incremental IFT exhibits a general linear correlation with the ionic strength in the above three electrolyte systems, and the slopes are almost identical and independent of the solution types. Based on this finding, a universal predictive formula for IFTs of CO2-complex electrolyte solution systems is established, as a function of ionic strength, temperature, and pressure. The predicted IFTs using the established formula agree perfectly (with a high statistical confidence level of ∼96%) with a wide range of experimental data for CO2 interfacing with different electrolyte solutions, such as those involving MgCl2 and Na2SO4. This work provides an efficient and accurate route to directly predict IFTs in supercritical CO2-complex electrolyte solution systems for practical engineering applications, such as geological CO2 sequestration in deep saline aquifers and other interfacial systems involving complex electrolyte solutions.

Plasma Electrolytic Oxidation Coatings on Pure Ti Substrate: Effects of Na3PO4 Concentration on Morphology and Corrosion Behavior of Coatings in Ringer's Physiological Solution

NASA Astrophysics Data System (ADS)

Roknian, Masoud; Fattah-alhosseini, Arash; Gashti, Seyed Omid

2018-03-01

Plasma electrolytic oxidation has been used as a relatively new method for applying ceramic coatings having different features. In the present study, commercially pure titanium is used as substrate, and effects of trisodium phosphate electrolyte concentration on the microstructure, as well as corrosion behavior of the coating in Ringer's physiological solution are investigated. The morphology and phase compositions of coatings were analyzed by using scanning electron microscopy (SEM) and x-ray diffraction patterns. The study on the corrosion behavior of samples in a Ringer's physiological solution was carried out using open-circuit potential potentiodynamic polarization and electrochemical impedance spectroscopy. The results of electrochemical analysis proved that higher concentration of phosphate electrolyte leads to increase in the corrosion resistance of applied coatings. Accordingly, obtained results revealed that the optimum electrolyte concentration for the best corrosion behavior was 20 g L-1. Furthermore, SEM images and reduction in the dielectric breakdown potential indicated that increase in the electrolyte concentration leads to morphological improvement and smoothening of the surface.

Isotherm-Based Thermodynamic Model for Solute Activities of Asymmetric Electrolyte Aqueous Solutions.

PubMed

Nandy, Lucy; Dutcher, Cari S

2017-09-21

Adsorption isotherm-based statistical thermodynamic models can be used to determine solute concentration and solute and solvent activities in aqueous solutions. Recently, the number of adjustable parameters in the isotherm model of Dutcher et al. J. Phys. Chem. A/C 2011, 2012, 2013 were reduced for neutral solutes as well as symmetric 1:1 electrolytes by using a Coulombic model to describe the solute-solvent energy interactions (Ohm et al. J. Phys. Chem. A 2015, Nandy et al. J. Phys. Chem. A 2016). Here, the Coulombic treatment for symmetric electrolytes is extended to establish improved isotherm model equations for asymmetric 1-2 and 1-3 electrolyte systems. The Coulombic model developed here results in prediction of activities and other thermodynamic properties in multicomponent systems containing ions of arbitrary charge. The model is found to accurately calculate the osmotic coefficient over the entire solute concentration range with two model parameters, related to intermolecular solute-solute and solute-solvent spacing. The inorganic salts and acids treated here are generally considered to be fully dissociated. However, there are certain weak acids that do not dissociate completely, such as the bisulfate ion. In this work, partial dissociation of the bisulfate ion from sulfuric acid is treated as a mixture, with an additional model parameter that accounts for the dissociation ratio of the dissociated ions to nondissociated ions.

Apparent Ionic Charge in Electrolyte and Polyelectrolyte Solutions

ERIC Educational Resources Information Center

Magdelenat, H.; And Others

1978-01-01

Compares average displacements of charged particles under thermal motion alone with those obtained by the action of an external electric field to develop a concept of "apparent charge" to approximate actual structural charge in an electrolyte solution. (SL)

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

PubMed

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

2017-07-10

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

Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries

DOE PAGES

Doan-Nguyen, Vicky V. T.; Subrahmanyam, Kota S.; Butala, Megan M.; ...

2016-11-09

Sulfur cathodes in conversion reaction batteries offer high gravimetric capacity but suffer from parasitic polysulfide shuttling. We demonstrate here that transition metal chalcogels of approximate formula MoS 3.4 achieve a high gravimetric capacity close to 600 mAh g –1 (close to 1000 mAh g –1 on a sulfur basis) as electrode materials for lithium-ion batteries. Transition metal chalcogels are amorphous and comprise polysulfide chains connected by inorganic linkers. The linkers appear to act as a “glue” in the electrode to prevent polysulfide shuttling. The Mo chalcogels function as electrodes in carbonate- and ether-based electrolytes, which further provides evidence of polysulfidemore » solubility not being a limiting issue. We employ X-ray spectroscopy and operando pair distribution function techniques to elucidate the structural evolution of the electrode. Raman and X-ray photoelectron spectroscopy track the chemical moieties that arise during the anion-redox-driven processes. As a result, we find the redox state of Mo remains unchanged across the electrochemical cycling and, correspondingly, the redox is anion-driven.« less

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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

PubMed

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

2016-12-08

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

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

PubMed

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

2016-07-13

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

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

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

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

Process for electrolytic deposition of metals on zirconium materials

DOEpatents

Donaghy, Robert E.

1979-01-30

A process for the electrolytic deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electrolytic plating solution containing the metal to be deposited on the article in the presence of an electrode receiving current.

High-Performance Cells Containing Lithium Metal Anodes, LiNi0.6Co0.2Mn0.2O2 (NCM 622) Cathodes, and Fluoroethylene Carbonate-Based Electrolyte Solution with Practical Loading.

PubMed

Salitra, Gregory; Markevich, Elena; Afri, Michal; Talyosef, Yosef; Hartmann, Pascal; Kulisch, Joern; Sun, Yang-Kook; Aurbach, Doron

2018-06-13

We report on the highly stable lithium metal|LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) cells with practical electrodes' loading of 3.3 mA h g -1 , which can undergo many hundreds of stable cycles, demonstrating high rate capability. A key issue was the use of fluoroethylene carbonate (FEC)-based electrolyte solutions (1 M LiPF 6 in FEC/dimethyl carbonate). Li|NCM 622 cells can be cycled at 1.5 mA cm -2 for more than 600 cycles, whereas symmetric Li|Li cells demonstrate stable performance for more than 1000 cycles even at higher areal capacity and current density. We attribute the excellent performance of both Li|NCM and Li|Li cells to the formation of a stable and efficient solid electrolyte interphase (SEI) on the surface of the Li metal electrodes cycled in FEC-based electrolyte solutions. The composition of the SEI on the Li and the NCM electrodes is analyzed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. A drastic capacity fading of Li|NCM cells is observed, followed by spontaneous capacity recovery during prolonged cycling. This phenomenon depends on the current density and the amount of the electrolyte solution and relates to kinetic limitations because of SEI formation on the Li anodes in the FEC-based electrolyte solution.

THE CONTRIBUTIONS OF NORMAL AND ANOMALOUS OSMOSIS TO THE OSMOTIC EFFECTS ARISING ACROSS CHARGED MEMBRANES WITH SOLUTIONS OF ELECTROLYTES

PubMed Central

Grim, Eugene; Sollner, Karl

1957-01-01

The osmotic effect arising across a porous membrane separating the solution of an electrolyte from water (or a more dilute solution) is ordinarily due to both normal osmosis, as it occurs also with non-electrolytes, and to "anomalous" osmosis. It is shown that the normal osmotic component cannot be measured quantitatively by the conventional comparison with a non-electrolytic reference solute. Anomalous osmosis does not occur with electroneutral membranes. Accordingly, with membranes which can be charged and discharged reversibly (without changes in geometrical structure), such as many proteinized membranes, the osmotic effects caused by an electrolyte can be measured both when only normal osmosis arises (with the membrane in the electroneutral state) and when normal as well as anomalous osmosis occurs (with the membrane in a charged state). The difference between these two effects is the true anomalous osmosis. Data are presented on the osmotic effects across an oxyhemoglobin membrane in the uncharged state at pH 6.75 and in two charged states, positive at pH 4.0 and negative at pH 10.0, with solutions of a variety of electrolytes using a concentration ratio of 2:1 over a wide range of concentrations. The rates of the movement of liquid across the membrane against an inconsequentially small hydrostatic head are recorded instead of, as conventional, the physiologically less significant pressure rises after a standard time. PMID:13439166

Selection of new Kynar-based electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Christie, Alasdair M.; Christie, Lynn; Vincent, Colin A.

New electrolyte solution compositions have been identified for use in lithium-ion batteries after gelling with an appropriate quantity of Kynar polymer. Since the Li + conducting medium is largely the liquid electrolyte component, the assessment of these solutions as suitable lithium-ion cell candidates were investigated before adding the polymer. Selected electrolyte solutions were then used in the preparation of polymer gels. The specific conductivities of Kynar-based gels were determined as a function of salt concentration and polymer concentration. Optimised self-supporting polymer films, based on mixtures of ethylene carbonate (EC), ethylmethyl carbonate (EMC) and lithium hexafluorophosphate (LiPF 6) or lithium tetrafluoroborate (LiBF 4), showed good high current density cycling performance when used as separators in coke and Li 1- xMn 2O 4 (spinel) half-cells.

Simultaneous anionic and cationic redox

NASA Astrophysics Data System (ADS)

Jung, Sung-Kyun; Kang, Kisuk

2017-12-01

It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

Design of organic dyes and cobalt polypyridine redox mediators for high-efficiency dye-sensitized solar cells.

PubMed

Feldt, Sandra M; Gibson, Elizabeth A; Gabrielsson, Erik; Sun, Licheng; Boschloo, Gerrit; Hagfeldt, Anders

2010-11-24

Dye-sensitized solar cells (DSCs) with cobalt-based mediators with efficiencies surpassing the record for DSCs with iodide-free electrolytes were developed by selecting a suitable combination of a cobalt polypyridine complex and an organic sensitizer. The effect of the steric properties of two triphenylamine-based organic sensitizers and a series of cobalt polypyridine redox mediators on the overall device performance in DSCs as well as on transport and recombination processes in these devices was compared. The recombination and mass-transport limitations that, previously, have been found to limit the performance of these mediators were avoided by matching the properties of the dye and the cobalt redox mediator. Organic dyes with higher extinction coefficients than the standard ruthenium sensitizers were employed in DSCs in combination with outer-sphere redox mediators, enabling thinner TiO(2) films to be used. Recombination was reduced further by introducing insulating butoxyl chains on the dye rather than on the cobalt redox mediator, enabling redox couples with higher diffusion coefficients and more suitable redox potential to be used, simultaneously improving the photocurrent and photovoltage of the device. Optimization of DSCs sensitized with a triphenylamine-based organic dye in combination with tris(2,2'-bipyridyl)cobalt(II/III) yielded solar cells with overall conversion efficiencies of 6.7% and open-circuit potentials of more than 0.9 V under 1000 W m(-2) AM1.5 G illumination. Excellent performance was also found under low light intensity indoor conditions.

Textile Inspired Lithium-Oxygen Battery Cathode with Decoupled Oxygen and Electrolyte Pathways.

PubMed

Xu, Shaomao; Yao, Yonggang; Guo, Yuanyuan; Zeng, Xiaoqiao; Lacey, Steven D; Song, Huiyu; Chen, Chaoji; Li, Yiju; Dai, Jiaqi; Wang, Yanbin; Chen, Yanan; Liu, Boyang; Fu, Kun; Amine, Khalil; Lu, Jun; Hu, Liangbing

2018-01-01

The lithium-air (Li-O 2 ) battery has been deemed one of the most promising next-generation energy-storage devices due to its ultrahigh energy density. However, in conventional porous carbon-air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile-based air cathode is developed with a triple-phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile-based Li-O 2 cathode exhibits a high discharge capacity of 8.6 mAh cm -2 , a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile-based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. The reported decoupled transport pathway design also spurs potential toward flexible/wearable Li-O 2 batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

All-in-One Gel-Based Electrochromic Devices: Strengths and Recent Developments

PubMed Central

Viñuales, Ana; Rodriguez, Javier; Tena-Zaera, Ramón

2018-01-01

Electrochromic devices (ECDs) have aroused great interest because of their potential applicability in displays and smart systems, including windows, rearview mirrors, and helmet visors. In the last decades, different device structures and materials have been proposed to meet the requirements of commercial applications to boost market entry. To this end, employing simple device architectures and achieving a competitive electrolyte are crucial to accomplish easily implementable, high-performance ECDs. The present review outlines devices comprising gel electrolytes as a single electroactive layer (“all-in-one”) ECD architecture, highlighting some advantages and opportunities they offer over other electrochromic systems. In this context, gel electrolytes not only overcome the drawbacks of liquid and solid electrolytes, such as liquid’s low chemical stability and risk of leaking and soil’s slow switching and lack of transparency, but also exhibit further strengths. These include easier processability, suitability for flexible substrates, and improved stabilization of the chemical species involved in redox processes, leading to better cyclability and opening wide possibilities to extend the electrochromic color palette, as discussed herein. Finally, conclusions and outlook are provided. PMID:29534466

The role of ionic liquid electrolyte in an aluminum–graphite electrochemical cell

DOE PAGES

Agiorgousis, Michael L.; Sun, Yi -Yang; Zhang, Shengbai

2017-02-17

Using first-principles calculations and molecular dynamics simulation, we study the working mechanism in an aluminum–graphite electrochemical cell, which was recently reported to exhibit attractive performance. We exclude the possibility of Al 3+ cation intercalation into graphite as in standard Li-ion batteries. Instead, we show that the AlCl 4 – anion intercalation mechanism is thermodynamically feasible. By including the ionic liquid electrolyte in the overall redox reaction, we are able to reproduce the high voltage observed in experiment. The active involvement of electrolyte in the reaction suggests that the evaluation of energy density needs to take the electrolyte into consideration. Here,more » our proposed structural model is consistent with the new peaks appearing in X-ray diffraction from the intercalation compound. The high rate capability is explained by the ultralow diffusion barriers of the AlCl 4 intercalant. With the clarified working mechanism, it becomes clear that the high voltage of the Al–graphite cell is a result of the thermodynamic instability of the AlCl 4-intercalated graphite.« less

A new type of high energy asymmetric capacitor with nanoporous carbon electrodes in aqueous electrolyte

NASA Astrophysics Data System (ADS)

Khomenko, V.; Raymundo-Piñero, E.; Béguin, F.

A new type of low cost and high energy asymmetric capacitor based on only activated carbons for both electrodes has been developed in a safe and environment friendly aqueous electrolyte. In such electrolyte, the charges are stored in the electrical double-layer and through fast faradaic charge transfer processes. By taking profit of different redox reactions occurring in the positive and negative ranges of potential, it is possible to optimize the capacitor either by balancing the mass of the electrodes or by using different optimized carbons for the positive and negative electrodes. The best results are obtained in the latter case, by utilizing different pseudo-faradaic properties of carbons in order to increase the capacitance and to shift the potentials of water decomposition and destructive oxidation of activated carbon to more negative and positive values, respectively. After an additional adjustment of potentials by mass-balancing the two electrodes, the electrochemical capacitor can be reversibly charged/discharged at 1.6 V in aqueous medium, with energy densities close to the values obtained with electrical double-layer capacitors working in organic electrolytes, while avoiding their disadvantages.

Metal-Free Aqueous Flow Battery with Novel Ultrafiltered Lignin as Electrolyte

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

Mukhopadhyay, Alolika; Hamel, Jonathan; Katahira, Rui

As the number of generation sources from intermittent renewable technologies on the electric grid increases, the need for large-scale energy storage devices is becoming essential to ensure grid stability. Flow batteries offer numerous advantages over conventional sealed batteries for grid storage. In this work, for the first time, we investigated lignin, the second most abundant wood derived biopolymer, as an anolyte for the aqueous flow battery. Lignosulfonate, a water-soluble derivative of lignin, is environmentally benign, low cost and abundant as it is obtained from the byproduct of paper and biofuel manufacturing. The lignosulfonate utilizes the redox chemistry of quinone tomore » store energy and undergoes a reversible redox reaction. Here, we paired lignosulfonate with Br2/Br-, and the full cell runs efficiently with high power density. Also, the large and complex molecular structure of lignin considerably reduces the electrolytic crossover, which ensures very high capacity retention. The flowcell was able to achieve current densities of up to 20 mA/cm2 and charge polarization resistance of 15 ohm cm2. This technology presents a unique opportunity for a low-cost, metal-free flow battery capable of large-scale sustainable energy storage.« less

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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