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At least 595 records · Page 33

Redox Flow Battery Having Metal-Ligand Complex

Researchers at Los Alamos National Laboratory have developed new non-aqueous electrolyte materials for redox flow batteries (RFB). These batteries are a viable technology for scalable energy storage beyond lithium ion batteries. Cost is currently limiting deployment, with poor energy density being the primary culprit. One way to improve energy density is by increasing the cell potential beyond the current limit in aqueous media. The higher cell potential and additional electrons stored per molecule will increase the energy density of the RFB medium, overcoming a critical limitation to the current RFBs. Like lithium ion batteries, RFB's can span from the kW to multi MW power storage systems. The nickel complexes described herein have demonstrated redox potentials >3 V which is at least twice the aqueous limit. We are interested in partnering with battery developers to further advance this technology to the product prototype stage.

25 ENERGY STORAGE↗

Where Have All of the Electrons Gone? Understanding the Role of Alternative Electron Flow and O 2 Reduction in Balancing Cellular Redox (Final Technical Report)

An informed understanding of the fundamentals of light-driven electron transfer reactions in photoautotrophic organisms is necessary to enable improved photosynthetic efficiencies for the production of renewable fuels and novel biomaterials. To obtain high photosynthetic yields, light energy must be efficiently coupled to the fixation of CO 2 . Sub-optimal environmental conditions and metabolic routing (caused by blocks in biosynthetic routes) can severely impact the conversion of light energy to biomass and lead to reactive oxygen production, which in turn can cause cellular damage and productivity losses. Hence, plants, algae, and photosynthetic bacteria have evolved a network of alternative outlets to sustain the flow of photosynthetically derived-electrons. Our research was focused on the nature and integration of these outlets. The data obtained in this project will inform efforts to rationally engineer crop plants and algae to improve photosynthetic yields by enhancing electron transfer reactions to CO 2 reduction and targeted biomass accumulation. A major project research thrust was focused on identifying and quantifying the flow of photosynthetic reductant through electron transfer circuits that result in the light-dependent reduction of O 2 . New energy management strategies were identified that are used when normal carbon assimilation pathways are compromised due to nutrient deprivation, and/or by a reduction in starch synthesis/carbon storage, all conditions resulting in highly reduced intracellular redox pools. The green alga Chlamydomonas reinhardtii, and likely many other algae, have multiple O 2 -reducing pathways that play critical roles in maintaining cellular metabolic balance and scavenging electrons that could potentially cause cellular damage, which in some instances leads to reduced photosynthetic yields but increased fitness. We explored the activities of three essential outlets associated with Chlamydomonas reinhardtii photosynthetic electron transport: (1) reduction of O 2 to H 2 O through Flavodiiron proteins (FLVs) and (2) Plastid Terminal Oxidases (PTOX), and (3) the synthesis of starch. Real-time measurements of O 2 exchange demonstrated that FLVs immediately engage during dark to light transitions, allowing electron transport when the CBBC is not fully activated. Under these conditions, we quantified, for the first time, maximal FLV activity and its overall capacity to direct photosynthetic electrons towards O 2 reduction. However, when starch synthesis is compromised, a greater proportion of electrons is directed toward O 2 reduction through the FLVs, while PTOX, which is sensitive to the PQ pool redox state, is activated. This suggests, that starch synthesis has an important role in priming/regulating CBBC and electron transport. We also identified a biological ‘switch’ in the green alga Chlamydomonas reinhardtii that reversibly restricts photosynthetic electron transport (PET) at the cytochrome b 6 f complex when reductant and ATP generated by PET are in excess of the capacity of carbon metabolism to utilize these products; we specifically show a restriction at this switch when sta6 mutant cells, which cannot synthesize starch, are limited for nitrogen (growth inhibition) and subjected to a dark to light transition. This restriction causes diminished electron flow to PSI, which prevents PSI photodamage, and the plastid alternative oxidase (PTOX) becomes fully activated, serving as an electron valve that dissipates excitation energy absorbed by PSII, thereby lessening PSII photoinhibition. Furthermore, illumination of the cells following the dark acclimation gradually diminishes the restriction at the switch. Future engineering of these switches may allow more effective electron transfer to lipid (biofuel) pathways and diminish the number of electrons “wasted” in the reduction of O 2 to water. Lastly, we explored metabolic routing of electrons during algal fermentation and discovered multiple novel pathways that are activated when the preferred anoxic routes are blocked. These provide valuable products (e.g. lactate, glycerol) that can be used in broad portfolio of biotechnological applications.

59 BASIC BIOLOGICAL SCIENCES↗

Supramolecular Control of Redox-Mediated Interactions for Ion-Selective Electroseparations

This report summarizes efforts from the Su Group at the University of Illinois at Urbana-Champaign in researching and developing materials and processes for the recovery of rare earth elements and other metal elements that are critical to the United States economy and national security, under DOE Award No. DE-SC0021409. This report highlights efforts in the recovery of: • Transition metal elements (including arsenic, chromium, molybdenum, rhenium, vanadium): Redox-active metallopolymers are able to capture these elements in their oxyanion form. Direct control of target ion capture/release through electrochemical-mediated switching of metallocene binding sites reduces chemical input and lowers generation of waste in element recovery processes. We study the effects of metallopolymer structure on targeted ion binding through a combination of experimental screening of ion selectivity from multi-component mixtures, computational efforts which elucidate the charge-transfer origins of metallocene binding and provide insight on how binding site structure influences selectivity, and state-of-the-art neutron reflectivity of metallocene polymer films to understand the interplay of polymer-ion (charge-transfer), polymer-solvent (polymer hydrophilicity/hydrophobicity), and ion-solvent (ion hydration) interactions with spatial resolution of polymer films. • Rare earth elements (including yttrium, neodymium, europium, gadolinium, dysprosium, cerium): Here we employ redox-copolymers for recovery of rare earth elements by electrochemically regenerated ion-exchange. Rare earth elements require an alternative route to capture/release than directly with metallopolymers since rare earth elements typically exist in cationic form in water. To address this, copolymerization of traditional ion-exchange moieties with metallocene moieties allowed for capture of rare earth elements with the ion-exchange moieties and electrochemical-mediated release of rare earth elements through oxidation of metallocene moieties.

36 MATERIALS SCIENCE↗

Radiation-Induced Late Actinides Redox Chemistry

The goal of this proposal was to understand how radiation alters actinide redox chemistry, especially via the generation of transient oxidation states that typically cannot be isolated in bulk and need to be measured on ultrafast timescales. While these studies are of fundamental importance, they also impact the recycling of used nuclear fuel because the radiation field not only alters the oxidation states of actinides, but also induces chemical transformations of the extractants, typically in a deleterious manner. The majority of actinide radiation chemistry knowledge is concentrated toward the beginning of the series especially for uranium and plutonium, for which radiation-induced reactions have been demonstrated to significantly impact the accessibility and lifetime of actinide oxidation states at both ultrafast (pico- to microseconds) and steady-state timescales. Furthermore, there is precedence for these radiation-induced actinide redox reactions altering the radiolytic integrity of their corresponding complexes, relative to the free ligand, through facilitation of inner- versus outer-sphere reaction pathways.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Predicting Radiation-Induced Plutonium Redox Chemistry using Multiscale Modeling Methods

Over the the last 70 years plutonium (Pu) has been integral in the development of several technologies that have changed the world, yet our fundamental understanding of its chemistry is still far from complete. This is a testament to this element?s unique and complex properties, such as its ability to coexist as multiple oxidation states in aqueous solution. Careful manipulation of plutonium oxidation states is essential in the study and utilization of its rich chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. For this reason, we have developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Scalable Solar Fuels Production in A Reactor Train System by Thermochemical Redox Cycling of Novel Nonstoichiometric Perovskites

Hydrogen production via two-step thermochemical water splitting redox cycles using nonstoichiometric redox-active metal oxides has the potential to dramatically increase fuel production rates. At moderate-to-low water splitting temperatures, surface reaction kinetics co-limit the process. In such cases, stable and high surface area microstructures that allow exploitation of the full thermodynamic potential of the materials are essential as is tight thermal integration of the reactor module. This project’s goals were the development of novel nonstoichiometric perovskite oxides with high stability and favorable thermodynamic and kinetic properties, to optimize their microstructure for maximizing the fuel productivity, and to build a prototype reactor train system (RTS) comprising at least one reactor to meet specific performance targets: (1) capable of an in-house solar thermochemical hydrogen (STCH) productivity ≥ 12 mL g -1 for stable continuous operation ≥ 20 cycles; and (2) demonstration of scalable solar fuels production at practical solar reactor level in an industrial-scale concentrated solar tower (CST) using developed perovskites to achieve a hydrogen production rate ≥ 1 g h -1 .

08 HYDROGEN↗

Ferrocene Bis(Sulfonate) Salt as Redoxmer for Fast and Steady Redox Flow Desalination

Desalination is considered a promising solution to alleviate water shortages, yet current methods are often restricted, due to challenges like high energy consumption, significant cost, or limited desalination capacity. In this study, we present a novel approach of redox flow desalination (RFD) utilizing the highly aqueous-soluble and reversible redox-active compound, potassium 1,1'-bis(sulfonate) ferrocene (1,1'-FcDS). This water-soluble organic compound yielded stable and rapid desalination, sustaining extended operation without notable decay and achieving an impressive desalination rate of up to 457.5 mmol·h -1 ·m -2 and energy consumption as low as 40.2 kJ·mol NaCl -1 . Specifically, the RFD device effectively desalinated a 50 mM NaCl solution to potable standards within 6000 s using 1,1'-FcDS. It maintained an average energy consumption of 178.16 kJ·mol NaCl -1 and exhibited negligible deterioration in desalination rate, energy efficiency, and charge efficiency throughout a rigorous 12,000 s cycling test. Furthermore, the versatility of this method was demonstrated by effectively treating saline water with varying initial concentrations from 10 mM to 50 mM, showcasing its potential across a broad spectrum of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrically rechargeable redox flow cells

Considering the topographical and sizing requirements for a typical pumped water storage installation and the immergence of energy conversion schemes that are time dependent as to their generating capability, a closer look is being given to nonpumped water storage schemes for storing electricity. An electrochemical bulk power storage concept, which was named a rechargeable redox flow cell is described. This scheme, based on pumping a redox couple through a power conversion section, appears to offer high overall efficiency, no cycle life limitations for the electrodes, and deep discharger capability.

Thaller, L. H.↗

Electrically rechargeable redox flow cells

Considering the topographical and sizing requirements for a typical pumped water storage installation and the immergence of energy conversion schemes that are time-dependent as to their generating capability, a closer look is being given to nonpumped water storage schemes for storing electricity. An electrochemical bulk power storage concept, called a rechargeable redox flow cell, is described. This scheme, based on pumping a redox couple through a power conversion section, appears to offer high overall efficiency, no cycle life limitations for the electrodes, and deep discharge capability.

Thaller, L. H.↗

Redox flow cell development and demonstration project, calendar year 1976

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

Source record↗

Redox equilibria of multivalent ions in silicate glasses

Experimental studies were made on the compositional dependence of the redox equilibrium of Eu in synthetic silicate liquids, together with an empirical model describing the observed compositional dependence. Electron paramagnetic resonance (EPR) was used to measure the concentration ratio of Eu(2+) to Eu(3+) in various glasses formed by rapidly quenching silicate liquids. The compositional field studied comprised mixtures of SiO2, TiO2, Al2O3, CaO, MgO, and Na2O. The proposed model describes the Eu(2+)/Eu(3+) ratio over the entire compositional field in terms of parameters easily related to each glass composition. The general applicability and utility of the model is further demonstrated by its application to the Fe(2+)-Fe(3+), Ce(3+)-Ce(4+), and Cr(3+)-Cr(6+) redox reactions in binary alkali oxide silicate glasses of Li, Na, and K.

Lauer, H. V., Jr.↗

Supply of reactants for Redox bulk energy storage systems

World resources, reserves, production, and costs of reactant materials, iron, chromium, titanium and bromine for proposed redox cell bulk energy storage systems are reviewed. Supplying required materials for multimegawatt hour systems appears to be feasible even at current production levels. Iron and chromium ores are the most abundant and lowest cost of four reactants. Chromium is not a domestic reserve, but redox system installations would represent a small fraction of U.S. imports. Vast quantities of bromine are available, but present production is low and therefore cost is high. Titanium is currently available at reasonable cost, with ample reserves available for the next fifty years.

Gahn, R. F.↗

Recent advances in redox flow cell storage systems

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

Thaller, L. H.↗

Recent advances in Redox flow cell storage systems

Attention is given to recent data pertaining to flow cell storage system-related features as well as the state of Redox membrane technology. In addition, the state of the technology as it relates to the two application areas of storage for photovoltaic/wind and distributed energy storage for electrical utility applications is addressed. Also covered are the cost and life advantages of Redox systems as well as a discussion of such cells as the open circuit voltage cell, the rebalance cell, and the trim cell. Finally, it is concluded that the main thrust of membrane development will be to reduce the interaction between the chloro complex of iron in the ferric state since this is the major factor in membrane area resistivity.

Thaller, L. H.↗

Catalyst surfaces for the chromous/chromic redox couple

An electricity producing cell of the reduction-oxidation (REDOX) type is described. The cell is divided into two compartments by a membrane, each compartment containing a solid inert electrode. A ferrous/ferric couple in a chloride solution serves as a cathode fluid which is circulated through one of the compartments to produce a positive electric potential disposed therein. A chromic/chromous couple in a chloride solution serves as an anode fluid which is circulated through the second compartment to produce a negative potential on an electrode disposed therein. The electrode is an electrically conductive, inert material plated with copper, silver or gold. A thin layer of lead plates onto the copper, silver or gold layer when the cell is being charged, the lead ions being available from lead chloride which was added to the anode fluid. If the REDOX cell is then discharged, the current flows between the electrodes causing the lead to deplate from the negative electrode and the metal coating on the electrode will act as a catalyst to cause increased current density.

Giner, J. D.↗

Redox storage systems for solar applications

The NASA Redox energy storage system is described. The system is based on soluble aqueous iron and chromium chloride redox couples. The needed technology advances in the two elements (electrodes and membranes) that are key to its technological feasibility have been achieved and system development has begun. The design, construction, and test of a 1 kilowatt system integrated with a solar photovoltaic array is discussed.

Hagedorn, N. H.↗

Improvement and scale-up of the NASA Redox storage system

A preprototype 1.0 kW redox system (2 kW peak) with 11 kWh storage capacity was built and integrated with the NASA/DOE photovoltaic test facility at NASA Lewis. This full function redox system includes four substacks of 39 cells each (1/3 cu ft active area) which are connected hydraulically in parallel and electrically in series. An open circuit voltage cell and a set of rebalance cells are used to continuously monitor the system state of charge and automatically maintain the anode and cathode reactants electrochemically in balance. Recent membrane and electrode advances are summarized and the results of multicell stack tests of 1 cu ft are described.

Reid, M. A.↗

Cost projections for Redox Energy storage systems

A preliminary design and system cost analysis was performed for the redox energy storage system. A conceptual design and cost estimate was prepared for each of two energy applications: (1) electric utility 100-MWh requirement (10-MW for ten hours) for energy storage for utility load leveling application, and (2) a 500-kWh requirement (10-kW for 50 hours) for use with a variety of residential or commercial applications, including stand alone solar photovoltaic systems. The conceptual designs were based on cell performance levels, system design parameters, and special material costs. These data were combined with estimated thermodynamic and hydraulic analysis to provide preliminary system designs. Results indicate that the redox cell stack to be amenable to mass production techniques with a relatively low material cost.

Michaels, K.↗