200-Fold Lifetime Extension of 2,6- Dihydroxyanthraquinone Electrolyte during Flow Battery Operation.

We study the capacity fade rate of a flow battery utilizing 2,6-dihydroxyanthraquinone (DHAQ) and its dependence on hydroxide concentration, state of charge, cutoff voltages for the discharge step and for the electrochemical regeneration (oxidation of decomposition compounds back to active species) step, and the period of performing the electrochemical regeneration events. Our observations confirm that the first decomposition product, 2,6-dihydroxyanthrone (DHA), is stable, but after electro-oxidative dimerization, the anthrone dimer decomposes. We identify conditions for which there is little time after dimerization until the dimer is rapidly reoxidized electrochemically to form DHAQ.

Reversible CO Capture and On-Demand Release by an Acidity-Matched Organic Photoswitch.

Separation of carbon dioxide (CO) from point sources or directly from the atmosphere can contribute crucially to climate change mitigation plans in the coming decades. A fundamental practical limitation for the current strategies is the considerable energy cost required to regenerate the sorbent and release the captured CO for storage or utilization. A directly photochemically driven system that demonstrates efficient passive capture and on-demand CO release triggered by sunlight as the sole external stimulus would provide an attractive alternative.

Membrane-Electrolyte System Approach to Understanding Ionic Conductivity and Crossover in Alkaline Flow Cells.

Membrane transport properties are crucial for electrochemical devices, and these properties are influenced by the composition and concentration of the electrolyte in contact with the membrane. We apply this general membrane-electrolyte system approach to alkaline flow batteries, studying the conductivity and ferricyanide crossover of Nafion and E-620. We report undetectable crossover for as-received Nafion and E-620 after both sodium and potassium exchange but high ferricyanide permeability of 10 to 10 cm s for Nafion subjected to pretreatment prevalent in the flow battery literature.

Low energy carbon capture via electrochemically induced pH swing with electrochemical rebalancing.

We demonstrate a carbon capture system based on pH swing cycles driven through proton-coupled electron transfer of sodium (3,3'-(phenazine-2,3-diylbis(oxy))bis(propane-1-sulfonate)) (DSPZ) molecules. Electrochemical reduction of DSPZ causes an increase of hydroxide concentration, which absorbs CO; subsequent electrochemical oxidation of the reduced DSPZ consumes the hydroxide, causing CO outgassing. The measured electrical work of separating CO from a binary mixture with N, at CO inlet partial pressures ranging from 0.

Alkalinity Concentration Swing for Direct Air Capture of Carbon Dioxide.

The alkalinity concentration swing (ACS) is a new process for direct air capture of carbon dioxide driven by concentrating an alkaline solution that has been exposed to the atmosphere and loaded with dissolved inorganic carbon. Upon concentration, the partial pressure of CO increases, allowing for extraction and compression. Higher concentration factors result in proportionally higher outgassing pressure, and higher initial alkalinity concentrations at the same concentration factor outgas a higher concentration of CO .

Functioning Water-Insoluble Ferrocenes for Aqueous Organic Flow Battery via Host-Guest Inclusion.

Ferrocene (Fc) is one of the very limited organic catholyte options for aqueous organic flow batteries (AOFBs), a potential electrochemical energy storage solution to the intermittency of renewable electricity. Commercially available Fc derivatives are barely soluble in water, while existing methods for making water-soluble Fc derivatives by appending hydrophilic or charged moieties are tedious and time-consuming, with low yields. Here, a strategy was developed based on host-guest inclusion to acquire water-soluble Fc-based catholytes by simply mixing Fc derivatives with β-cyclodextrins (β-CDs) in water.

Electrolyte Lifetime in Aqueous Organic Redox Flow Batteries: A Critical Review.

Aqueous organic redox flow batteries (RFBs) could enable widespread integration of renewable energy, but only if costs are sufficiently low. Because the levelized cost of storage for an RFB is a function of electrolyte lifetime, understanding and improving the chemical stability of active reactants in RFBs is a critical research challenge. We review known or hypothesized molecular decomposition mechanisms for all five classes of aqueous redox-active organics and organometallics for which cycling lifetime results have been reported: quinones, viologens, aza-aromatics, iron coordination complexes, and nitroxide radicals.

Extending the Lifetime of Organic Flow Batteries via Redox State Management.

Redox flow batteries based on quinone-bearing aqueous electrolytes have emerged as promising systems for energy storage from intermittent renewable sources. The lifetime of these batteries is limited by quinone stability. Here, we confirm that 2,6-dihydroxyanthrahydroquinone tends to form an anthrone intermediate that is vulnerable to subsequent irreversible dimerization.

Potential revenue and breakeven of energy storage systems in PJM energy markets.

The operation in energy arbitrage markets is an attractive possibility to energy storage systems developers and owners to justify an investment in this sector. The size and the point of connection to the grid can have significant impact on the net revenue in transmission and distribution systems. The decision to install an energy storage system cannot be based only on the cost of the equipment but also in its potential revenue, operation costs, and depreciation through its life cycle.

Sawtooth structure formation under nonlinear-regime ion bombardment.

Linear-regime Ar bombardment of Si produces symmetrical ripple structures at ion incidence angles above 45° measured off-normal (Madi 2009 J. Phys.: Condens.

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

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) ∼ 80 M.

Distinguishing physical mechanisms using GISAXS experiments and linear theory: the importance of high wavenumbers.

In this work we analyze GISAXS measurements of the structure factor of Si surfaces evolving during 1 keV Ar+ ion bombardment. Using newly-developed methods sensitive to the full range of experimentally-available wavenumbers q, we extract the linear amplification rate R(q) governing surface stability over a range of wavenumbers 4-5 times larger than has previously been obtained. Comparing with theoretical models also retaining full wavenumber-dependence, we find an excellent fit of the experimental data over the full range of irradiation angles and wavenumbers.

Designing steep, sharp patterns on uniformly ion-bombarded surfaces.

We propose and experimentally test a method to fabricate patterns of steep, sharp features on surfaces, by exploiting the nonlinear dynamics of uniformly ion-bombarded surfaces. We show via theory, simulation, and experiment that the steepest parts of the surface evolve as one-dimensional curves that move in the normal direction at constant velocity. The curves are a special solution to the nonlinear equations that arises spontaneously whenever the initial patterning on the surface contains slopes larger than a critical value; mathematically they are traveling waves (shocks) that have the special property of being undercompressive.

Alkaline quinone flow battery.

Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments.

Room-temperature sub-band gap optoelectronic response of hyperdoped silicon.

Room-temperature infrared sub-band gap photoresponse in silicon is of interest for telecommunications, imaging and solid-state energy conversion. Attempts to induce infrared response in silicon largely centred on combining the modification of its electronic structure via controlled defect formation (for example, vacancies and dislocations) with waveguide coupling, or integration with foreign materials. Impurity-mediated sub-band gap photoresponse in silicon is an alternative to these methods but it has only been studied at low temperature.

Insulator-to-metal transition in selenium-hyperdoped silicon: observation and origin.

Hyperdoping has emerged as a promising method for designing semiconductors with unique optical and electronic properties, although such properties currently lack a clear microscopic explanation. Combining computational and experimental evidence, we probe the origin of sub-band-gap optical absorption and metallicity in Se-hyperdoped Si. We show that sub-band-gap absorption arises from direct defect-to-conduction-band transitions rather than free carrier absorption.

Insulator-to-metal transition in sulfur-doped silicon.

We observe an insulator-to-metal transition in crystalline silicon doped with sulfur to nonequilibrium concentrations using ion implantation followed by pulsed-laser melting and rapid resolidification. This insulator-to-metal transition is due to a dopant known to produce only deep levels at equilibrium concentrations. Temperature-dependent conductivity and Hall effect measurements for temperatures T>1.

Thermal activation and saturation of ion beam sculpting.

We report a material-dependent critical temperature for ion beam sculpting of nanopores in amorphous materials under keV ion irradiation. At temperatures below the critical temperature, irradiated pores open at a rate that soon saturates with decreasing temperature. At temperatures above the critical temperature, the pore closing rate rises rapidly and eventually saturates with increasing temperature.

Molecular dynamics of single-particle impacts predicts phase diagrams for large scale pattern formation.

Energetic particle irradiation can cause surface ultra-smoothening, self-organized nanoscale pattern formation or degradation of the structural integrity of nuclear reactor components. A fundamental understanding of the mechanisms governing the selection among these outcomes has been elusive. Here we predict the mechanism governing the transition from pattern formation to flatness using only parameter-free molecular dynamics simulations of single-ion impacts as input into a multiscale analysis, obtaining good agreement with experiment.

Mass redistribution causes the structural richness of ion-irradiated surfaces.

We show that the "sputter patterning" topographical instability is determined by the effects of ion impact-induced prompt atomic redistribution and that erosion--the consensus predominant cause--is essentially irrelevant. We use grazing incidence small angle x-ray scattering to measure in situ the damping of noise or its amplification into patterns via the linear dispersion relation. A model based on the effects of impact-induced redistribution of those atoms that are not sputtered away explains both the observed ultrasmoothening at low angles from normal incidence and the instability at higher angles.

Nanopore fabrication in amorphous Si: Viscous flow model and comparison to experiment.

Nanopores fabricated in free-standing amorphous silicon thin films were observed to close under 3 keV argon ion irradiation. The closing rate, measured in situ, exhibited a memory effect: at the same instantaneous radius, pores that started larger close more slowly. An ion-stimulated viscous flow model is developed and solved in both a simple analytical approximation for the small-deformation limit and in a finite element solution for large deformations.