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 10-7 to 10-8 cm2 s-1 for Nafion subjected to pretreatment prevalent in the flow battery literature. We show how the electrolyte mass fraction in hydrated membranes regulates the influence of ion concentration on membrane conductivity, identifying that increasing electrolyte concentration may not increase membrane conductivity even when it increases electrolyte conductivity. To illustrate this behavior, we introduce a new metric, the membrane penalty, as the ratio of the conductivity of the electrolyte to that of the membrane equilibrated with the electrolyte. We discuss the trade-off between flow battery volumetric capacity and areal power density that arises from these findings. Finally, we apply insights from this approach to provide recommendations for use of membranes in alkaline flow cells and electrochemical reactors in general.

Reversible CO2 Capture and On-Demand Release by an Acidity-Matched Organic Photoswitch.

Separation of carbon dioxide (CO2) 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 CO2 for storage or utilization. A directly photochemically driven system that demonstrates efficient passive capture and on-demand CO2 release triggered by sunlight as the sole external stimulus would provide an attractive alternative. However, little is known about the thermodynamic requirements for such a process or mechanisms for modulating the stability of CO2-derived dissolved species by using photoinduced metastable states. Here, we show that an organic photoswitchable molecule of precisely tuned effective acidity can repeatedly capture and release a near-stoichiometric quantity of CO2 according to dark-light cycles. The CO2-derived species rests as a solvent-separated ion pair, and key aspects of its excited-state dynamics that regulate the photorelease efficiency are characterized by transient absorption spectroscopy. The thermodynamic and kinetic concepts established herein will serve as guiding principles for the development of viable solar-powered negative emission technologies.

In situ electrochemical recomposition of decomposed redox-active species in aqueous organic flow batteries.

Aqueous organic redox flow batteries offer a safe and potentially inexpensive solution to the problem of storing massive amounts of electricity produced from intermittent renewables. However, molecular decomposition represents a major barrier to commercialization-and although structural modifications can improve stability, it comes at the expense of synthetic cost and molecular weight. Now, utilizing 2,6-dihydroxy-anthraquinone (DHAQ) without further structural modification, we demonstrate that the regeneration of the original molecule after decomposition represents a viable route to achieve low-cost, long-lifetime aqueous organic redox flow batteries. We used in situ (online) NMR and electron paramagnetic resonance, and complementary electrochemical analyses to show that the decomposition compound 2,6-dihydroxy-anthrone (DHA) and its tautomer, 2,6-dihydroxy-anthranol (DHAL) can be recomposed to DHAQ electrochemically through two steps: oxidation of DHA(L)2- to the dimer (DHA)24- by one-electron transfer followed by oxidation of (DHA)24- to DHAQ2- by three-electron transfer per DHAQ molecule. This electrochemical regeneration process also rejuvenates the positive electrolyte-rebalancing the states of charge of both electrolytes without introducing extra ions.

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 CO2; subsequent electrochemical oxidation of the reduced DSPZ consumes the hydroxide, causing CO2 outgassing. The measured electrical work of separating CO2 from a binary mixture with N2, at CO2 inlet partial pressures ranging from 0.1 to 0.5 bar, and releasing to a pure CO2 exit stream at 1.0 bar, was measured for electrical current densities of 20-150 mA cm-2. The work for separating CO2 from a 0.1 bar inlet and concentrating into a 1 bar exit is 61.3 kJ molCO2-1 at a current density of 20 mA cm-2. Depending on the initial composition of the electrolyte, the molar cycle work for capture from 0.4 mbar extrapolates to 121-237 kJ molCO2-1 at 20 mA cm-2. We also introduce an electrochemical rebalancing method that extends cell lifetime by recovering the initial electrolyte composition after it is perturbed by side reactions. We discuss the implications of these results for future low-energy electrochemical carbon capture devices.

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 CO2 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 CO2 . Two desalination technologies, reverse osmosis and capacitive deionization, are examined as possible ACS implementations, and two corresponding energy models are evaluated. The ACS is compared to incumbent technologies and estimates for water, land, and energy requirements for capturing one million tonnes of CO2 per year are made. Estimates for the lower end of the energy range for both approaches compare favorably to other approaches, such as solid sorbent and calcining methods.

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. This paper illustrates the potential revenue of a generic energy storage system with 70% round trip efficiency and 1-14 h energy/power ratio, considering a price-taking dispatch. The breakeven overnight installed cost is also calculated to provide the cost below which energy arbitrage would have been profitable for a flow battery. The analysis of the potential revenue was performed for 13 locations within the PJM Real-time market. We considered hourly data of day-ahead and real-time locational marginal prices over 7 years (2008-2014). Breakeven installed cost per MW ranged from $30 (1 MW, 14 MWh, 2009) to $340 (1 MW, 1 MWh, 2008).

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 ß-cyclodextrins (ß-CDs) in water. Factors determining the stability and the electrochemical behavior of the inclusion complexes were identified. When adopted in a neutral pH AOFB, the origin of capacity loss was identified to be a chemical degradation caused by the nucleophilic attack on the center FeIII atom of the oxidized Fc derivatives. By limiting the state of charge, a low capacity fade rate of 0.0073 % h-1 (or 0.0020 % per cycle) was achieved. The proposed strategy may be extended to other families of electrochemically active water-insoluble organic compounds, bringing more electrolyte options for practical AOFB applications.

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. We collect, analyze, and compare capacity fade rates from all aqueous organic electrolytes that have been utilized in the capacity-limiting side of flow or hybrid flow/nonflow cells, noting also their redox potentials and demonstrated concentrations of transferrable electrons. We categorize capacity fade rates as being "high" (>1%/day), "moderate" (0.1-1%/day), "low" (0.02-0.1%/day), and "extremely low" (≤0.02%/day) and discuss the degree to which the fade rates have been linked to decomposition mechanisms. Capacity fade is observed to be time-denominated rather than cycle-denominated, with a temporal rate that can depend on molecular concentrations and electrolyte state of charge through, e.g., bimolecular decomposition mechanisms. We then review measurement methods for capacity fade rate and find that simple galvanostatic charge-discharge cycling is inadequate for assessing capacity fade when fade rates are low or extremely low and recommend refining methods to include potential holds for accurately assessing molecular lifetimes under such circumstances. We consider separately symmetric cell cycling results, the interpretation of which is simplified by the absence of a different counter-electrolyte. We point out the chemistries with low or extremely low established fade rates that also exhibit open circuit potentials of 1.0 V or higher and transferrable electron concentrations of 1.0 M or higher, which are promising performance characteristics for RFB commercialization. We point out important directions for future research.

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. We demonstrate quantitatively that this decomposition pathway is responsible for the loss of battery capacity. Computational studies indicate that the driving force for anthrone formation is greater for anthraquinones with lower reduction potentials. We show that the decomposition can be substantially mitigated. We demonstrate that conditions minimizing anthrone formation and avoiding anthrone dimerization slow the capacity loss rate by over an order of magnitude. We anticipate that this mitigation strategy readily extends to other anthraquinone-based flow batteries and is thus an important step toward realizing renewable electricity storage through long-lived organic flow batteries.

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. Matter 21). In the nonlinear regime, new behaviors emerge. In this paper, we present experimental results of ion bombardment that continues into the nonlinear regime until pattern saturation at multiple ion incidence angles, showing the evolution of their grazing incidence small-angle x-ray scattering (GISAXS) spectra as well as atomic force microscopy topographs of the final, saturated structures. Asymmetric structures emerge parallel to the direction of the projected ion beam on the sample surface, constituting a height asymmetry not found in the linear regime. We then present simulations of surface height evolution under ion bombardment using a nonlinear partial differential equation developed by Pearson and Bradley (2015 J. Phys.: Condens. Matter 27 015010). We present simulated GISAXS spectra from these simulations, as well as simulated scattering from a sawtooth structure using the FitGISAXS software package (Babonneau 2010 J. Appl. Crystallogr. 43 929-36), and compare the simulated spectra to those observed experimentally. We find that these simulations reproduce many features of the sawtooth structures, as well as the nearly-flat final GISAXS spectra observed experimentally perpendicular to the sawtooth structures. However, the model fails to reproduce the final GISAXS spectra observed parallel to the sawtooth structures.

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 (KQHQ) ∼ 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.

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. Moreover, the fitted parameter values represent experimental evaluation of the magnitudes of most physical mechanisms currently believed to be important to the pattern-formation process. In all cases, the extracted values agree well with direct observations or atomistic simulations of the same quantities, suggesting that GISAXS analysis may allow more powerful comparison between experiment and theory than had previously been thought.

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. We derive the evolution equation for the curves by considering long-wavelength perturbations to the one-dimensional traveling wave, using the unusual boundary conditions required for an undercompressive shock, and we show this equation accurately describes the evolution of shapes on surfaces, both in simulations and in experiments. Because evolving a collection of one-dimensional curves is fast, this equation gives a computationally efficient and intuitive method for solving the inverse problem of finding the initial surface so the evolution leads to a desired target pattern. We illustrate this method by solving for the initial surface that will produce a lattice of diamonds connected by steep, sharp ridges, and we experimentally demonstrate the evolution of the initial surface into the target pattern.

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. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy.

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. Here we demonstrate impurity-mediated room-temperature sub-band gap photoresponse in single-crystal silicon-based planar photodiodes. A rapid and repeatable laser-based hyperdoping method incorporates supersaturated gold dopant concentrations on the order of 10(20) cm(-3) into a single-crystal surface layer ~150 nm thin. We demonstrate room-temperature silicon spectral response extending to wavelengths as long as 2,200 nm, with response increasing monotonically with supersaturated gold dopant concentration. This hyperdoping approach offers a possible path to tunable, broadband infrared imaging using silicon at room temperature.

A metal-free organic-inorganic aqueous flow battery.

As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br(-) redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals represents a new and promising direction for realizing massive electrical energy storage at greatly reduced cost.

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. Density functional theory predicts the Se-induced insulator-to-metal transition arises from merging of defect and conduction bands, at a concentration in excellent agreement with experiment. Quantum Monte Carlo calculations confirm the critical concentration, demonstrate that correlation is important to describing the transition accurately, and suggest that it is a classic impurity-driven Mott transition.

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>1.7 K both indicate that a transition from insulating to metallic conduction occurs at a sulfur concentration between 1.8 and 4.3×10(20) cm(-3). Conduction in insulating samples is consistent with variable-range hopping with a Coulomb gap. The capacity for deep states to effect metallic conduction by delocalization is the only known route to bulk intermediate band photovoltaics in silicon.