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DOE OSTI2016

Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

The excited state relaxation dynamics of the solvated electron in H{sub 2}O and D{sub 2}O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H{sub 2}O and 102 ± 8 fs in D{sub 2}O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Understanding the chemical contribution to the enhancement mechanism in SERS: Connection with Hammett parameters

The enhancement mechanism due to the molecule-surface chemical interaction in surface-enhanced Raman scattering (SERS) has been characterized using a theoretical approach based on time dependent density functional theory. This includes a systematic study of the chemical mechanism (CM) to the SERS enhancement for halogen substituted benzenethiols interacting with a silver cluster. Changing the halogen on benzenethiol enables us to systematically modulate interactions between the benzenethiol ring and the metal cluster. We observe a decrease in the CM enhancement factor with an increase in atomic number of the halogen for para- substitutions. For meta- substitutions, there is no such trend. However, the results scale linearly with the Hammett parameters for both meta and para halogens, which provides an important predictive tool for interpreting chemical enhancements. We also study the effect of solvation on the CM, showing that there is a systematic increase in enhancement with increasing solvent dielectric constant. As a result, the correlation of CM with other properties, such as the amount of charge transfer between adsorbate and metal, or the excitation energies of charge transfer states, is much less predictive than the Hammett parameter correlation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Localized high concentration electrolytes decomposition under electron-rich environments

Localized high concentration electrolytes have been proposed as an effective route to construct stable solid–electrolyte interphase (SEI) layers near Li-metal anodes. However, there is still a limited understanding of decomposition mechanisms of electrolyte components during SEI formation. In this work, we investigate reactivities of lithium bis(fluorosulfonyl)imide (LiFSI, salt), 1,2-dimethoxyethane (DME, solvent) and tris(2,2,2-trifluoroethyl)orthoformate (TFEO, diluent) species in DME+TFEO mixed solvents and 1M LiFSI/DME/TFEO solutions. By supplying excess of electrons into the simulation cell, LiFSI is initially reduced via a 4-electron charge transferring reaction yielding F - and N(SO 2 ) 2 3- . The local solvation environment has little effect on the subsequent TFEO reaction, which typically requires 6 |e| to decompose into F - , HCOO - , CH2CF and - OCH 2 CF 3 . Besides, TFEO dehydrogenation reaction mechanism under the attack of anions is also identified. Unlike salt and diluent, DME shows good stability with any excess of electrons. Here, the energetics of most relevant reactions are characterized. Most reactions are thermodynamically favorable with low activation barriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions

Ultraviolet (UV) photolysis of nitrite ions (NO 2 – ) in aqueous solutions produces a suite of radicals, viz., NO · , O – , · OH, and · NO 2 . The O – and NO · radicals are initially formed from the dissociation of photoexcited NO 2 – . The O – radical undergoes reversible proton transfer with water to generate · OH. Both · OH and O – oxidize the NO 2 – to · NO 2 radicals. The reactions of · OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO · , · OH, and · NO 2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO 2 – solvation were determined to alter the initial yields of · NO and · OH radicals as well as alter the reactivity of NO 2 – toward · OH, impacting the production of · NO 2 . The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

How the choice of exchange–correlation functional affects DFT-based simulations of the hydrated electron

Hydrated electrons are anionic species that are formed when an excess electron is introduced into liquid water. Building an understanding of how hydrated electrons behave in solution has been a long-standing effort of simulation methods, of which density functional theory (DFT) has come to the fore in recent years. The ability of DFT to model the reactive chemistry of hydrated electrons is an attractive advantage over semi-classical methodologies; however, relatively few density functional approximations (DFAs) have been used for the hydrated electron simulations presented in the literature. Here, we simulate hydrated electron systems using a series of exchange–correlation (XC) functionals spanning Jacob’s ladder. We calculate a variety of experimental and other observables of the hydrated electron and compare the XC functional dependence for each quantity. We find that the formation of a stable localized hydrated electron is not necessarily limited to hybrid XC functionals and that some hybrid functionals produce delocalized hydrated electrons or electrons that react with the surrounding water at an unphysically fast rate. Here, we further characterize how different DFAs impact the solvent structure and predicted spectroscopy of the hydrated electron, considering several methods for calculating the hydrated electron’s absorption spectrum for the best comparison between structures generated using different density functionals. None of the dozen or so DFAs that we investigated are able to correctly predict the hydrated electron’s spectroscopy, vertical detachment energy, or molar solvation volume.

Ab-initio molecular dynamics↗

DOE OSTI2021

Nuclear quantum effects on the quasiparticle properties of the chloride anion aqueous solution within the GW approximation

Photoelectron spectroscopy experiments in ionic solutions reveal important electronic structure information, in which the interaction between hydrated ions and water solvent can be inferred. Based on many-body perturbation theory with GW approximation, we theoretically compute the quasiparticle electronic structure of chloride anion solution, which is modeled by path-integral abinitio molecular dynamics simulation by taking account the nuclear quantum effects (NQEs). The electronic levels of hydrated anion as well as water are determined and compared with the recent experimental photoelectron spectra. It is found that NQEs improve the agreement between theoretical prediction and experiment because NQEs effectively weaken the hybridization of the between the Cl – anion and water. Furthermore, our study indicates that NQEs plays a small but non-negligible role in predicting the electronic structure of the aqueous solvation of ions of the Hofmeister series.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Operando Measurements of Electrolyte Li-ion Concentration during fast charging with FTIR/ATR

The ability to charge a Li-ion battery at high charging rates is critical for electric vehicle adoption; however, further study of ion transport is required to develop electrolytes suitable for fast charge. Fourier transform infrared spectroscopy (FTIR) used with attenuated total reflection (ATR) enables operando measurements of liquid electrolytes. This research focused on solvation shifting of solvent infrared absorption bands in the presence of lithium ions. Lithium-shifted infrared absorption bands and non-shifted bands of ethyl methyl carbonate (EMC) and ethylene carbonate (EC) were compared to infer ion concentration changes during cycling. Lithium concentrations were calibrated using EC/EMC/LiPF 6 electrolytes with known lithium concentrations. A Li-ion half-cell with a graphite anode and EC/EMC/LiPF 6 electrolyte was observed with FTIR/ATR. The results showed that the magnitude of lithium concentration changes increased with increasing C-rate. During a galvanostatic intermittent titration technique (GITT) test, changes in lithium concentration could be observed. During intercalation, a lithium depletion occurred when a negative current was applied, and a lithium surplus occurred during deintercalation when a positive current was applied. The capability of observing lithium concentration has significant implications for the utility of operando studies and the potential to link lithium movement to battery performance.

25 ENERGY STORAGE↗

DOE OSTI2011

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+ ), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22 Na and 13 C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+ , Na + , lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2 ] x ; (with x > 1). By substituting lanthanum (La 3+ ) for Nd 3+ in this system, NMR scoping experiments using 23 Na, 31 P nuclei and 13 C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+ ) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+ ) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Microemulsions and Aggregation Formation in Extraction Processes for Used Nuclear Fuel: Thermodynamic and Structural Studies

Advanced nuclear fuel cycles rely on successful chemical separation of various elements in the used fuel. Numerous solvent extraction (SX) processes have been developed for the recovery and purification of metal ions from this used material. However, the predictability of process operations has been challenged by the lack of a fundamental understanding of the chemical interactions in several of these separation systems. For example, gaps in the thermodynamic description of the mechanism and the complexes formed will make predictions very challenging. Recent studies of certain extraction systems under development and a number of more established SX processes have suggested that aggregate formation in the organic phase results in a transformation of its selectivity and efficiency. Aggregation phenomena have consistently been interfering in SX process development, and have, over the years, become synonymous with an undesirable effect that must be prevented. This multiyear, multicollaborative research effort was carried out to study solvation and self-organization in non-aqueous solutions at conditions promoting aggregation phenomena. Our approach to this challenging topic was to investigate extraction systems comprising more than one extraction reagent where synergy of the metal ion could be observed. These systems were probed for the existence of stable microemulsions in the organic phase, and a number of high-end characterization tools were employed to elucidate the role of the aggregates in metal ion extraction. The ultimate goal was to find connections between synergy of metal ion extraction and reverse micellar formation. Our main accomplishment for this project was the expansion of the understanding of metal ion complexation in the extraction system combining tributyl phosphate (TBP) and dibutyl phosphoric acid (HDBP). We have found that for this system no direct correlation exists for the metal ion extraction and the formation of aggregates, meaning that the metal ion is not solubilized in a reverse micelle core. Rather we have found solid evidence that the metal ions are extracted and coordinated by the organic ligands as suggested by classic SX theories. However, we have challenged the existence of mixed complexes that have been suggested to exist in this particular extraction system. Most importantly we have generated a wealth of information and trained students on important lab techniques and strengthened the collaboration between the DOE national laboratories and US educational institution involved in this work.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Characterize and control the multi-range structure of solution-phase systems with resonant x-ray scattering

This work aims at demonstrating the feasibility and impact of Anomalous X-ray Scattering (AXS) in characterizing the multi-range structures of solution-state systems. We will show preliminary investigation of long-range correlations in concentrated aqueous electrolytes with a combination of AXS and molecular dynamics (MD) simulations. We will also start exploring the capability of AXS to capture intra- and inter-molecular structure of dilute molecular systems, and specifically its sensitivity to the chemical environment surrounding active metal sites. We anticipate that the development of this method will help us to understand ion solvation and transport, which affect the performances of, for instance, electrocatalytic cells, as well as to identify/control the intrinsic structural factors that lead to selectivity, efficiency, and stability control during catalysis.

36 MATERIALS SCIENCE↗

DOE OSTI2010

Multiscale schemes for the predictive description and virtual engineering of materials.

This report documents research carried out by the author throughout his 3-years Truman fellowship. The overarching goal consisted of developing multiscale schemes which permit not only the predictive description but also the computational design of improved materials. Identifying new materials through changes in atomic composition and configuration requires the use of versatile first principles methods, such as density functional theory (DFT). Using DFT, its predictive reliability has been investigated with respect to pseudopotential construction, band-gap, van-der-Waals forces, and nuclear quantum effects. Continuous variation of chemical composition and derivation of accurate energy gradients in compound space has been developed within a DFT framework for free energies of solvation, reaction energetics, and frontier orbital eigenvalues. Similar variations have been leveraged within classical molecular dynamics in order to address thermal properties of molten salt candidates for heat transfer fluids used in solar thermal power facilities. Finally, a combination of DFT and statistical methods has been used to devise quantitative structure property relationships for the rapid prediction of charge mobilities in polyaromatic hydrocarbons.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Importance of Heat and Pressure for Solubilization of Recombinant Spider Silk Proteins in Aqueous Solution

The production of recombinant spider silk proteins continues to be a key area of interest for a number of research groups. Several key obstacles exist in their production as well as in their formulation into useable products. The original reported method to solubilize recombinant spider silk proteins (rSSp) in an aqueous solution involved using microwaves to quickly generate heat and pressure inside of a sealed vial containing rSSp and water. Fibers produced from this system are remarkable in their mechanical ability and demonstrate the ability to be stretched and recover 100 times. The microwave method dissolves the rSSPs with dissolution time increasing with higher molecular weight constructs, increasing concentration of rSSPs, protein type, and salt concentration. It has proven successful in solvating a number of different rSSPs including native-like sequences (MaSp1, MaSp2, piriform, and aggregate) as well as chimeric sequences (FlAS) in varied concentrations that have been spun into fibers and formed into films, foams, sponges, gels, coatings, macro and micro spheres and adhesives. The system is effective but inherently unpredictable and difficult to control. Provided that the materials that can be generated from this method of dissolution are impressive, an alternative means of applying heat and pressure that is controllable and predictable has been developed. Results indicate that there are combinations of heat and pressure (135 °C and 140 psi) that result in maximal dissolution without degrading the recombinant MaSp2 protein tested, and that heat and pressure are the key elements to the method of dissolution.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2011

Dynamics of Confined Water Molecules in Aqueous Salt Hydrates

The unusual properties of water are largely dictated by the dynamics of the H bond network. A single water molecule has more H bonding sites than atoms, hence new experimental and theoretical investigations about this peculiar liquid have not ceased to appear. Confinement of water to nanodroplets or small molecular clusters drastically changes many of the liquid’s properties. Such confined water plays a major role in the solvation of macro molecules such as proteins and can even be essential to their properties. Despite the vast results available on bulk and confined water, discussions about the correlation between spectral and structural properties continue to this day. The fast relaxation of the OH stretching vibration in bulk water, and the variance of sample geometries in the experiments on confined water obfuscate definite interpretation of the spectroscopic results in terms of structural parameters. We present first time-resolved investigations on a new model system that is ideally suited to overcome many of the problems faced in spectroscopical investigation of the H bond network of water. Aqueous hydrates of inorganic salts provide water molecules in a crystal grid, that enables unambiguous correlations of spectroscopic and structural features. Furthermore, the confined water clusters are well isolated from each other in the crystal matrix, so different degrees of confinement can be achieved by selection of the appropriate salt.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

MILESTONES AND FUTURE DIRECTIONS IN THE SOLVENT EXTRACTION OF CAESIUM

The remarkable development of solvent-extraction (SX) chemistry for caesium separation over the past half a century as driven by the needs of the nuclear industry now constitutes an instructive case study in exploring the limits of selectivity and cycle efficiency in SX. In this review, key milestones in the pursuit of both fundamentals and applications of caesium extraction will be highlighted along with a look at future prospects. The high-yield fission-product 137Cs constitutes a major fraction of the radioactivity in nuclear wastes, and in view of its heat production, environmental mobility, radiation hazard, and even uses as a radiation source, methods have long been sought for its separation. Toward this end, the evolving science has been challenged by daunting requirements for decontamination in the presence of high concentrations of competing cations, and demands for small footprint, modular design, and high throughput place a premium on selectivity and efficiency. Fortunately, the science has also benefited from the peculiar economics of nuclear separations, which have afforded the development of wonderfully sophisticated reagents. With its location in the lower left side of the periodic table, the Cs+ cation has the distinction of having the lowest charge density of any metal cation except short-lived francium. For practical purposes, Cs+ is thus the least hydrated and, in principle, the most directly extractable metal cation. Technologies employing liquid-liquid cation exchange with very large, durable anions like those from the dicarbollide family have therefore been quite effective based solely on solvation principles. Alternatively, researchers have turned to macrocyclic coordinating extractants, such as calix-crown ethers, following principles of molecular recognition, with dramatic results. Overall, strides continue along these lines, though it is apparent that caesium SX has reached a state of excellent fundamental understanding and technical maturity, evidenced by a suite of highly effective technologies.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2010

RADIATION CHEMISTRY 2010 GORDON RESEARCH CONFERENCE JULY 18-23

The 2010 Gordon Conference on Radiation Chemistry will present cutting edge research regarding the study of radiation-induced chemical transformations. Radiation Chemistry or 'high energy' chemistry is primarily initiated by ionizing radiation: i.e. photons or particles with energy sufficient to create conduction band electrons and 'holes', excitons, ionic and neutral free radicals, highly excited states, and solvated electrons. These transients often interact or 'react' to form products vastly different than those produced under thermal equilibrium conditions. The non-equilibrium, non-thermal conditions driving radiation chemistry exist in plasmas, star-forming regions, the outer solar system, nuclear reactors, nuclear waste repositories, radiation-based medical/clinical treatment centers and in radiation/materials processing facilities. The 2010 conference has a strong interdisciplinary flavor with focus areas spanning (1) the fundamental physics and chemistry involved in ultrafast (atto/femtosecond) energy deposition events, (2) radiation-induced processes in biology (particularly spatially resolved studies), (3) radiation-induced modification of materials at the nanoscale and cosmic ray/x-ray mediated processes in planetary science/astrochemistry. While the conference concentrates on fundamental science, topical applied areas covered will also include nuclear power, materials/polymer processing, and clinical/radiation treatment in medicine. The Conference will bring together investigators at the forefront of their field, and will provide opportunities for junior scientists and graduate students to present work in poster format or as contributors to the Young Investigator session. The program and format provides excellent avenues to promote cross-disciplinary collaborations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2011

Multiphase Flow Modeling of Biofuel Production Processes

As part of the Idaho National Laboratory's (INL's) Secure Energy Initiative, the INL is performing research in areas that are vital to ensuring clean, secure energy supplies for the future. The INL Hybrid Energy Systems Testing (HYTEST) Laboratory is being established to develop and test hybrid energy systems with the principal objective to safeguard U.S. Energy Security by reducing dependence on foreign petroleum. HYTEST involves producing liquid fuels in a Hybrid Energy System (HES) by integrating carbon-based (i.e., bio-mass, oil-shale, etc.) with non-carbon based energy sources (i.e., wind energy, hydro, geothermal, nuclear, etc.). Advances in process development, control and modeling are the unifying vision for HES. This paper describes new modeling tools and methodologies to simulate advanced energy processes. Needs are emerging that require advanced computational modeling of multiphase reacting systems in the energy arena, driven by the 2007 Energy Independence and Security Act, which requires production of 36 billion gal/yr of biofuels by 2022, with 21 billion gal of this as advanced biofuels. Advanced biofuels derived from microalgal biomass have the potential to help achieve the 21 billion gal mandate, as well as reduce greenhouse gas emissions. Production of biofuels from microalgae is receiving considerable interest due to their potentially high oil yields (around 600 gal/acre). Microalgae have a high lipid content (up to 50%) and grow 10 to 100 times faster than terrestrial plants. The use of environmentally friendly alternatives to solvents and reagents commonly employed in reaction and phase separation processes is being explored. This is accomplished through the use of hydrothermal technologies, which are chemical and physical transformations in high-temperature (200-600 C), high-pressure (5-40 MPa) liquid or supercritical water. Figure 1 shows a simplified diagram of the production of biofuels from algae. Hydrothermal processing has significant advantages over other biomass processing methods with respect to separations. These 'green' alternatives employ a hybrid medium that, when operated supercritically, offers the prospect of tunable physicochemical properties. Solubility can be rapidly altered and phases partitioned selectively to precipitate or dissolve certain components by altering temperature or pressure in the near-critical region. The ability to tune the solvation properties of water in the highly compressible near-critical region facilitates partitioning of products or by-products into separate phases to separate and purify products. Since most challenges related to lipid extraction are associated with the industrial scale-up of integrated extraction systems, the new modeling capability offers the prospect of addressing previously untenable scaling issues.

02 PETROLEUM↗

DOE OSTI2011

Complex Capacitance Scaling in Ionic Liquids-Filled Nanopores

Recent experiments have shown that the capacitance of subnanometer pores increases anomalously as the pore width decreases, thereby opening a new avenue for developing supercapacitors with enhanced energy density. However, this behavior is still subject to some controversy since its physical origins are not well understood. Using atomistic simulations, we show that the capacitance of slit-shaped nanopores in contact with room-temperature ionic liquids exhibits a U-shaped scaling behavior in pores with widths from 0.75 to 1.26 nm. The left branch of the capacitance scaling curve directly corresponds to the anomalous capacitance increase and thus reproduces the experimental observations. The right branch of the curve indirectly agrees with experimental findings that so far have received little attention. The overall U-shaped scaling behavior provides insights on the origins of the difficulty in experimentally observing the pore-width-dependent capacitance. We establish a theoretical framework for understanding the capacitance of electrical double layers in nanopores and provide mechanistic details into the origins of the observed scaling behavior. The framework highlights the critical role of 'ion solvation' in controlling pore capacitance and the importance of choosing anion/cation couples carefully for optimal energy storage in a given pore system.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2011

Complex Capacitance Scaling in Ionic Liquids-filled Nanopores

Recent experiments have shown that the capacitance of sub-nanometer pores increases anomalously as the pore width decreases, thereby opening a new avenue for developing supercapacitors with enhanced energy density. However, this behavior is still subject to some controversy since its physical origins are not well understood. Using atomistic simulations, we show that the capacitance of slit-shaped nanopores in contact with room-temperature ionic liquids exhibits a U-shaped scaling behavior in pores with width from 0.75 to 1.26 nm. The left branch of the capacitance scaling curve directly corresponds to the anomalous capacitance increase and thus reproduces the experimental observations. The right branch of the curve indirectly agrees with experimental findings that so far have received little attention. The overall U-shaped scaling behavior provides insights on the origins of the difficulty in experimentally observing the pore-width dependent capacitance. We establish a theoretical framework for understanding the capacitance of electrical double layers in nanopores and provide mechanistic details into the origins of the observed scaling behavior. The framework highlights the critical role of ion solvation in controlling pore capacitance and the importance of choosing anion/cation couples carefully for optimal energy storage in a given pore system.

25 ENERGY STORAGE↗