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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Ionic diffusioosmotic transport in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory

In this paper, we study the diffusioosmotic (DOS) transport in a nanochannel grafted with pH-responsive polyelectrolyte (PE) brushes and establish brush-functionalization-driven enhancement in induced nanofluidic electric field and electrokinetic transport. The PE brushes are modelled using our recently developed augmented strong stretching theory (SST). We consider the generation of the DOS transport due to the imposition of a salt concentration gradient along the length of the nanochannel. The presence of the salt concentration gradient induces an electric field that has an osmotic (associated with the flow-driven migration of the ions in the induced electric double layer) and an ionic (associated with the conduction current) component. These two components evolve in a manner such that the electric field in the brush-grafted nanochannel is larger (smaller) in magnitude than that in the brush-less nanochannels for the case where the electric field is positive (negative). Furthermore, we quantify the DOS flow velocity and establish that for most of the parameter choices, the DOS velocity, which is a combination of the induced pressure-gradient-driven chemiosmotic component and the induced electric field driven electroosmotic transport, is significantly larger for the nanochannels grafted with backbone-charged PE brushes (i.e., brushes where the charge is distributed along the entire length of the brushes) as compared to brush-free nanochannels or nanochannels grafted with PE brushes containing charges on their non-grafted ends.

42 ENGINEERING↗
DOE OSTI2025

The Origin of Improved Performance in Boron‐Alloyed Silicon Nanoparticle‐Based Anodes for Lithium‐Ion Batteries

Stabilizing the solid electrolyte interphase (SEI) remains a key challenge for silicon‐based lithium‐ion battery anodes. Alloying silicon with secondary elements like boron has emerged as a promising strategy to improve the cycle life of silicon anodes, yet the underlying mechanism remains unclear. To address this knowledge gap, how boron concentration influences battery performance is systematically investigated. These results show a near‐monotonic increase in cycle lifetime with higher boron content, with boron‐rich electrodes significantly outperforming pure silicon. Additionally, silicon‐boron alloy anodes exhibit nearly three times longer calendar life than pure silicon. Through detailed mechanistic analysis, alternative contributing factors are systematically ruled out, and it is proposed that improved passivation arises from a strong permanent dipole at the nanoparticle surface. This dipole, formed by undercoordinated and highly Lewis acidic boron, creates a static, ion‐dense layer that stabilizes the electrochemical interface, reducing parasitic electrolyte decomposition and enhancing long‐term stability. These findings suggest that, within the SEI framework, the electric double layer is an important consideration in surface passivation. This insight provides an underexplored parameter space for optimizing silicon anodes in next‐generation lithium‐ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Dopant Sensitive Electrolytic Etching of Germanium with High Selectivity

Abstract The enhanced charge carrier mobility and photon absorption compared to silicon make germanium attractive for next-generation photo diodes. However, the complex oxidation behavior of germanium challenges dopant-dependent selective etching that is desired for the fabrication of backside imaging architectures. This report demonstrates electrolytic wet etching of p-doped germanium which proceeds up to 17,500x faster than etching of intrinsic germanium. Homoepitaxially grown layers of germanium were electrolytically etched in potassium hydroxide over a range of biases. Intermittent acquisition of cyclic voltammetry spectra during etching has suppressed the formation of electric double layers, maintained appreciable etch rates, and allowed for in operando process control. The observed etch rates scaled with dopant concentration. An effective etch rate of germanium removal of 2.100±0.044 µm/min was accomplished for a boron dopant concentration of 6E18cm-3. For nominally intrinsic germanium, however, an effective etch rate of only 0.00012±0.00011 µm/min was observed. A series of systematic electrolytic etch experiments have revealed the transfer of 4 electrons per germanium atom removed.

Wood, Joseph G.↗
NASA NTRS1977

Electric currents in cosmic plasmas

It is suggested that dualism is essential for the physics of cosmic plasmas, that is, that some phenomena should be described by a magnetic field formalism, and others by an electric current formalism. While in earlier work the magnetic field aspect has dominated, at present there is a systematic exploration of the particle (or current) aspect. A number of phenomena which can be understood only from the particle aspect are surveyed. Topics include the formation of electric double layers, the origin of 'explosive' events like magnetic substorms and solar flares, and the transfer of energy from one region to another. A method for exploring many of these phenomena is to draw the electric circuit in which the current flows and then study its properties. A number of simple circuits are analyzed in this way.

Alfven, H.↗
DOE OSTI2023

Electric Field Effects on Water and Ion Structure and Diffusion at the Orthoclase (001)–Water Interface

Understanding the electrochemical properties of mineral–water interfaces tends to rely upon electrical double layer (EDL) models, but these models are based on the assumption that electrostatic equilibrium is constantly maintained. In reality, interfacial reactions, ion diffusion, and their electrochemical signatures are based in nonequilibrium conditions of locally or globally imbalanced electrical fields where current EDL models have limited purview. In this work, we performed molecular dynamics (MD) simulations of the orthoclase (001) surface in contact with a 1 M NaCl aqueous solution under various electric fields, to explore the interplay between EDL structure and dynamics when perturbed by electric fields of different direction and strength, by confinement, and by different distributions of structural surface charge. The simulations showed that confinement between two opposing (001) surfaces led to the development of an induced field when the applied field was perpendicular to the surfaces and, as a result, to ionic diffusion coefficients that were independent of electric field strength. In contrast, when the applied field was parallel to the surfaces, confinement resulted in ionic diffusion coefficients that were more strongly dependent on the magnitude of the electric field than in bulk water. Differences in the density and distribution of aluminol groups on the two surfaces had a significant impact on how the interfacial structure and dynamics varied in the presence of an electric field. Notably, these differences resulted in an electro-osmotic flow with opposite directions at the two surfaces under parallel applied electric field. Overall, the MD simulations highlighted the importance of considering atomic-level structure and heterogeneities when developing models of the electrochemical properties of mineral–water interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Mitigating CaCO 3 crystal nucleation and growth through continuous ion displacement via alternating electric fields

Mineral crystal formation poses a challenge on surfaces (e.g., heat exchangers, pipes, membranes, etc.) in contact with super-saturated fluids. Applying alternating currents (AC) to such surfaces can prevent surface crystallization under certain conditions. Here, we demonstrate that ion displacement induced by periodic charging and discharging of the electrical double layer (EDL) inhibits both heterogeneous and homogeneous nucleation (and crystal growth) of CaCO 3 . Titanium sheets (meant to simulate metallic heat exchanger surfaces) are immersed in super-saturated CaCO 3 solutions with a saturation index >11. We show that at relatively high AC frequencies, incomplete EDL formation leads to an alternating electric field that propagates far into the bulk solution, inducing rapid ion migration that overwhelms the Brownian motion of ions. Electrochemical characterization reveals EDL charging/discharging under AC conditions that greatly inhibits precipitation. Operating at 4 V pp , 0.1–10 Hz reduces turbidity by over 96% and reduces CaCO 3 coverage on the metal plates by over 92%. Based on electrokinetic and crystallization models, the ion displacement velocity (exceeding the mean Brownian velocity) and displacement length disrupts ion collision and crystal nucleation. Overall, the technique has potential for preventing mineral crystal formation in heat exchangers and many other industrially relevant systems.

42 ENGINEERING↗
DOE OSTI2025

Quantifying Stern layer water alignment before and during the oxygen evolution reaction

While water’s oxygen is the electron source in the industrially important oxygen evolution reaction, the strong absorber problem clouds our view of how the Stern layer water molecules orient themselves in response to applied potentials. Here, we report nonlinear optical measurements on nickel electrodes held at pH 13 indicating a disorder-to-order transition in the Stern layer water molecules before the onset of Faradaic current. A full water monolayer (1.1 × 10 15 centimeter −2 ) aligns with oxygen atoms pointing toward the electrode at +0.8 volt and the associated work is 80 kilojoule per mole. Our experiments identify water flipping energetics as a target for understanding overpotentials, advance molecular electrochemistry, provide benchmarks for electrical double layer models, and serve as a diagnostic tool for understanding electrocatalysis.

Science & Technology - Other Topics↗
NASA NTRS1986

An updated theory of the polar wind

The 'classical' polar wind is an ambipolar outflow of thermal plasma from the terrestrial ionosphere at high latitudes. As the plasma escapes along diverging geomagnetic flux tubes, it undergoes four major transitions, including a transition from chemical to diffusion dominance, a transition from subsonic to supersonic flow, a transition from collision-dominated to collisionless regimes, and a transition from a heavy to a light ion. A further complication arises because of horizontal convection of the flux tubes owing to magnetospheric electric fields. Recent modelling predictions indicate that the polar wind has the following characteristics: (1) the ion and electron distributions are anisotropic and asymmetric in the collisionless regime; (2) elevated electron temperatures act to produce significant escape fluxes of suprathermal O(+) ions; (3) the interaction of the hot magnetospheric and cold ionospheric electron population leads to a localized (double layer) electric field which accelerates the polar wind ions; (4) a time-dependent expansion produces suprathermal ions; and (5) large perturbations lead to the formation of forward and reverse shocks. These and other results are reviewed.

Schunk, R. W.↗
DOE OSTI2024

Dynamics of Electric Polarization and Relaxation of Ions at Humid Calcite Surfaces

Mobile ions at mineral surfaces can respond to an applied electric field, adopting a new distribution that effectively represents polarization of the electrical double layer. When the field is released, the ions relax to their equilibrium distribution. In both cases, the dynamics are characteristic of the interface. However, current models of electrokinetic phenomena are not sufficiently robust to accurately predict collective ion dynamics at structurally and chemically specific mineral–water interfaces. Here, in this study, we use electrostatic force microscopy (EFM) to investigate the dynamics of ion relaxation at hydrated calcite (104) surfaces at controlled relative humidity (RH). Electrically biased probes are used to polarize the distributions of calcium and carbonate ions that are intrinsic to this interface across a range of RH values. Polarization kinetics are tracked by monitoring the tip–sample force gradient during charging, and EFM imaging is used to characterize the spatial relaxation dynamics after the applied field is released. Electrostatic finite element modeling of the sample/probe system across length-scales from nanometers to millimeters reproduces the observed stretched exponential charging response. Together, these results allow us to estimate the ion diffusivities at the interface across a wide range of RH values. These diffusivities increase by roughly 5 orders of magnitude as the RH is increased from 5 to 90%, highlighting the critical role of adsorbed water for surface ion solvation that enables ion mobility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electrical Conductivity of Clayey Rocks and Soils: A Non-Linear Model

It is well-accepted that Archie's law is only applicable to “clean” rocks and soils but fails in “dirty” ones where clay minerals possess an additional component of surface conductivity. Although several models, for example, Waxman-Smits model, were presented to account for this phenomenon, surface conductivity is always inappropriately treated as constant, which actually only holds at high salinities. The essential non-linear characteristic differing over fluid salinities has not been physically or mathematically explained well in those models. Here, we scrutinize the conduction mechanism of clayey rocks and soils and ascribe this non-linear feature to (a) variation of the electrical double layer and (b) the intrinsic clay-and-water conduction pattern. With effective medium theory, we develop an easy-to-use non-linear model that both reflects electrochemical theories and explains the measurement data well. Our model can be used to produce more accurate results for laboratory- and field-scale petrophysical parameter evaluations than the previous models.

58 GEOSCIENCES↗
DOE OSTI2023

Ultra-thin on-chip ALD LiPON capacitors for high frequency application

Multi-layer ceramic capacitors have been used for high frequency decoupling application due to a lower overall impedance leading to fast current response. However, high parasitic inductance limits the application of these capacitors in ultra-high frequency domain. Thus, Multlayer Ceramic Capacitors (MLCCs) are placed close to the IC to improve circuit efficiency and reduce inductance. With next generation applications, the demand for frequency range has further increased which not only requires enhanced capacitor material but improved manufacturing techniques to limit the inductive path. Here, we demonstrate ALD of two different polymorphs of ultra-thin film lithium phosphorus oxynitride (LiPON) as an inorganic solid state electrolyte (SSE) for on chip capacitors for decoupling application. Both the LiPON capacitors shows an electric double layer behavior with a capacitance of 15 μF/cm 2 and a low leakage current (<20 nA/cm 2 ) at 2V. The LiPON shows EDLC behavior up to 10 kHz and beyond, both the polymorphs show an electrostatic behavior with a high dielectric constant (14). Furthermore, this dual frequency behavior along with low parasitic inductance and on chip integration allows for operation in extended frequency ranges.

25 ENERGY STORAGE↗
DOE OSTI2020

Tracking ion intercalation into layered Ti 3 C 2 MXene films across length scales

Enhancing the energy stored and power delivered by layered materials relies strongly on improved understanding of the intricate interplay of electrolyte ions, solvents, and electrode interactions as well as the role of confinement. Here we report a highly integrated study with multiscale theory/modelling and experiments to track the intercalation of aqueous Li + , Na + , K + , Cs + , and Mg 2+ ions into Ti 3 C 2 MXene. The integrated analysis of experiments assisted by theory/modelling allows for a deep understanding of energy storage processes highlighting the importance of the dynamics of cations, their positionings between MXene sheets, their effects on mechanical properties and capacitive energy storage. Computational simulations and operando calorimetry measurements prove the processes involving cation dehydration and H+ rehydration, showing a good correlation for heat variations between experiments and theory. Operando liquid AFM mapped energy dissipation of ions appears non-uniformly across the MXene surface, indicating heterogeneities of ions inside the MXene and confirming partially the ion behaviour obtained in theory. We directly demonstrate that the average distance between the cation and MXene surface follows a modified two-sided Helmholtz model when plotted versus the open circuit potential capacitance, revealing a different electrical double layer mechanism in confinement. This new fundamental understanding lays the foundation for improved functional devices utilizing electrodes and membranes made of two-dimensional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Interfacial Cation Arrangement Controls Electrocatalytic Kinetics in CO 2 Reduction

The identity of electrolyte cations is known to strongly influence electrocatalytic activity, but the relationship between their interfacial arrangement and observed performance remains poorly understood. Organic cations, with their molecular tunability, provide a powerful platform for systematically probing these effects. Here, we leverage phosphonium-based geminal dications to control interfacial cation arrangement and identify the variables that most strongly influence catalytic rates. As a case study, we examine CO 2 reduction to CO over polycrystalline silver electrodes in dry aprotic acetonitrile. Through a combination of rotating disk electrode measurements, electrochemical impedance spectroscopy, and molecular dynamics simulations, we decouple the effects of cation–electrode distance and interfacial cation density on catalytic rates. We find that smaller, more densely packed cations induce stronger interfacial electric fields, which lower the activation barrier for CO 2 adsorption and increase reaction rates. Using geminal phosphonium dications [C n (P mmm ) 2 ][ClO 4 ] 2 , we demonstrate that both the vertical and lateral positioning of organic cations within the electrical double layer independently affect reactivity. These results demonstrate that electrolyte cation identity primarily influences catalytic kinetics by determining how efficiently charge can be arranged at electrochemical interfaces. Altogether, our findings support an electrostatic view of cation effects in catalysis and provide design principles for next-generation electrolytes.

Cations↗
DOE OSTI2024

Structure and Dynamics of Aqueous Electrolytes at Quartz (001) and (101) Surfaces

Here, understanding and describing reactivity at mineral-water interfaces such as ion adsorption, the kinetics of dissolution, or surface charge development depends on our ability to improve the accuracy of electrical double layer (EDL) models. While molecular dynamics (MD) simulations are routinely used to investigate the structure and energetics of adsorbed ions comprising the EDL, less attention is paid to their self-diffusion dynamics, which can uniquely inform on coupling to interfacial reactions. Here we use MD to investigate both the organization and diffusion dynamics of water and electrolyte ions (NaCl, KCl, CaCl 2 ) at hydroxylated quartz (001) and (101) surfaces, a comparison which allowed us to assess surface structural effects of corrugation and silanol density. We found that inner- versus outer-sphere complex formation depends on cation size and charge but not necessarily hydration energies. Participation of surface silanols in the hydration spheres of Na + and K + generally indicated their preference for inner-sphere complexation, but this depends strongly on the orientation of the surface considered through its influence over the organization and dynamics of adsorbed water layers. In particular, surface orientation substantially affects the diffusive behavior of the near-surface water. Na + was found to decrease the mobility of water in the first layer, consistent with an increasing frequency of hydrolysis implied by faster quartz dissolution rates observed in experiments via the well known salt effect. Our results are also in good agreement with the observed dissolution rate of quartz vs. surface adsorption strength measure by Dove and Nix. This study sets the stage for a forthcoming paper examining how the dynamics at quartz/electrolyte interfaces are influenced by externally applied electric fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Alkali Cation Inhibition of Imidazolium-Mediated Electrochemical CO 2 Reduction on Silver

Imidazolium-based ionic liquids have led to enhanced CO 2 electroreduction activity due to cation effects at the cathode surface, stabilizing the reaction intermediates and decreasing the activation energy. In aqueous media, alkali cations are also known to improve CO 2 reduction activity on metals such as Ag, with the enhancement attributed to electrical double layer effects and trending with the size of the alkali cation. However, the effect of a mixed catholyte solution of alkali cations in the presence of an imidazolium-based ionic liquid has not been well-explored. Herein, 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF 4 ], in water was investigated with alkali salts to unravel the interaction effects for CO 2 electroreduction on Ag. Although both [EMIM] + and alkali cations have individually improved CO 2 to CO conversion on Ag in water, electrochemical results showed that alkali cations hindered imidazolium-mediated CO 2 electroreduction in most conditions. Li + , in particular, was sharply inhibitory compared to other alkali cations and strongly redirected the selectivity to hydrogen evolution. The nature of the alkali cation inhibition was investigated with spectroscopic techniques, including in situ surface-enhanced Raman spectroscopy (SERS) and dynamic electrochemical impedance spectroscopy (DEIS). Along with computational insights from density functional theory (DFT), the electrochemical and spectroscopic data suggest that alkali cations inhibit [EMIM]-mediated CO 2 reduction by competing for surface adsorption sites, preventing the potential-dependent structural reorientation of imidazolium, and promoting hydrogen evolution by bringing solvated water to the cathode surface.

cations↗
DOE OSTI2020

In Operando Calorimetric Measurements for Activated Carbon Electrodes in Ionic Liquid Electrolytes under Large Potential Windows

This study aims to investigate the effect of the potential window on heat generation in carbon-based electrical double layer capacitors (EDLCs) with ionic-liquid (IL)-based electrolytes using in operando calorimetry. The EDLCs consisted of two identical activated-carbon electrodes with either neat 1-butyl-1-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide ([Pyr 14 ][TFSI]) electrolyte or 1.0 m [Pyr 14 ][TFSI] in propylene carbonate (PC) as electrolyte. The instantaneous heat generation rate at each electrode was measured under galvanostatic cycling for different potential windows ranging from 1 to 4 V. First, the heat generation rates at the positive and negative electrodes differed significantly in neat IL owing to the differences in the ion sizes and diffusion coefficients. However, these differences were minimized when the IL was diluted in PC. Second, for EDLC in neat [Pyr 14 ][TFSI] at high potential window (4 V), a pronounced endothermic peak was observed at the beginning of the charging step at the positive electrode owing to TFSI - intercalation in the activated carbon. On the other hand, for EDLC in 1.0 m [Pyr 14 ][TFSI] in PC at potential window above 3 V, an endothermic peak was observed only at the negative electrode owing to the decomposition of PC. Third, for both neat and diluted [Pyr 14 ][TFSI] electrolytes, the irreversible heat generation rate increased with increasing potential window and exceeded Joule heating. This was attributed to the effect of potential-dependent charge redistribution resistance. Additionally, a further increase in the irreversible heat generation rate was observed for the largest potential windows owing to the degradation of the PC solvent. Finally, for both types of electrolyte, the reversible heat generation rate increased with increasing potential window because of the increase in the amount of ion adsorbed/desorbed at the electrode/electrolyte interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Quantitative Analysis of the Semiconductor–Electrolyte Interface Using Cyclic Voltammetry Measurements

Small changes in the chemical potential at a semiconductor interface can result in dramatic changes to the space-charge layer that underpins applications in the electronic and photovoltaic industries as well as in photoelectrochemical cells for fuel production. There has hence been great interest in techniques that directly probe the space-charge layer, yet many fail at the semiconductor–electrolyte interface due to the potential drop in the electric double-layer region of the electrolyte. This article demonstrates that photovoltages, obtained from straightforward cyclic voltammetry measurements, provide an experimental and quantitative approach for characterizing the semiconductor–electrolyte interface. Key parameters accessible through this approach include the flat-band potential ( E fb ), the fraction of the total potential that drops across the space-charge layer (γ sc ) and the electric double layer, as well as the surface recombination lifetime (τ s ). Here, we report photovoltage measurements for p -type Si(111) photoelectrodes in contact with electrolytes containing redox-active species with a range of known reduction potentials that exceed the 1.1 eV bandgap. In tetrabutylammonium [NBu 4 ] + electrolyte, the flat-band potential determined for hydrogen-terminated ( p -Si–H), methyl-terminated ( p -Si–CH 3 ), and chemically oxidized ( p -Si–cSiO x ) surfaces were −0.02, −0.31, and 0.30 V vs Fc +/0 , respectively, agreeing well with expected shifts arising from surface dipole modifications. The quantitative analysis also reveals that 67% of the applied bias drops across the space-charge layer for p -Si–H, 73% for p -Si–CH 3 , and only 44% for p -Si–cSiO x . The remaining potential drop is attributed to the interfacial surface layer, which consists of a molecular dipole or oxide overlayer, and the Helmholtz layer within the electrolyte. When the larger [NBu 4 ] + electrolyte was replaced with Li + , the flat-band position showed minimal changes, but the fraction of the potential drop across the space-charge layer increased significantly, consistent with the small cation altering the structure of the electric double layer.

electrolytes↗
DOE OSTI2020

Blocking Ion Migration Stabilizes the High Thermoelectric Performance in Cu 2 Se Composites

The applications of mixed ionic–electronic conductors are limited due to phase instability under a high direct current and large temperature difference. Here, it is shown that Cu 2 Se is stabilized through regulating the behaviors of Cu + ions and electrons in a Schottky heterojunction between the Cu 2 Se host matrix and in-situ-formed BiCuSeO nanoparticles. The accumulation of Cu + ions via an ionic capacitive effect at the Schottky junction under the direct current modifies the space-charge distribution in the electric double layer, which blocks the long-range migration of Cu + and produces a drastic reduction of Cu + ion migration by nearly two orders of magnitude. Moreover, this heterojunction impedes electrons transferring from BiCuSeO to Cu 2 Se, obstructing the reduction reaction of Cu + into Cu metal at the interface and hence stabilizes the β-Cu 2 Se phase. Furthermore, incorporation of BiCuSeO in Cu 2 Se optimizes the carrier concentration and intensifies phonon scattering, contributing to the peak figure of merit ZT value of ≈2.7 at 973 K and high average ZT value of ≈1.5 between 400 and 973 K for the Cu 2 Se/ BiCuSeO composites. Here, this discovery provides a new avenue for stabilizing mixed ionic–electronic conduction thermoelectrics, and gives fresh insights into controlling ion migration in these ionic-transport-dominated materials.

36 MATERIALS SCIENCE↗