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Results for “Electrical impedance spectroscopy”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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138 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Imaginary admittance and charge transfer resistance correlate to the physiological status of Shewanella oneidensis cultures in real time

Monitoring microbial activity is essential for industrial and environmental applications to proceed efficiently. To minimize time and labor-intensive monitoring, a new paradigm is required for in-situ, real time analysis. Since bioconversion of organics is accomplished by microorganisms through the oxidation of feedstocks linked to the reduction of electron acceptors, microorganisms can be viewed as electrochemical catalysts. In this respect, cell membranes have an electrical potential, which is analogous to a conventional capacitor and linked dynamically to cellular activity. Here, in this study, we demonstrate the use of electrochemical impedance spectrometry (EIS) and cyclic voltammetry (CV) for monitoring microbial metabolic activity in real time, in-situ. The effect of organic electron donors as a function of concentration to the physiological status of strains of Shewanella oneidensis was determined. In this study, the pyomelanin overproducer (S. oneidensis ΔhmgA) and the pyomelanin deficient mutant (S. oneidensis ΔmelA) were chosen due to different surface electrochemical characteristics along with differences in oxygen utilization efficiency. CV, relative admittance, phase shift and permittivity changed with growth status and correlated with electron flow from organic carbon sources and terminal electron acceptor availability. This work offers a novel and inexpensive approach to real time monitoring with the advantage of abundant data.

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

Accurately measuring the ionic conductivity of membranes via the direct contact method

Accurately measuring the ionic conductivity of membranes is important both for assessing the performance of new membranes as well as for advancing the fundamental understanding of electric field-driven ion transport in membranes. Yet, despite a considerable number of reports on the topic, there is no standardized method for ionic conductivity measurements. One of the main challenges with ionic conductivity measurements is isolating the membrane resistance from the other resistances in the electrochemical cell. In this study, we present a detailed discussion of factors that affect ionic conductivity measurements with the commonly used direct contact method, in which the membrane contacts the electrodes. Such factors include external resistances due to imperfect contact between the membrane and electrodes, residual impedances due to the sample holder and wiring, and fringe effects. Further, we also present and validate simple methods for isolating the true membrane ionic conductivity in both the through-plane and in-plane orientations. These methods can be implemented with virtually any membrane to obtain accurate and reproducible ionic conductivity values. Finally, we outline recommendations for performing ionic conductivity measurements with the direct contact method and a set of parameters to verify when reporting these results.

36 MATERIALS SCIENCE↗
NASA NTRS2001

Micromachined TWTs for THz Radiation Sources

The Terahertz (THz) region of the electromagnetic spectrum (about 300 - 3000 GHz in frequency or about 0.1 - 1 mm free space wavelength) has enormous potential for high-data-rate communications, spectroscopy, astronomy, space research, medicine, biology, surveillance, remote sensing, industrial process control, etc. It has been characterized as the most scientifically rich, yet under-utilized, region of the electromagnetic spectrum. The most critical roadblock to full exploitation of the THz band is lack of coherent radiation sources that are powerful (0.001 - 1.0 W continuous wave), efficient (> 1%), frequency agile (instantaneously tunable over 1% bandwidths or more), reliable, and comparatively inexpensive. To develop vacuum electron device (VED) radiation sources satisfying these requirements, fabrication and packaging approaches must be heavily considered to minimize costs, in addition to the basic interaction physics and circuit design. To minimize size of the prime power supply, beam voltage must be minimized, preferably 10 kV. Solid state sources satisfy the low voltage requirement, but are many orders of magnitude below power, efficiency, and bandwidth requirements. On the other hand, typical fast-wave VED sources in this regime (e.g., gyrotrons, FELs) tend to be large, expensive, high voltage and very high power devices unsuitable for most of the applications cited above. VEDs based on grating or inter-digital (ID) circuits have been researched and developed. However, achieving forward-wave amplifier operation with instantaneous fractional bandwidths > 1% is problematic for these devices with low-energy (< 15 kV) electron beams. Moreover, the interaction impedance is quite low unless the beam-circuit spacing is kept particularly narrow, often leading to significant beam interception. One solution to satisfy the THz source requirements mentioned above is to develop micromachined VEDs, or "micro-VEDs". Among other benefits, micro-machining technologies provide superior high frequency wall conductivity as a result of superior surface smoothness compared with conventional mechanical or electric discharge machining approaches. Micro-VED technologies are already being applied to the development of millimeter-wave klystrons at Stanford Linear Accelerator Center and submillimeter-wave klystrons at the University of Leeds. We are investigating the use of micro-machining technologies to develop THz regime TWTs, with emphasis on folded-waveguide TWTs. The folded-waveguide TWT (FW-TWT) has several features that make it attractive for THz-regime micro-VED applications. It is a relatively simple circuit to design and fabricate, it is amenable to precision pattern replication by micro-machining, and it is has been demonstrated capable of forward-wave amplification with appreciable bandwidth. We are conducting experimental and computational studies of micro-VED FW-TWTs to examine their feasibility for applications at frequencies from 200 - 1000 GHz.

Booske, John H.↗
DOE OSTI2019

Electroanalytical Investigation of the Electrode–Electrolyte Interface of Quaternary Ammonium Ionic Liquids: Impact of Alkyl Chain Length and Ether Functionality

The influence of ionic associations and potential-dependent interactions on the electrode–electrolyte interfacial structure of ionic liquids (ILs) is studied by electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS) for a variety of asymmetric quaternary ammonium ILs. Specifically, the impact of cation alkyl chain length (C = 4, 8 and 16) and ether functionality on the interfacial structuring of ILs at the glassy carbon electrode surface is examined. Ammonium cations with alkyl chain length of 8 and 16 carbons are found to stabilize the formation of the bis(trifluorosulfonyl)imide, [TFSI], anion dense Stern layer at positive electrode potentials leading to larger capacitances. The longer alkyl chain of the cation is believed to screen the ion–ion repulsion among the anions by intruding into the interfacial anion layer. SERS suggests the presence of carbon-containing rings at the interface at both positive and negative electrode potentials, which can be explained by the buckling of the long alkyl chains. Inclusion of an ether functionality allowed for more symmetry in the camel-shaped potential-dependent differential capacitance curves, suggesting similar excess ion density at both positive and negative potentials. This work contributes to understanding and predicting the interfacial electrode capacitance in ILs by understanding the balance of ionic interactions and the associated repulsions at electrode–electrolyte interfaces that are pertinent to electrochemical energy storage, electrocatalysis, and electrochemical sensors.

25 ENERGY STORAGE↗
DOE OSTI2024

Oxidation Temperature-Dependent Electrochemical Doping of WO 3 Deposited via Atomic Layer Deposition

Silicon-based photoelectrochemical devices show promise for the performance of light-driven CO 2 reduction but suffer from instability under photoelectrochemical conditions relevant to CO 2 reduction. Coating silicon electrodes with thin layers of metal oxides has shown promise to passivate unstable silicon surfaces, and many different metal oxides can be deposited on silicon using various techniques. In this study, we investigate the fundamental photoelectrochemical performance of WO 3 -coated silicon photoelectrodes, which were generated by oxidation of W-metal films deposited via atomic layer deposition on both degenerately doped (nSi + ) and low-doped (pSi) silicon. Two different oxidation temperatures were investigated (400 and 600 °C), and it was found that the monoclinic phase of WO 3 predominates at both temperatures but that more grain boundaries are present in the 600 °C film. From X-ray photoelectron spectroscopy, the stoichiometry of both films was found to be 1:3 W:O, and low electron energy loss experiments indicate band gaps of 3.0 and 3.1 eV for 400 and 600 °C films, respectively. Cyclic voltammetry experiments showed that the electron transfer kinetics increased after continued redox cycling, particularly for the material produced at 400 °C. X-ray photoelectron spectra suggest that the observed increase in electrode conductivity is due to the formation of oxygen vacancies in the film. Electrochemical impedance spectroscopy indicated that charge transport through the films was impacted by the grain boundaries that formed during oxidation of the film. Photoelectrochemical studies on pSi/WO 3 electrodes were highly variable, only producing a photocurrent and photovoltage with some samples. Our best sample, formed at 400 °C, produced a photovoltage of 180 mV, which is lower than what has previously been reported for WO 3 -coated silicon (500 mV). We hypothesize that the variability in photoelectrochemical experiments arose from a roughened WSiO x interface that is generated during film preparation. WO 3 shows promise as a metal oxide coating for silicon, but our results suggest that formation of a high-quality interface between Si and WO 3 is vital for best performance.

Charge transfer↗
DOE OSTI2020

Near-Zero Power MOF-Based Sensors for NO 2 Detection

Detection and capture of toxic nitrogen oxides (NO x ) is important for emissions control of exhaust gases and general public health. The ability to directly electrically detect trace (0.5–5 ppm) NO 2 by a metal–organic framework (MOF)-74-based sensor at relatively low temperatures (50 °C) is demonstrated via changes in electrical properties of M-MOF-74, M = Co, Mg, Ni. The magnitude of the change is ordered Ni > Co > Mg and explained by each variant's NO 2 adsorption capacity and specific chemical interaction. Ni-MOF-74 provides the highest sensitivity to NO 2 ; a 725× decrease in resistance at 5 ppm NO2 and detection limit <0.5 ppm, levels relevant for industry and public health. Furthermore, the Ni-MOF-74-based sensor is selective to NO 2 over N 2 , SO 2 , and air. Linking this fundamental research with future technologies, the high impedance of MOF-74 enables applications requiring a near-zero power sensor or dosimeter, with the active material drawing <15 pW for a macroscale device 35 mm 2 with 0.8 mg MOF-74. Finally, this represents a 10 4 –10 6 × decrease in power consumption compared to other MOF sensors and demonstrates the potential for MOFs as active components for long-lived, near-zero power chemical sensors in smart industrial systems and the internet of things.

47 OTHER INSTRUMENTATION↗
DOE OSTI2026

Coupled Interfacial Kinetics and Transport Resistances Govern High-Current Behavior in Bipolar Membranes

Bipolar membranes (BPMs) enable electrochemical systems that operate across large pH gradients; however, high-current operation is often limited by voltage losses whose origins remain difficult to resolve in membrane−electrode assemblies. Here, we combine electrochemical impedance spectroscopy with distribution of relaxation times (EIS–DRT) analysis and operando synchrotron X-ray diffraction to examine interfacial polarization, membrane hydration, and transport in commercial and synthesized BPMs. EIS–DRT isolates the BPM-associated interfacial contribution and shows that the commercial BPM exhibits larger water-dissociation-associated overpotentials than the synthesized BPM. Operando hydration mapping shows that both membranes retain water at the bipolar junction during high-current operation, while anode-adjacent hydration gradients are more pronounced in the commercial membrane. These results indicate that high-current voltage losses are not governed by junction water starvation alone but by coupled interfacial polarization and transport resistances.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The Effects of Morphology and Hydration on Anion Transport in Self-Assembled Nanoporous Membranes

Ordered nanoporous polymer membranes offer opportunities for systematically probing the mechanisms of ion transport under confinement and for realizing useful materials for electrochemical devices. Here, we examine the impact of morphology and ion hydration on the transport of hydroxide and bromide anions in nanostructured polymer membranes with 1 nm scale pores. We use aqueous lyotropic self-assembly of an amphiphilic monomer, with a polymerizable surfactant to create direct hexagonal (H I ) and gyroid mesophases. UV-induced cross-linking leads to the formation of nanoporous polymers with water continuous channels. The membranes are mechanically robust and chemically durable, resisting degradation during extended exposure to 1 M NaOH solutions. We use a combination of electrochemical impedance spectroscopy, pulsed-field gradient NMR spectroscopy, and molecular simulations to elucidate anion and water transport. The as-prepared hexagonal systems display higher conductivity and lower activation energies for both anions relative to the gyroid system. When compared at equivalent hydration, however, gyroid and hexagonal membranes show similar activation energies, with nearly identical conductivities at ambient temperatures. Both ionic conductivity and water diffusivity increase with increasing hydration. Here, the water uptake as a function of relative humidity for the hexagonal and gyroid mesophases ultimately dictates the water diffusion and magnitude of the ionic conductivity, with the hexagonal system showing overall higher capacity for hydration and thus faster ion transport. The durability of these materials under aggressive alkaline conditions and their relatively high hydroxide ion conductivity suggest that these nanostructured polymers could be of interest as membranes for alkaline fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Determining blood and plasma volumes using bioelectrical response spectroscopy

We hypothesized that an electric field (inductance) produced by charged blood components passing through the many branches of arteries and veins could assess total blood volume (TBV) or plasma volume (PV). Individual (N = 29) electrical circuits (inductors, two resistors, and a capacitor) were determined from bioelectrical response spectroscopy (BERS) using a Hewlett Packard 4284A Precision LCR Meter. Inductance, capacitance, and resistance from the circuits of 19 subjects modeled TBV (sum of PV and computed red cell volume) and PV (based on 125I-albumin). Each model (N = 10, cross validation group) had good validity based on 1) mean differences (-2.3 to 1.5%) between the methods that were not significant and less than the propagated errors (+/- 5.2% for TBV and PV), 2) high correlations (r > 0.92) with low SEE (< 7.7%) between dilution and BERS assessments, and 3) Bland-Altman pairwise comparisons that indicated "clinical equivalency" between the methods. Given the limitation of this study (10 validity subjects), we concluded that BERS models accurately assessed TBV and PV. Further evaluations of the models' validities are needed before they are used in clinical or research settings.

NASA Discipline Number 00-00↗
DOE OSTI2023

Single Ion Conducting Hairy Nanoparticle Additive to Improve Cycling Stability of Solid Polymer Electrolytes

The development of a solid electrolyte that can impede dendrite growth while still maintaining an appropriate level of conductivity is essential for improving performance of solid-state Li-ion battery. In this paper, we report the synthesis of single Li-ion conducting hairy nanoparticle (NP) materials that improved the cycling stability of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-doped poly(ethylene oxide) (PEO) solid electrolyte without significant reduction in conductivity. To unveil mechanisms leading to improved cycling stability, several characterization techniques including broadband dielectric spectroscopy, differential scanning calorimetry, small angle X-ray scattering, transmission electron microscopy, and shear rheology were used to study properties of polymer composites (PC) with added hairy NPs. It was found that hairy NPs influenced the Li/electrolyte interface and improved mechanical properties of bulk composites, all of which contributed to homogenous Li plating and stripping. The improved performance has been found in composites with concentrations of 4.8 and 9.1 weight % of added hairy NPs, which enabled Li cycling stability at 0.2 mA cm–2 critical current density (>300 h) that was otherwise not possible in either PEO-LiTFSI alone or PEO-LiTFSI composites containing a polymer identical to that attached to hairy NPs. Based on the discovered ability of hairy NP to influence bulk and interfacial properties of solid electrolyte, their use as additives is expected to be equally effective in reducing dendrite formation in other electrolytes relevant for the design of solid-state battery.

25 ENERGY STORAGE↗
DOE OSTI2020

Tuning the dynamics of imidazolium-based ionic liquids via hydrogen bonding. I. The viscous regime

Combining results from impedance spectroscopy and oscillatory shear rheology, this study focuses on the relation between the mass and charge flows and on how these are affected by the H-bonding in viscous ionic liquids (ILs). In particular, we compare the relaxational behaviors of the paradigmatic IL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI) and its OH-functionalized counterpart 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (OHEMIM-TFSI). Our results and their analysis demonstrate that the presence of cationic OH-groups bears a strong impact on the overall dynamics of OHEMIM-TFSI, although no signatures of suprastructural relaxation modes could be identified in their dielectric and mechanical responses. To check whether at the origin of this strong variation is the H-bonding or merely the difference between the corresponding cation sizes (controlling both the hydrodynamic volume and the inter-charge distance), the present study includes 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (PMIM-TFSI), mixtures of EMIM-TFSI and PMIM-TFSI with lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI), and mixtures of OHEMIM-TFSI with PMIM-TFSI. Their investigation clearly reveals that the dynamical changes induced by H-bonding are significantly larger than those that can be attributed to the change in the ion size. Moreover, in the mixtures of OHEMIM-TFSI with PMIM-TFSI, a dilution of the OH-groups leads to strong deviations from ideal mixing behavior, thus highlighting the common phenomenological ground of hydroxy-functionalized ILs and other H-bonded liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Exceptional Electrical Detection of Trace NO 2 via Mixed Metal MOF-on-MOF Film-Based Sensors

The tunability of metal–organic frameworks (MOFs) makes them exceptional materials for the development of highly selective, low-power sensors for toxic gas detection. Herein, we demonstrate enhanced detection of NO 2 gas by a MOF-based electrical impedance sensor made using a unique mixed metal MOF-on-MOF synthesis. For this work, a combined experimental and computational study was performed using the exemplar Ni x Mg 1–x -MOF-74 to understand the fundamental structure–property relationships behind metal mixing and MOF film synthesis methods on sensor performance. Density functional theory results indicated that the presence of Ni in Mg-MOF-74 increased framework stability and increased the electron density of states at lower energies near the HOMO, as well as enhanced the NO 2 –Mg adsorption interaction. Impedance data of the Ni x Mg 1–x -MOF-74 films with larger Ni contents showed greater impedance change after exposure to 1 ppm of NO 2 gas. Furthermore, when synthesized through either a drop-cast or direct solvothermal film growth approach, the monometallic Ni-based sensors had the best performance. However, the mixed metal Ni x Mg 1–x -MOF-74 sensors synthesized through a MOF-on-MOF approach resulted in the highest impedance change, outperforming all monometallic Ni-based sensors. In particular, the mixed metal Ni-on-Mg-MOF-74 film was the best-performing sensor with an impedance change of 309 upon trace NO 2 exposure. Change in impedance response after NO 2 exposure was improved by 52% compared to the best monometallic Ni-on-Ni-MOF-74 sensor. Structural analysis of the Ni-on-Mg film showed that the first Mg-MOF-74 layer acts as a structural template controlling the structural features of the final film after metal exchange with Ni. This led to improved film quality, evidenced by the greater crystallinity and larger MOF grain sizes, and resulted in enhanced sensor performance which was not achievable through other metal mixing methods. Altogether, this study identifies structure–property relationships and synthetic templating methods that inform MOF-based sensor design, allowing for improved detection of toxic compounds.

36 MATERIALS SCIENCE↗