Graphitic carbon nitride nanosheet electrode-based high-performance ionic actuator

PubMed Central

Wu, Guan; Hu, Ying; Liu, Yang; Zhao, Jingjing; Chen, Xueli; Whoehling, Vincent; Plesse, Cédric; Nguyen, Giao T. M.; Vidal, Frédéric; Chen, Wei

2015-01-01

Ionic actuators have attracted attention due to their remarkably large strain under low-voltage stimulation. Because actuation performance is mainly dominated by the electrochemical and electromechanical processes of the electrode layer, the electrode material and structure are crucial. Here, we report a graphitic carbon nitride nanosheet electrode-based ionic actuator that displays high electrochemical activity and electromechanical conversion abilities, including large specific capacitance (259.4 F g−1) with ionic liquid as the electrolyte, fast actuation response (0.5±0.03% in 300 ms), large electromechanical strain (0.93±0.03%) and high actuation stability (100,000 cycles) under 3 V. The key to the high performance lies in the hierarchical pore structure with dominant size <2 nm, optimal pyridinic nitrogen active sites (6.78%) and effective conductivity (382 S m−1) of the electrode. Our study represents an important step towards artificial muscle technology in which heteroatom modulation in electrodes plays an important role in promoting electrochemical actuation performance. PMID:26028354

Developments in ICP-MS: electrochemically modulated liquid chromatography for the clean-up of ICP-MS blanks and reduction of matrix effects by flow injection ICP-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gross, Cory Thomas

2008-01-01

The focus of this dissertation is the development of techniques with which to enhance the existing abilities of inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS is a powerful technique for trace metal analysis in samples of many types, but like any technique it has certain strengths and weaknesses. Attempts are made to improve upon those strengths and to overcome certain weaknesses.

Topics in electrochemical degradation of photovoltaic modules

NASA Technical Reports Server (NTRS)

Mon, G. R.

1984-01-01

Electrochemical degradation of photovoltaic modules was examined. It is found that the extent of electrochemical damage is dependent on the integrated leakage current. The PV electrochemical degradation mechanisms in the two polarities are different: (1) degradation rates in the two polarities are of the same order of magnitude; (2) center tapped grounded arrays are a preferred system configuration to minimize electrochemical degradation. The use of thicker pottant layers and polymer substrate films to reduce equilibrium leakage current values is suggested. A metallized substrate layer, if used, should be isolated from the pottant and the frame by polyester layers, and EVA modules appear to be consistent with 30 year life allocation levels for electrochemical damage. Temperature acceleration factors are well behaved and moderately well understood; humidity acceleration factors vary radically with module construction and materials and require additional research.

Kelvin Probe Force Microscopy in liquid using Electrochemical Force Microscopy

DOE PAGES

Collins, Liam; Jesse, Stephen; Kilpatrick, J.; ...

2015-01-19

Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid-gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid–liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe-sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q watermore » and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid–liquid interface.« less

An electrochemical study of a liquid crystal used in information displays

NASA Technical Reports Server (NTRS)

Oglesby, D. M.; Kern, J. B.; Robertson, J. B.

1974-01-01

The operational lifetime of liquid crystal displays were investigated. Electrochemical reaction at the electrodes of the display can cause failure after 2000 to 3000 hours of operation. Studies using cyclic voltametry of electrochemical reactions of N (p-methoxybenzilidene p-butylaniline (MBBA), a nematic liquid crystal were made. These studies indicate the presence of a reversible reduction of MBBA at the cathode, and that the reduction product undergoes a further reaction leading to products which are not reversibly oxidized. It is concluded that the degradation of the liquid crystal in displays can be reduced with a suitable frequency of alternating voltage.

Simulation of lubricating behavior of a thioether liquid lubricant by an electrochemical method

NASA Technical Reports Server (NTRS)

Morales, W.

1984-01-01

An electrochemical cell was constructed to explore the possible radical anion forming behavior of a thioether liquid lubricant. The electrochemical behavior of the thioether was compared with the electrochemical behavior of biphenyl, which is known to form radical anions. Under controlled conditions biphenyl undergoes a reversible reaction to a radical anion, whereas the thioether undergoes an irreversible reduction yielding several products. These results are discussed in relation to boundary lubrication.

Probing Electrochemical Reactions at a Plasma-Liquid Interface

DTIC Science & Technology

2015-03-16

at a Plasma- Liquid Interface,” AVS International Symposium and Exhibition, Baltimore, MD , 2014. (presented by P. Rumbach) (c) Presentations Number of... liquid interfacial environment produces different solvated electron behavior than other approaches to generating solvated electrons (e.g., pulse...Mar-2015 Approved for Public Release; Distribution Unlimited Final Report: STIR: Probing Electrochemical Reactions at a Plasma- Liquid Interface (7.2

Electrochemically induced actuation of liquid metal marbles

NASA Astrophysics Data System (ADS)

Tang, Shi-Yang; Sivan, Vijay; Khoshmanesh, Khashayar; O'Mullane, Anthony P.; Tang, Xinke; Gol, Berrak; Eshtiaghi, Nicky; Lieder, Felix; Petersen, Phred; Mitchell, Arnan; Kalantar-Zadeh, Kourosh

2013-06-01

Controlled actuation of soft objects with functional surfaces in aqueous environments presents opportunities for liquid phase electronics, novel assembled super-structures and unusual mechanical properties. We show the extraordinary electrochemically induced actuation of liquid metal droplets coated with nanoparticles, so-called ``liquid metal marbles''. We demonstrate that nanoparticle coatings of these marbles offer an extra dimension for affecting the bipolar electrochemically induced actuation. The nanoparticles can readily migrate along the surface of liquid metals, upon the application of electric fields, altering the capacitive behaviour and surface tension in a highly asymmetric fashion. Surprising actuation behaviours are observed illustrating that nanoparticle coatings can have a strong effect on the movement of these marbles. This significant novel phenomenon, combined with unique properties of liquid metal marbles, represents an exciting platform for enabling diverse applications that cannot be achieved using rigid metal beads.Controlled actuation of soft objects with functional surfaces in aqueous environments presents opportunities for liquid phase electronics, novel assembled super-structures and unusual mechanical properties. We show the extraordinary electrochemically induced actuation of liquid metal droplets coated with nanoparticles, so-called ``liquid metal marbles''. We demonstrate that nanoparticle coatings of these marbles offer an extra dimension for affecting the bipolar electrochemically induced actuation. The nanoparticles can readily migrate along the surface of liquid metals, upon the application of electric fields, altering the capacitive behaviour and surface tension in a highly asymmetric fashion. Surprising actuation behaviours are observed illustrating that nanoparticle coatings can have a strong effect on the movement of these marbles. This significant novel phenomenon, combined with unique properties of liquid metal marbles, represents an exciting platform for enabling diverse applications that cannot be achieved using rigid metal beads. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00185g

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

Wick-and-pool electrodes for electrochemical cell

DOEpatents

Roche, Michael F.; Faist, Suzan M.; Eberhart, James G.; Ross, Laurids E.

1977-01-01

An electrode system includes a reservoir of liquid-metal reactant, and a wick extending from a submersed location within the reservoir into the molten electrolyte of an electrochemical cell structure. The wick is flooded with the liquid metal and thereby serves as one electrode within the cell. This electrode system has application in high-temperature batteries employing molten alkali metals or their alloys as active material within an electrode submersed within a molten salt electrolyte. It also can be used in electrochemical cells where the purification, separation or electrowinning of liquid metals is accomplished.

Wick-and-pool electrodes for electrochemical cell

DOEpatents

Roche, Michael F.; Faist, Suzan M.; Eberhart, James G.; Ross, Laurids E.

1980-01-01

An electrode system includes a reservoir of liquid-metal reactant, and a wick extending from a submersed location within the reservoir into the molten electrolyte of an electrochemical cell structure. The wick is flooded with the liquid metal and thereby serves as one electrode within the cell. This electrode system has application in high-temperature batteries employing molten alkali metals or their alloys as active material within an electrode submersed within a molten salt electrolyte. It also can be used in electrochemical cells where the purification, separation or electrowinning of liquid metals is accomplished.

Electrochemically Based Modules for Sterilization in the Field. Phase 2.

DTIC Science & Technology

1995-09-30

NO: DAMD 17-91-C-1105 TITLE: Electrochemically Based Modules for Sterilization in the Field PRINCIPAL INVESTIGATOR(S) : G. Duncan Hitchens, Ph.D. Tom...NUMBERS Electrochemically Based Modules for Sterilization in the Field 6. AUTHOR(S) DAMD17-91-C-1105 G. Duncan Hitchens, Ph.D. Tom C. Allen, Tom D. Rogers...of high concentration ozone as an alternative to ethylene oxide for use in medical sterilization systems. Evaluations of high concentration

Full data acquisition in Kelvin Probe Force Microscopy: Mapping dynamic electric phenomena in real space.

PubMed

Collins, Liam; Belianinov, Alex; Somnath, Suhas; Balke, Nina; Kalinin, Sergei V; Jesse, Stephen

2016-08-12

Kelvin probe force microscopy (KPFM) has provided deep insights into the local electronic, ionic and electrochemical functionalities in a broad range of materials and devices. In classical KPFM, which utilizes heterodyne detection and closed loop bias feedback, the cantilever response is down-sampled to a single measurement of the contact potential difference (CPD) per pixel. This level of detail, however, is insufficient for materials and devices involving bias and time dependent electrochemical events; or at solid-liquid interfaces, where non-linear or lossy dielectrics are present. Here, we demonstrate direct recovery of the bias dependence of the electrostatic force at high temporal resolution using General acquisition Mode (G-Mode) KPFM. G-Mode KPFM utilizes high speed detection, compression, and storage of the raw cantilever deflection signal in its entirety at high sampling rates. We show how G-Mode KPFM can be used to capture nanoscale CPD and capacitance information with a temporal resolution much faster than the cantilever bandwidth, determined by the modulation frequency of the AC voltage. In this way, G-Mode KPFM offers a new paradigm to study dynamic electric phenomena in electroactive interfaces as well as a promising route to extend KPFM to the solid-liquid interface.

f-Elements in ionic liquids: A synthetic, spectroscopic and electrochemical study

NASA Astrophysics Data System (ADS)

Bhatt, Anand Indravadan

This thesis reports on chemical research directed towards the utilisation of low temperature ionic liquids (LTILs) for the electrorefming of uranium and plutonium from spent nuclear fuel. Initial studies focus on evaluating the relevant physical and electrochemical properties of LTILs. One room temperature ionic liquid, [(CH[3])[3]N(n-C[4]H[9])][N(SO[2]CF[3])[2

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors.

PubMed

Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

2015-12-04

Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO₂) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO₂ sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review.

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

PubMed Central

Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

2015-01-01

Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO2) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO2 sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review. PMID:26690155

Non-haloaluminate room-temperature ionic liquids in electrochemistry--a review.

PubMed

Buzzeo, Marisa C; Evans, Russell G; Compton, Richard G

2004-08-20

Some twenty-five years after they first came to prominence as alternative electrochemical solvents, room temperature ionic liquids (RTILs) are currently being employed across an increasingly wide range of chemical fields. This review examines the current state of ionic liquid-based electrochemistry, with particular focus on the work of the last decade. Being composed entirely of ions and possesing wide electrochemical windows (often in excess of 5 volts), it is not difficult to see why these compounds are seen by electrochemists as attractive potential solvents. Accordingly, an examination of the pertinent properties of ionic liquids is presented, followed by an assessment of their application to date across the various electrochemical disciplines, concluding with an outlook viewing current problems and directions.

Room-Temperature Ionic Liquids for Electrochemical Capacitors

NASA Technical Reports Server (NTRS)

Fireman, Heather; Yowell, Leonard; Moloney, Padraig G.; Arepalli, Sivaram; Nikolaev, P.; Huffman, C.; Ready, Jud; Higgins, C.D.; Turano, S. P.; Kohl, P.A.;

One-man electrochemical air revitalization system evaluation

NASA Technical Reports Server (NTRS)

Schbert, F. H.; Marshall, R. D.; Hallick, T. M.; Woods, R. R.

1976-01-01

A program to evaluate the performance of a one man capacity, self contained electrochemical air revitalization system was successfully completed. The technology readiness of this concept was demonstrated by characterizing the performance of this one man system over wide ranges in cabin atmospheric conditions. The electrochemical air revitalization system consists of a water vapor electrolysis module to generate oxygen from water vapor in the cabin air, and an electrochemical depolarized carbon dioxide concentrator module to remove carbon dioxide from the cabin air. A control/monitor instrumentation package that uses the electrochemical depolarized concentrator module power generated to partially offset the water vapor electrolysis module power requirements and various structural fluid routing components are also part of the system. The system was designed to meet the one man metabolic oxygen generation and carbon dioxide removal requirements, thereby controlling cabin partial pressure of oxygen at 22 kN/sq m and cabin pressure of carbon dioxide at 400 N/sq m over a wide range in cabin air relative humidity conditions.

Metal-air cell with performance enhancing additive

DOEpatents

Friesen, Cody A; Buttry, Daniel

2015-11-10

Systems and methods drawn to an electrochemical cell comprising a low temperature ionic liquid comprising positive ions and negative ions and a performance enhancing additive added to the low temperature ionic liquid. The additive dissolves in the ionic liquid to form cations, which are coordinated with one or more negative ions forming ion complexes. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. The ion complexes improve oxygen reduction thermodynamics and/or kinetics relative to the ionic liquid without the additive.

Application of ionic liquids in electrochemical sensing systems.

PubMed

Shiddiky, Muhammad J A; Torriero, Angel A J

2011-01-15

Since 1992, when the room temperature ionic liquids (ILs) based on the 1-alkyl-3-methylimidazolium cation were reported to provide an attractive combination of an electrochemical solvent and electrolyte, ILs have been widely used in electrodeposition, electrosynthesis, electrocatalysis, electrochemical capacitor, and lithium batteries. However, it has only been in the last few years that electrochemical biosensors based on carbon ionic liquid electrodes (CILEs) and IL-modified macrodisk electrodes have been reported. However, there are still a lot of challenges in achieving IL-based sensitive, selective, and reproducible biosensors for high speed analysis of biological and environmental compounds of interest. This review discusses the principles of operation of electrochemical biosensors based on CILEs and IL/composite-modified macrodisk electrodes. Subsequently, recent developments and major strategies for enhancing sensing performance are discussed. Key challenges and opportunities of IL-based biosensors to further development and use are considered. Emphasis is given to direct electron-transfer reaction and electrocatalysis of hemeproteins and enzyme-modified composite electrodes. Copyright © 2010 Elsevier B.V. All rights reserved.

The role of upstream distal electrodes in mitigating electrochemical degradation of ionic liquid ion sources

NASA Astrophysics Data System (ADS)

Brikner, Natalya; Lozano, Paulo C.

2012-11-01

Ionic liquid ion sources produce molecular ions from micro-tip emitters wetted with room-temperature molten salts. When a single ion polarity is extracted, counterions accumulate and generate electrochemical reactions that limit the source lifetime. The dynamics of double layer formation are reviewed and distal electrode contacts are introduced to resolve detrimental electrochemical decomposition effects at the micro-tip apex. By having the emitter follow the ionic liquid potential, operation can be achieved for an extended period of time with no apparent degradation of the material, indicating that electrochemistry can be curtailed and isolated to the upstream distal electrode.

Electrochemical determination of hydroquinone using hydrophobic ionic liquid-type carbon paste electrodes

PubMed Central

2010-01-01

Three types of carbon paste electrodes (CPEs) with different liquid binders were fabricated, and their electrochemical behavior was characterized via a potassium hexacyanoferrate(II) probe. 1-Octyl-3-methylimidazolium hexafluorophosphate ionic liquid (IL) as a hydrophobic conductive pasting binder showed better electrochemical performance compared with the commonly employed binder. The IL-contained CPEs demonstrated excellent electroactivity for oxidation of hydroquinone. A diffusion control mechanism was confirmed and the diffusion coefficient (D) of 5.05 × 10-4 cm2 s-1 was obtained. The hydrophobic IL-CPE is promising for the determination of hydroquinone in terms of high sensitivity, easy operation, and good durability. PMID:20977733

Electrochemical Sensing and Imaging Based on Ion Transfer at Liquid/Liquid Interfaces

PubMed Central

Amemiya, Shigeru; Kim, Jiyeon; Izadyar, Anahita; Kabagambe, Benjamin; Shen, Mei; Ishimatsu, Ryoichi

2013-01-01

Here we review the recent applications of ion transfer (IT) at the interface between two immiscible electrolyte solutions (ITIES) for electrochemical sensing and imaging. In particular, we focus on the development and recent applications of the nanopipet-supported ITIES and double-polymer-modified electrode, which enable the dynamic electrochemical measurements of IT at nanoscopic and macroscopic ITIES, respectively. High-quality IT voltammograms are obtainable using either technique to quantitatively assess the kinetics and dynamic mechanism of IT at the ITIES. Nanopipet-supported ITIES serves as an amperometric tip for scanning electrochemical microscopy to allow for unprecedentedly high-resolution electrochemical imaging. Voltammetric ion sensing at double-polymer-modified electrodes offers high sensitivity and unique multiple-ion selectivity. The promising future applications of these dynamic approaches for bioanalysis and electrochemical imaging are also discussed. PMID:24363454

Synthesis of hetero compounds using dialkylcarbonate quaternation

DOEpatents

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2017-10-17

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Synthesis of hetero ionic compounds using dialkylcarbonate quaternization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2017-09-19

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Synthesis of hetero ionic compounds using dialkylcarbonate quaternization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2018-04-03

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Ionic Liquid-Doped Gel Polymer Electrolyte for Flexible Lithium-Ion Polymer Batteries

PubMed Central

Zhang, Ruisi; Chen, Yuanfen; Montazami, Reza

2015-01-01

Application of gel polymer electrolytes (GPE) in lithium-ion polymer batteries can address many shortcomings associated with liquid electrolyte lithium-ion batteries. Due to their physical structure, GPEs exhibit lower ion conductivity compared to their liquid counterparts. In this work, we have investigated and report improved ion conductivity in GPEs doped with ionic liquid. Samples containing ionic liquid at a variety of volume percentages (vol %) were characterized for their electrochemical and ionic properties. It is concluded that excess ionic liquid can damage internal structure of the batteries and result in unwanted electrochemical reactions; however, samples containing 40–50 vol % ionic liquid exhibit superior ionic properties and lower internal resistance compared to those containing less or more ionic liquids.

From Two-Phase to Three-Phase: The New Electrochemical Interface by Oxide Electrocatalysts

NASA Astrophysics Data System (ADS)

Xu, Zhichuan J.

2018-03-01

Electrochemical reactions typically occur at the interface between a solid electrode and a liquid electrolyte. The charge exchange behaviour between these two phases determines the kinetics of electrochemical reactions. In the past few years, significant advances have been made in the development of metal oxide electrocatalysts for fuel cell and electrolyser reactions. However, considerable gaps remain in the fundamental understanding of the charge transfer pathways and the interaction between the metal oxides and the conducting substrate on which they are located. In particular, the electrochemical interfaces of metal oxides are significantly different from the traditional (metal) ones, where only a conductive solid electrode and a liquid electrolyte are considered. Oxides are insulating and have to be combined with carbon as a conductive mediator. This electrode configuration results in a three-phase electrochemical interface, consisting of the insulating oxide, the conductive carbon, and the liquid electrolyte. To date, the mechanistic insights into this kind of non-traditional electrochemical interface remain unclear. Consequently conventional electrochemistry concepts, established on classical electrode materials and their two-phase interfaces, are facing challenges when employed for explaining these new electrode materials. [Figure not available: see fulltext.

Method of making electrodes for electrochemical cell

DOEpatents

Kaun, Thomas D.; Kilsdonk, Dennis J.

1983-01-01

A method of making an electrode for an electrochemical cell in which particulate electrode-active material is mixed with a liquid organic carrier chemically inert with respect to the electrode-active material, mixing the liquid carrier to form an extrudable slurry. The liquid carrier is present in an amount of from about 10 to about 50 percent by volume of the slurry, and then the carrier is removed from the slurry leaving the electrode-active material.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Electrochemical Polishing Applications and EIS of a Novel Choline Chloride-Based Ionic Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Minimal surface roughness is a critical feature for high-field superconducting radio frequency (SRF) cavities used to engineer particle accelerators. Current methods for polishing Niobium cavities typically utilize solutions containing a mixture of concentrated sulfuric and hydrofluoric acid. Polishing processes such as these are effective, yet there are many hazards and costs associated with the use (and safe disposal) of the concentrated acid solutions. An alternative method for electrochemical polishing of the cavities was explored using a novel ionic liquid solution containing choline chloride. Potentiostatic electrochemical impedance spectroscopy (EIS) was used to analyze the ionic polishing solution. Final surface roughness ofmore » the Nb was found to be comparable to that of the acid-polishing method, as assessed by atomic force microscopy (AFM). This indicates that ionic liquid-based electrochemical polishing of Nb is a viable replacement for acid-based methods for preparation of SRF cavities.« less

Electrochemical Detection in Stacked Paper Networks.

PubMed

Liu, Xiyuan; Lillehoj, Peter B

2015-08-01

Paper-based electrochemical biosensors are a promising technology that enables rapid, quantitative measurements on an inexpensive platform. However, the control of liquids in paper networks is generally limited to a single sample delivery step. Here, we propose a simple method to automate the loading and delivery of liquid samples to sensing electrodes on paper networks by stacking multiple layers of paper. Using these stacked paper devices (SPDs), we demonstrate a unique strategy to fully immerse planar electrodes by aqueous liquids via capillary flow. Amperometric measurements of xanthine oxidase revealed that electrochemical sensors on four-layer SPDs generated detection signals up to 75% higher compared with those on single-layer paper devices. Furthermore, measurements could be performed with minimal user involvement and completed within 30 min. Due to its simplicity, enhanced automation, and capability for quantitative measurements, stacked paper electrochemical biosensors can be useful tools for point-of-care testing in resource-limited settings. © 2015 Society for Laboratory Automation and Screening.

Young coconut water ameliorates depression via modulation of neurotransmitters: possible mechanism of action.

PubMed

Rao, Sadia Saleem; Najam, Rahila

2016-10-01

In the current era, plants are frequently tested for its antidepressant potential. Therefore young coconut water, a commonly used plant based beverage, was selected to explore its antidepressant potential. Rodents were selected for this study and forced swim test was conducted to explore antidepressant activity. Analysis of brain biogenic amines using high performance liquid chromatography coupled with electrochemical detection and potentiation of noradrenaline toxicity model were also incorporated in this study to demonstrate probable antidepressant mechanism of action. Coconut water was administered orally at the dose of 4 ml/100 g. Young coconut water showed highly significant increase in struggling time (p < 0.001) in forced swim test. This suggests antidepressant effect of young coconut water. In noradrenaline toxicity model, it was observed that young coconut water is not a good adrenergic component as its lethality percentage in this test was observed 0 % unlike imipramine which showed lethality of 100 %. High performance liquid chromatography-electrochemical detection of rodent's brain revealed decline in 5-hydroxytryptamine, noradrenaline and dopamine, with concomitant decline in metabolites 5-hydroxyindoleacetic acid, 3,4-dihydroxyphenylacetic acid, homovanillic acid and increase in 5-hydroxyindoleacetic acid/5-hydroxytryptamine ratio. Findings from the exploration of monoamines suggest antidepressant effect of young coconut water via homeostasis of monoamines synthesis.

Electrochemical Deburring

NASA Technical Reports Server (NTRS)

Burley, R. K.

1983-01-01

Electrochemical deburring removes burrs from assembled injector tubes. Since process uses liquid anodic dissolution in liquid electrolyte to proide deburring action, smoothes surfaces and edges in otherwise inaccessible areas. Tool consists of sleeve that contains metallic ring cathode. Sleeve is placed over tube, and electrolytic solution is forced to flow between tube and sleeve. The workpiece serves an anode.

Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

NASA Astrophysics Data System (ADS)

Meng, Jianbing; Dong, Xiaojuan; Wei, Xiuting; Yin, Zhanmin

2014-03-01

Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The results show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.

Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meng, Jianbing, E-mail: jianbingmeng@126.com; Dong, Xiaojuan; Wei, Xiuting

Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The resultsmore » show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.« less

The determination of fenspiride in human plasma and urine by liquid chromatography with electrochemical or ultraviolet detection.

PubMed

Sauveur, C; Baune, A; Vergnes, N; Jeanniot, J P

1989-01-01

A selective and sensitive method for the determination of fenspiride in biological fluids is described. The method involves liquid-liquid extraction followed by separation on a reversed-phase column with electrochemical detection for low levels of the drug in plasma (less than or equal to 100 ng ml-1) or UV absorption for higher concentrations in plasma or urine. The method is suitable for pharmacokinetic analyses and drug monitoring studies.

Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors.

PubMed

Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre; Zigah, Dodzi; Mehdi, Ahmad; Vioux, André; Freunberger, Stefan A; Favier, Frédéric; Fontaine, Olivier

2017-04-01

Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

Resonant tunneling modulation in quasi-2D Cu(2)O/SnO(2) p-n horizontal-multi-layer heterostructure for room temperature H(2)S sensor application.

PubMed

Cui, Guangliang; Zhang, Mingzhe; Zou, Guangtian

2013-01-01

Heterostructure material that acts as resonant tunneling system is a major scientific challenge in applied physics. Herein, we report a resonant tunneling system, quasi-2D Cu(2)O/SnO(2) p-n heterostructure multi-layer film, prepared by electrochemical deposition in a quasi-2D ultra-thin liquid layer. By applying a special half-sine deposition potential across the electrodes, Cu(2)O and SnO(2) selectively and periodically deposited according to their reduction potentials. The as-prepared heterostructure film displays excellent sensitivity to H(2)S at room temperature due to the resonant tunneling modulation. Furthermore, it is found that the laser illumination could enhance the gas response, and the mechanism with laser illumination is discussed. It is the first report on gas sensing application of resonant tunneling modulation. Hence, heterostructure material act as resonant tunneling system is believed to be an ideal candidate for further improvement of room temperature gas sensing.

Electrochemical Deposition of Niobium onto the Surface of Copper Using a Novel Choline Chloride-Based Ionic Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wixtroma, Alex I.; Buhlera, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride-based solutions can be used to replace acid-based electrochemical polishing solutions. In this study niobium metal was successfully deposited on the surface of copper substrate via electrochemical deposition using a novel choline chloride-based ionic liquid. The niobium metal used for deposition on the Cu had been dissolved in the solution from electrochemical polishing of a solid niobium piece prior to the deposition. The visible coating on the surface of the Cu was analyzed using scanning electron microscopy (SEM) and electron dispersive x-ray spectroscopy (EDX). This deposition method effectively recycles previously dissolved niobium from electrochemicalmore » polishing.« less

Atomistic Simulation and Electronic Structure of Lithium Doped Ionic Liquids: Structure, Transport, and Electrochemical Stability

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bauschlicher, Charles W.; Lawson, John W.

2015-01-01

Zero-temperature density functional theory (DFT), density functional theory molecular dynamics (DFT-MD), and classical molecular dynamics using polarizable force fields (PFF-MD) are employed to evaluate the influence of Lithium ion on the structure, transport, and electrochemical stability of three potential ionic liquid electrolytes: N--methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([pyr14][TFSI]), N--methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ([pyr13][FSI]), and 1-ethyl-3--methylimidazolium boron tetrafluoride ([EMIM][BF4]). We characterize the Lithium ion solvation shell through zero-temperature DFT simulations of [Li(Anion)sub n](exp n-1) -clusters, DFT-MD simulations of isolated lithium ions in small ionic liquid systems, and PFF-MD simulations with high Li-doping levels in large ionic liquid systems. At low levels of Li-salt doping, highly stable solvation shells having 2-3 anions are seen in both [pyr14][TFSI] and [pyr13][FSI], while solvation shells with 4 anions dominate in [EMIM][BF sub 4]. At higher levels of doping, we find the formation of complex Li-network structures that increase the frequency of 4 anion-coordinated solvation shells. A comparison of computational and experimental Raman spectra for a wide range of [Li(Anion) sub n](exp n -1) - clusters shows that our proposed structures are consistent with experiment. We estimate the ion diffusion coefficients and quantify both size and simulation time effects. We find estimates of lithium ion diffusion are a reasonable order of magnitude and can be corrected for simulation time effects. Simulation size, on the other hand, is also important, with diffusion coefficients from long PFF-MD simulations of small cells having 20-40% error compared to large-cell values. Finally, we compute the electrochemical window using differences in electronic energy levels of both isolated cation/anion pairs and small ionic liquid systems with Li-salt doping. The single pair and liquid-phase systems provide similar estimates of electrochemical window, while Li-doping in the liquid-phase systems results in electrochemical windows little changed from the neat systems. Pure and hybrid functionals systematically provide an upper and lower bound, respectively, to the experimental electrochemical window for the systems studied here.

Lubricant-impregnated surfaces for electrochemical applications, and devices and systems using same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Solomon, Brian Richmond; Chen, Xinwei; Chiang, Yet-Ming

In certain embodiments, the invention relates to an electrochemical device having a liquid lubricant impregnated surface. At least a portion of the interior surface of the electrochemical device includes a portion that includes a plurality of solid features disposed therein. The plurality of solid features define a plurality of regions therebetween. A lubricant is disposed in the plurality of regions which retain the liquid lubricant in the plurality of regions during operation of the device. An electroactive phase comes in contact with at least the portion of the interior surface. The liquid lubricant impregnated surface introduces a slip at themore » surface when the electroactive phase flows along the surface. The electroactive phase may be a yield stress fluid.« less

Performance of Liquid Phase Exfoliated Graphene As Electrochemical Double Layer Capacitors Electrodes

NASA Astrophysics Data System (ADS)

Huffstutler, Jacob; Wasala, Milinda; Richie, Julianna; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

2014-03-01

We will present the results of our investigations of electrochemical double layer capacitors (EDLCs) or supercapacitors (SC) fabricated using liquid-phase exfoliated graphene. Several electrolytes, such as aqueous potassium hydroxide KOH (6M), ionic 1-Butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and ionic 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate[BMP][FAP] were used. These EDLC's show good performance compared to other carbon nanomaterials based EDLC's devices. We found that the liquid phase exfoliated graphene based devices possess specific capacitance values as high as 262 F/g, when used with ionic liquid electrolyte[BMP][FAP], with power densities (~ 454 W/kg) and energy densities (~ 0.38Wh/kg). Further, these devices indicated rapid charge transfer response even without the use of any binders or specially prepared current collectors. A detailed electrochemical impedance spectroscopy analysis in order to understand the phenomenon of charge storage in these materials will be presented.

Apparatus and method for electrochemical modification of liquids

DOEpatents

James, Patrick I

2015-04-21

An apparatus for electrochemical modification of liquid streams employing an electrolytic cell which includes an anode compartment defined by an anode structure where oxidation is effected, containing a liquid electrolyte anolyte, and a cathode compartment defined by a cathode structure where reduction is effected containing a liquid electrolyte catholyte. In addition, the electrolytic cell includes at least one additional compartment arranged at least partially between the anode compartment and the cathode compartment and separated from the anode compartment and the cathode compartment by a separator structure arranged to supports ionic conduction of current between the anode structure and the cathode structure.

Electrochemical methods for monitoring of environmental carcinogens.

PubMed

Barek, J; Cvacka, J; Muck, A; Quaiserová, V; Zima, J

2001-04-01

The use of modern electroanalytical techniques, namely differential pulse polarography, differential pulse voltammetry on hanging mercury drop electrode or carbon paste electrode, adsorptive stripping voltammetry and high performance liquid chromatography with electrochemical detection for the determination of trace amounts of carcinogenic N-nitroso compounds, azo compounds, heterocyclic compounds, nitrated polycyclic aromatic hydrocarbons and aromatic and heterocyclic amines is discussed. Scope and limitations of these methods are described and some practical applications based on their combination with liquid-liquid or solid phase extraction are given.

CMOS Amperometric ADC With High Sensitivity, Dynamic Range and Power Efficiency for Air Quality Monitoring.

PubMed

Li, Haitao; Boling, C Sam; Mason, Andrew J

2016-08-01

Airborne pollutants are a leading cause of illness and mortality globally. Electrochemical gas sensors show great promise for personal air quality monitoring to address this worldwide health crisis. However, implementing miniaturized arrays of such sensors demands high performance instrumentation circuits that simultaneously meet challenging power, area, sensitivity, noise and dynamic range goals. This paper presents a new multi-channel CMOS amperometric ADC featuring pixel-level architecture for gas sensor arrays. The circuit combines digital modulation of input currents and an incremental Σ∆ ADC to achieve wide dynamic range and high sensitivity with very high power efficiency and compact size. Fabricated in 0.5 [Formula: see text] CMOS, the circuit was measured to have 164 dB cross-scale dynamic range, 100 fA sensitivity while consuming only 241 [Formula: see text] and 0.157 [Formula: see text] active area per channel. Electrochemical experiments with liquid and gas targets demonstrate the circuit's real-time response to a wide range of analyte concentrations.

Advanced air revitalization system testing

NASA Technical Reports Server (NTRS)

Heppner, D. B.; Hallick, T. M.; Schubert, F. H.

1983-01-01

A previously developed experimental air revitalization system was tested cyclically and parametrically. One-button startup without manual interventions; extension by 1350 hours of tests with the system; capability for varying process air carbon dioxide partial pressure and humidity and coolant source for simulation of realistic space vehicle interfaces; dynamic system performance response on the interaction of the electrochemical depolarized carbon dioxide concentrator, the Sabatier carbon dioxide reduction subsystem, and the static feed water electrolysis oxygen generation subsystem, the carbon dioxide concentrator module with unitized core technology for the liquid cooled cell; and a preliminary design for a regenerative air revitalization system for the space station are discussed.

A reconfigurable liquid metal antenna driven by electrochemically controlled capillarity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, M.; Adams, J. J., E-mail: jjadams2@ncsu.edu; Trlica, C.

2015-05-21

We describe a new electrochemical method for reversible, pump-free control of liquid eutectic gallium and indium (EGaIn) in a capillary. Electrochemical deposition (or removal) of a surface oxide on the EGaIn significantly lowers (or increases) its interfacial tension as a means to induce the liquid metal in (or out) of the capillary. A fabricated prototype demonstrates this method in a reconfigurable antenna application in which EGaIn forms the radiating element. By inducing a change in the physical length of the EGaIn, the operating frequency of the antenna tunes over a large bandwidth. This purely electrochemical mechanism uses low, DC voltagesmore » to tune the antenna continuously and reversibly between 0.66 GHz and 3.4 GHz resulting in a 5:1 tuning range. Gain and radiation pattern measurements agree with electromagnetic simulations of the device, and its measured radiation efficiency varies from 41% to 70% over its tuning range.« less

Noncovalent Pi-Pi Stacking at the Carbon-Electrolyte Interface: Controlling the Voltage Window of Electrochemical Supercapacitors.

PubMed

Li, Mengya; Westover, Andrew S; Carter, Rachel; Oakes, Landon; Muralidharan, Nitin; Boire, Timothy C; Sung, Hak-Joon; Pint, Cary L

2016-08-03

A key parameter in the operation of an electrochemical double-layer capacitor is the voltage window, which dictates the device energy density and power density. Here we demonstrate experimental evidence that π-π stacking at a carbon-ionic liquid interface can modify the operation voltage of a supercapacitor device by up to 30%, and this can be recovered by steric hindrance at the electrode-electrolyte interface introduced by poly(ethylene oxide) polymer electrolyte additives. This observation is supported by Raman spectroscopy, electrochemical impedance spectroscopy, and differential scanning calorimetry that each independently elucidates the signature of π-π stacking between imidazole groups in the ionic liquid and the carbon surface and the role this plays to lower the energy barrier for charge transfer at the electrode-electrolyte interface. This effect is further observed universally across two separate ionic liquid electrolyte systems and is validated by control experiments showing an invariant electrochemical window in the absence of a carbon-ionic liquid electrode-electrolyte interface. As interfacial or noncovalent interactions are usually neglected in the mechanistic picture of double-layer capacitors, this work highlights the importance of understanding chemical properties at supercapacitor interfaces to engineer voltage and energy capability.

Bias-induced modulation of ultrafast carrier dynamics in metallic single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Maekawa, Keisuke; Yanagi, Kazuhiro; Minami, Yasuo; Kitajima, Masahiro; Katayama, Ikufumi; Takeda, Jun

2018-02-01

The gate bias dependence of excited-state relaxation dynamics in metallic single-walled carbon nanotubes (MCNTs) was investigated using pump-probe transient absorption spectroscopy coupled with electrochemical doping through an ionic liquid. The transient transmittance decayed exponentially with the pump-probe delay time, whose value could be tuned via the Fermi-level modulation of Dirac electrons under a bias voltage. The obtained relaxation time was the shortest when the Fermi level was at the Dirac point of the MCNTs, and exhibited a U-shaped dependence on the bias voltage. Because optical dipole transitions between the Dirac bands are forbidden in MCNTs, the observed dynamics were attributed to carrier relaxation from the E11 band to the Dirac band. Using a model that considers the suppression of electron-electron scattering (impact ionization) due to Pauli blocking, we could qualitatively explain the obtained bias dependence of the relaxation time.

Refined method for predicting electrochemical windows of ionic liquids and experimental validation studies.

PubMed

Zhang, Yong; Shi, Chaojun; Brennecke, Joan F; Maginn, Edward J

2014-06-12

A combined classical molecular dynamics (MD) and ab initio MD (AIMD) method was developed for the calculation of electrochemical windows (ECWs) of ionic liquids. In the method, the liquid phase of ionic liquid is explicitly sampled using classical MD. The electrochemical window, estimated by the energy difference between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), is calculated at the density functional theory (DFT) level based on snapshots obtained from classical MD trajectories. The snapshots were relaxed using AIMD and quenched to their local energy minima, which assures that the HOMO/LUMO calculations are based on stable configurations on the same potential energy surface. The new procedure was applied to a group of ionic liquids for which the ECWs were also experimentally measured in a self-consistent manner. It was found that the predicted ECWs not only agree with the experimental trend very well but also the values are quantitatively accurate. The proposed method provides an efficient way to compare ECWs of ionic liquids in the same context, which has been difficult in experiments or simulation due to the fact that ECW values sensitively depend on experimental setup and conditions.

Oxidation-Mediated Fingering in Liquid Metals

NASA Astrophysics Data System (ADS)

Eaker, Collin B.; Hight, David C.; O'Regan, John D.; Dickey, Michael D.; Daniels, Karen E.

2017-10-01

We identify and characterize a new class of fingering instabilities in liquid metals; these instabilities are unexpected due to the large interfacial tension of metals. Electrochemical oxidation lowers the effective interfacial tension of a gallium-based liquid metal alloy to values approaching zero, thereby inducing drastic shape changes, including the formation of fractals. The measured fractal dimension (D =1.3 ±0.05 ) places the instability in a different universality class than other fingering instabilities. By characterizing changes in morphology and dynamics as a function of droplet volume and applied electric potential, we identify the three main forces involved in this process: interfacial tension, gravity, and oxidative stress. Importantly, we find that electrochemical oxidation can generate compressive interfacial forces that oppose the tensile forces at a liquid interface. The surface oxide layer ultimately provides a physical and electrochemical barrier that halts the instabilities at larger positive potentials. Controlling the competition between interfacial tension and oxidative (compressive) stresses at the interface is important for the development of reconfigurable electronic, electromagnetic, and optical devices that take advantage of the metallic properties of liquid metals.

Advanced EMU electrochemically regenerable CO2 and moisture absorber module breadboard

NASA Technical Reports Server (NTRS)

Lee, M. C.; Sudar, M.; Chang, B. J.

1988-01-01

The applicability of the Electrochemically Regenerable Carbon Dioxide and Moisture Absorption Technology to the advanced extravehicular mobility unit was demonstrated by designing, fabricating, and testing a breadboard Absorber Module and an Electrochemical Regenerator. Test results indicated that the absorber module meets or exceeds the carbon dioxide removal requirements specified for the design and can meet the moisture removal requirement when proper cooling is provided. CO2 concentration in the vent gas stream was reduced from 0.52 to 0.027 kPa (3.9 to 0.20 mm Hg) for the full five hour test period. Vent gas dew point was reduced from inlet values of 294 K (69 F) to 278 K (41 F) at the outlet. The regeneration of expended absorbent was achieved by the electrochemical method employed in the testing. An absorbent bed using microporous hydrophobic membrane sheets with circulating absorbent is shown to be the best approach to the design of an Absorber Module based on sizing and performance. Absorber Module safety design, comparison of various absorbents and their characteristics, moisture absorption and cooling study and subsystem design and operation time-lining study were also performed.

Product selectivity control induced by using liquid-liquid parallel laminar flow in a microreactor.

PubMed

Amemiya, Fumihiro; Matsumoto, Hideyuki; Fuse, Keishi; Kashiwagi, Tsuneo; Kuroda, Chiaki; Fuchigami, Toshio; Atobe, Mahito

2011-06-07

Product selectivity control based on a liquid-liquid parallel laminar flow has been successfully demonstrated by using a microreactor. Our electrochemical microreactor system enables regioselective cross-coupling reaction of aldehyde with allylic chloride via chemoselective cathodic reduction of substrate by the combined use of suitable flow mode and corresponding cathode material. The formation of liquid-liquid parallel laminar flow in the microreactor was supported by the estimation of benzaldehyde diffusion coefficient and computational fluid dynamics simulation. The diffusion coefficient for benzaldehyde in Bu(4)NClO(4)-HMPA medium was determined to be 1.32 × 10(-7) cm(2) s(-1) by electrochemical measurements, and the flow simulation using this value revealed the formation of clear concentration gradient of benzaldehyde in the microreactor channel over a specific channel length. In addition, the necessity of the liquid-liquid parallel laminar flow was confirmed by flow mode experiments.

Acetylcholinesterase-Based Electrochemical Multiphase Microreactor for Detection of Organophosphorous Compounds (Preprint)

DTIC Science & Technology

2007-04-01

target molecules, we are interested in incorporating the existing, liquid AChE sensor chemistry into a multiphase microreactor . The multiphase... microreactor will play a critical role in combining microsensor technology with analytical biochemistry and increase reaction time, sensitivity and... microreactor with a micro-scale gas- liquid interface, 2) to adapt AChE biochemistry into the microreactor in order to develop an electrochemical biosensor for

Nafion(TM) Coats For Electrodes In Liquid-Feed Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R.; Surampudi, Subbarao; Halpert, Gerald; Vamos, Eugene; Frank, Harvey A.

1995-01-01

Coating or impregnation with commercially available material enables oxidation of organic liquid fuels. Nafion(TM) investigated for use in application because of known combination of desirable characteristics: It is perfluorinated, hydrophilic, proton-conducting ion-exchange polymer exhibiting relatively high thermal and electrochemical stability and not detrimental to kinetics of electrochemical processes. Available in solubilized form and used to apply stable coats to surfaces of electrodes.

In situ TEM study of the Li-Au reaction in an electrochemical liquid cell.

PubMed

Zeng, Zhiyuan; Liang, Wen-I; Chu, Ying-Hao; Zheng, Haimei

2014-01-01

We study the lithiation of a Au electrode in an electrochemical liquid cell using transmission electron microscopy (TEM). The commercial liquid electrolyte for lithium ion batteries (1 M lithium hexafluorophosphate LiPF6 dissolved in 1 : 1 (v/v) ethylene carbonate (EC) and diethyl carbonate (DEC)) was used. Three distinct types of morphology change during the reaction, including gradual dissolution, explosive reaction and local expansion/shrinkage, are observed. It is expected that significant stress is generated from lattice expansion during lithium-gold alloy formation. There is vigorous bubble formation from electrolyte decomposition, likely due to the catalytic effect of Au, while the bubble generation is less severe with titanium electrodes. There is an increase of current in response to electron beam irradiation, and electron beam effects on the observed electrochemical reaction are discussed.

High Performance Liquid Chromatography Experiments to Undergraduate Laboratories

ERIC Educational Resources Information Center

Kissinger, Peter T.; And Others

1977-01-01

Reviews the principles of liquid chromatography with electrochemical detection (LCEC), an analytical technique that incorporates the advantages of both liquids chromatography and electrochemistry. Also suggests laboratory experiments using this technique. (MLH)

A High-Q AFM Sensor Using a Balanced Trolling Quartz Tuning Fork in the Liquid

PubMed Central

Li, Yingzi; Song, Zihang; Lin, Rui; Chen, Yifu; Qian, Jianqiang

2018-01-01

A quartz tuning fork (QTF) has been widely used as a force sensor of the frequency modulation atomic force microscope due to its ultrahigh stiffness, high quality factor and self-sensing nature. However, due to the bulky structure and exposed surface electrode arrangement, its application is limited, especially in liquid imaging of in situ biological samples, ionic liquids, electrochemical reaction, etc. Although the complication can be resolved by coating insulating materials on the QTF surface and then immersing the whole QTF into the liquid, it would result in a sharp drop of the quality factor, which will reduce the sensitivity of the QTF. To solve the problem, a novel method, called the balanced trolling quartz tuning fork (BT-QTF), is introduced here. In this method, two same probes are glued on both prongs of the QTF separately while only one probe immersed in the liquid. With the method, the hydrodynamic interaction can be reduced, thus the BT-QTF can retain a high quality factor and constant resonance frequency. The stable small vibration of the BT-QTF can be achieved in the liquid. Initially, a theoretical model is presented to analyze the sensing performance of the BT-QTF in the liquid. Then, the sensing performance analysis experiments of the BT-QTF have been performed. At last, the proposed method is applied to atomic force microscope imaging different samples in the liquid, which proves its feasibility. PMID:29783740

By-products of electrochemical synthesis of suberic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirobokova, O.I.; Adamov, A.A.; Freidlin, G.N.

By-products of the electrochemical synthesis of dimethyl suberate from glutaric anhydride were studied. This is isolated by thermal dehydration of a mixture of lower dicarboxylic acids that are wastes from the production of adipic acid. To isolate the by-products, they used the methods of vacuum rectification and preparative gas-liquid chromatography, and for their identification, PMR, IR spectroscopy, gas-liquid chromatography, and other known physicochemical methods of investigation.

Electrical, structural, thermal and electrochemical properties of corn starch-based biopolymer electrolytes.

PubMed

Liew, Chiam-Wen; Ramesh, S

2015-06-25

Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF6) and ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) are prepared by solution casting technique. Temperature dependence-ionic conductivity studies reveal Vogel-Tamman-Fulcher (VTF) relationship which is associated with free volume theory. Ionic liquid-based biopolymer electrolytes show lower glass transition temperature (Tg) than ionic liquid-free biopolymer electrolyte. X-ray diffraction (XRD) studies demonstrate higher amorphous region of ionic liquid-added biopolymer electrolytes. In addition, the potential stability window of the biopolymer electrolyte becomes wider and stable up to 2.9V. Conclusively, the fabricated electric double layer capacitor (EDLC) shows improved electrochemical performance upon addition of ionic liquid into the biopolymer electrolyte. The specific capacitance of EDLC based on ionic liquid-added polymer electrolyte is relatively higher than that of ionic liquid-free polymer electrolyte as depicted in cyclic voltammogram. Copyright © 2015 Elsevier Ltd. All rights reserved.

Analysis of microdialysate monoamines, including noradrenaline, dopamine and serotonin, using capillary ultra-high performance liquid chromatography and electrochemical detection.

PubMed

Ferry, Barbara; Gifu, Elena-Patricia; Sandu, Ioana; Denoroy, Luc; Parrot, Sandrine

2014-03-01

Electrochemical methods are very often used to detect catecholamine and indolamine neurotransmitters separated by conventional reverse-phase high performance liquid chromatography (HPLC). The present paper presents the development of a chromatographic method to detect monoamines present in low-volume brain dialysis samples using a capillary column filled with sub-2μm particles. Several parameters (repeatability, linearity, accuracy, limit of detection) for this new ultrahigh performance liquid chromatography (UHPLC) method with electrochemical detection were examined after optimization of the analytical conditions. Noradrenaline, adrenaline, serotonin, dopamine and its metabolite 3-methoxytyramine were separated in 1μL of injected sample volume; they were detected above concentrations of 0.5-1nmol/L, with 2.1-9.5% accuracy and intra-assay repeatability equal to or less than 6%. The final method was applied to very low volume dialysates from rat brain containing monoamine traces. The study demonstrates that capillary UHPLC with electrochemical detection is suitable for monitoring dialysate monoamines collected at high sampling rate. Copyright © 2014 Elsevier B.V. All rights reserved.

Frontiers in poly(ionic liquid)s: syntheses and applications.

PubMed

Qian, Wenjing; Texter, John; Yan, Feng

2017-02-20

We review recent works on the synthesis and application of poly(ionic liquid)s (PILs). Novel chemical structures, different synthetic strategies and controllable morphologies are introduced as a supplement to PIL systems already reported. The primary properties determining applications, such as ionic conductivity, aqueous solubility, thermodynamic stability and electrochemical/chemical durability, are discussed. Furthermore, the near-term applications of PILs in multiple fields, such as their use in electrochemical energy materials, stimuli-responsive materials, carbon materials, and antimicrobial materials, in catalysis, in sensors, in absorption and in separation materials, as well as several special-interest applications, are described in detail. We also discuss the limitations of PIL applications, efforts to improve PIL physics, and likely future developments.

Electrochemical carbon dioxide concentrator advanced technology tasks

NASA Technical Reports Server (NTRS)

Schneider, J. J.; Schubert, F. H.; Hallick, T. M.; Woods, R. R.

1975-01-01

Technology advancement studies are reported on the basic electrochemical CO2 removal process to provide a basis for the design of the next generation cell, module and subsystem hardware. An Advanced Electrochemical Depolarized Concentrator Module (AEDCM) is developed that has the characteristics of low weight, low volume, high CO2, removal, good electrical performance and low process air pressure drop. Component weight and noise reduction for the hardware of a six man capacity CO2 collection subsystem was developed for the air revitalization group of the Space Station Prototype (SSP).

Ionic liquid containing hydroxamate and N-alkyl sulfamate ions

DOEpatents

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2016-03-15

Embodiments of the invention are related to ionic liquids and more specifically to ionic liquids used in electrochemical metal-air cells in which the ionic liquid includes a cation and an anion selected from hydroxamate and/or N-alkyl sulfamate anions.

Method of making electrodes for electrochemical cell. [Li-Al alloy

DOEpatents

Kaun, T.D.; Kilsdonk, D.J.

1981-07-29

A method is described for making an electrode for an electrochemical cell in which particulate electrode-active material is mixed with a liquid organic carrier chemically inert with respect to the electrode-active material, mixing the liquid carrier to form an extrudable slurry. The liquid carrier is present in an amount of from about 10 to about 50% by volume of the slurry, and then the carrier is removed from the slurry leaving the electrode-active material. The method is particularly suited for making a lithium-aluminum alloy negative electrode for a high-temperature cell.

Resonant tunneling modulation in quasi-2D Cu2O/SnO2 p-n horizontal-multi-layer heterostructure for room temperature H2S sensor application

PubMed Central

Cui, Guangliang; Zhang, Mingzhe; Zou, Guangtian

2013-01-01

Heterostructure material that acts as resonant tunneling system is a major scientific challenge in applied physics. Herein, we report a resonant tunneling system, quasi-2D Cu2O/SnO2 p-n heterostructure multi-layer film, prepared by electrochemical deposition in a quasi-2D ultra-thin liquid layer. By applying a special half-sine deposition potential across the electrodes, Cu2O and SnO2 selectively and periodically deposited according to their reduction potentials. The as-prepared heterostructure film displays excellent sensitivity to H2S at room temperature due to the resonant tunneling modulation. Furthermore, it is found that the laser illumination could enhance the gas response, and the mechanism with laser illumination is discussed. It is the first report on gas sensing application of resonant tunneling modulation. Hence, heterostructure material act as resonant tunneling system is believed to be an ideal candidate for further improvement of room temperature gas sensing. PMID:23409241

Application of N-doped graphene modified carbon ionic liquid electrode for direct electrochemistry of hemoglobin.

PubMed

Sun, Wei; Dong, Lifeng; Deng, Ying; Yu, Jianhua; Wang, Wencheng; Zhu, Qianqian

2014-06-01

Nitrogen-doped graphene (NG) was synthesized and used for the investigation on direct electrochemistry of hemoglobin (Hb) with a carbon ionic liquid electrode as the substrate electrode. Due to specific characteristics of NG such as excellent electrocatalytic property and large surface area, direct electron transfer of Hb was realized with enhanced electrochemical responses appearing. Electrochemical behaviors of Hb on the NG modified electrode were carefully investigated with the electrochemical parameters calculated. The Hb modified electrode exhibited excellent electrocatalytic reduction activity toward different substrates, such as trichloroacetic acid and H2O2, with wider dynamic range and lower detection limit. These findings show that NG can be used for the preparation of chemically modified electrodes with improved performance and has potential applications in electrochemical sensing. Copyright © 2014 Elsevier B.V. All rights reserved.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries.

PubMed

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M

2014-08-29

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

NASA Astrophysics Data System (ADS)

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-08-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

PubMed Central

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-01-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

Liquid electrode

DOEpatents

Ekechukwu, Amy A.

1994-01-01

A dropping electrolyte electrode for use in electrochemical analysis of non-polar sample solutions, such as benzene or cyclohexane. The liquid electrode, preferably an aqueous salt solution immiscible in the sample solution, is introduced into the solution in dropwise fashion from a capillary. The electrolyte is introduced at a known rate, thus, the droplets each have the same volume and surface area. The electrode is used in making standard electrochemical measurements in order to determine properties of non-polar sample solutions.

A simple and sensitive determination of histamine and N tau-methylhistamine in biological fluids by high-performance liquid chromatography with electrochemical detection.

PubMed

Houdi, A A; Crooks, P A; Van Loon, G R; Schubert, C A

1987-05-01

The determination of picomolar levels of histamine and its major metabolite, N tau-methylhistamine, in biological fluids was achieved using reversed-phase liquid chromatography coupled with electrochemical detection. A simple sample purification procedure for blood and urine samples was carried out prior to analysis using an Amberlite CG-50 cation-exchange resin, which afforded an excellent recovery of both compounds.

Electrochemical Liquid Phase Epitaxy (ec-LPE): A New Methodology for the Synthesis of Crystalline Group IV Semiconductor Epifilms.

PubMed

Demuth, Joshua; Fahrenkrug, Eli; Ma, Luyao; Shodiya, Titilayo; Deitz, Julia I; Grassman, Tyler J; Maldonado, Stephen

2017-05-24

Deposition of epitaxial germanium (Ge) thin films on silicon (Si) wafers has been achieved over large areas with aqueous feedstock solutions using electrochemical liquid phase epitaxy (ec-LPE) at low temperatures (T ≤ 90 °C). The ec-LPE method uniquely blends the simplicity and control of traditional electrodeposition with the material quality of melt growth. A new electrochemical cell design based on the compression of a liquid metal electrode into a thin cavity that enables ec-LPE is described. The epitaxial nature, low strain character, and crystallographic defect content of the resultant solid Ge films were analyzed by electron backscatter diffraction, scanning transmission electron microscopy, high resolution X-ray diffraction, and electron channeling contrast imaging. The results here show the first step toward a manufacturing infrastructure for traditional crystalline inorganic semiconductor epifilms that does not require high temperature, gaseous precursors, or complex apparatus.

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

NASA Technical Reports Server (NTRS)

Hernandez-Lugo, Dionne M.; Wu, James; Bennett, William; Ming, Yu; Zhu, Yu

2015-01-01

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

Liquid Hydrocarbon Production from CO2 : Recent Development in Metal-Based Electrocatalysis.

PubMed

Daiyan, Rahman; Lu, Xunyu; Ng, Yun Hau; Amal, Rose

2017-11-23

Rising levels of CO 2 accumulation in the atmosphere have attracted considerable interest in technologies capable of CO 2 capture, storage and conversion. The electrochemical reduction of CO 2 into high-value liquid organic products could be of vital importance to mitigate this issue. The conversion of CO 2 into liquid fuels by using photovoltaic cells, which can readily be integrated in the current infrastructure, will help realize the creation of a sustainable cycle of carbon-based fuel that will promote zero net CO 2 emissions. Despite promising findings, significant challenges still persist that must be circumvented to make the technology profitable for large-scale utilization. With such possibilities, this Minireview presents the current high-performing catalysts for the electrochemical reduction of CO 2 to liquid hydrocarbons, address the limitations and unify the current understanding of the different reaction mechanisms. The Minireview also explores current research directions to improve process efficiencies and production rate and discusses the scope of using photo-assisted electrochemical reduction systems to find stable, highly efficient catalysts that can harvest solar energy directly to convert CO 2 into liquid hydrocarbons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and properties of alkoxy- and alkenyl-substituted peralkylated imidazolium ionic liquids.

PubMed

Maton, Cedric; Brooks, Neil R; Van Meervelt, Luc; Binnemans, Koen; Schaltin, Stijn; Fransaer, Jan; Stevens, Christian V

2013-10-21

Novel peralkylated imidazolium ionic liquids bearing alkoxy and/or alkenyl side chains have been synthesized and studied. Different synthetic routes towards the imidazoles and the ionic liquids comprising bromide, iodide, methanesulfonate, bis(trifluoromethylsulfonyl)imide ([NTf2](-)), and dicyanamide {[N(CN)2](-)} as the anion were evaluated, and this led to a library of analogues, for which the melting points, viscosities, and electrochemical windows were determined. Incorporation of alkenyl moieties hindered solidification, except for cations with high symmetry. The alkoxy-derivatized ionic liquids are often crystalline; however, room-temperature ionic liquids (RTILs) were obtained with the weakly coordinating anions [NTf2](-) and [N(CN)2](-). For the viscosities of the peralkylated RTILs, an opposite trend was found, that is, the alkoxy derivatives are less viscous than their alkenyl-substituted analogues. Of the crystalline compounds, X-ray diffraction data were recorded and related to their molecular properties. Upon alkoxy substitution, the electrochemical cathodic limit potential was found to be more positive, whereas the complete electrochemical window of the alkenyl-substituted imidazolium salts was shifted to somewhat more positive potentials. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

NASA Astrophysics Data System (ADS)

Tiruye, Girum Ayalneh; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

2016-09-01

Four Ionic Liquid based Polymer Electrolytes (IL-b-PE) were prepared by blending a Polymeric Ionic Liquid, Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PILTFSI), with four different ionic liquids: 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (IL-b-PE1), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (IL-b-PE2), 1-(2-hydroxy ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HEMimTFSI) (IL-b-PE3), and 1-Butyl-1-methylpyrrolidinium dicyanamide, (PYR14DCA) (IL-b-PE4). Physicochemical properties of IL-b-PE such as ionic conductivity, thermal and electrochemical stability were found to be dependent on the IL properties. For instance, ionic conductivity was significantly higher for IL-b-PE2 and IL-b-PE4 containing IL with small size anions (FSI and DCA) than IL-b-PE1 and IL-b-PE3 bearing IL with bigger anion (TFSI). On the other hand, wider electrochemical stability window (ESW) was found for IL-b-PE1 and IL-b-PE2 having ILs with electrochemically stable pyrrolidinium cation and FSI and TFSI anions. Solid state Supercapacitors (SCs) were assembled with activated carbon electrodes and their electrochemical performance was correlated with the polymer electrolyte properties. Best performance was obtained with SC having IL-b-PE2 that exhibited a good compromise between ionic conductivity and electrochemical window. Specific capacitance (Cam), real energy (Ereal) & real power densities (Preal) as high as 150 F g-1, 36 Wh kg-1 & 1170 W kg-1 were found at operating voltage of 3.5 V.

Flow Visualization of Low Prandtl Number Fluids using Electrochemical Measurements

NASA Technical Reports Server (NTRS)

Crunkleton, D.; Anderson, T.; Narayanan, R.; Labrosse, G.

2003-01-01

It is well established that residual flows exist in contained liquid metal processes. In 1-g processing, buoyancy forces often drive these flows and their magnitudes can be substantial. It is also known that residual flows can exist during microgravity processing, and although greatly reduced in magnitude, they can influence the properties of the processed materials. Unfortunately, there are very few techniques to visualize flows in opaque, high temperature liquid metals, and those available are not easily adapted to flight investigation. In this study, a novel technique is developed that uses liquid tin as the model fluid and solid-state electrochemical cells constructed from Yttria-Stabilized Zirconia (YSZ) to establish and measure dissolved oxygen boundary conditions. The melt serves as a common electrode for each of the electrochemical cells in this design, while independent reference electrodes are maintained at the outside surfaces of the electrolyte. By constructing isolated electrochemical cells at various locations along the container walls, oxygen is introduced or extracted by imposing a known electrical potential or passing a given current between the melt and the reference electrode. This programmed titration then establishes a known oxygen concentration boundary condition at the selected electrolyte-melt interface. Using the other cells, the concentration of oxygen at the electrolyte-melt interface is also monitored by measuring the open-circuit potentials developed between the melt and reference electrodes. Thus the electrochemical cells serve to both establish boundary conditions for the passive tracer and sense its path. Rayleigh-Benard convection was used to validate the electrochemical approach to flow visualization. Thus, a numerical characterization of the second critical Rayleigh numbers in liquid tin was conducted for a variety of Cartesian aspect ratios. The extremely low Prandtl number of tin represents the lowest value studied numerically. Additionally, flow field oscillations are visualized and the effect of tilt on convecting systems is quantified. Experimental studies of the effect of convection in liquid tin are presented. Three geometries are studied: (1) double electrochemical cell with vertical concentration gradients; (2) double cell with horizontal concentration gradients; and (3) multiple cells with vertical temperature gradients. The first critical Rayleigh number transition is detected with geometry (1) and it is concluded that current measurements are not as affected by convection as EMF measurements. The system is compared with numerical simulations in geometry (2), and oscillating convection is detected with geometry (3).

Ionic-liquid materials for the electrochemical challenges of the future.

PubMed

Armand, Michel; Endres, Frank; MacFarlane, Douglas R; Ohno, Hiroyuki; Scrosati, Bruno

2009-08-01

Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Ionic-liquid materials for the electrochemical challenges of the future

NASA Astrophysics Data System (ADS)

Armand, Michel; Endres, Frank; Macfarlane, Douglas R.; Ohno, Hiroyuki; Scrosati, Bruno

2009-08-01

Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Thermally-Rechargeable Electrochemical Cell

NASA Technical Reports Server (NTRS)

Richter, R.

1985-01-01

Proposed liquid-sodium/sulfur electrochemical cell recharged by heat, rather than electric generator. Concept suitable for energy storage for utilites, mobile electronic equipment, and solar thermoelectric power systems. Sodium ions driven across membrane with aid of temperature differential.

Extension of nano-scaled exploration into solution/liquid systems using tip-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Pienpinijtham, Prompong; Vantasin, Sanpon; Kitahama, Yasutaka; Ekgasit, Sanong; Ozaki, Yukihiro

2017-08-01

This review shows updated experimental cases of tip-enhanced Raman scattering (TERS) operated in solution/liquid systems. TERS in solution/liquid is still infancy, but very essential and challenging because crucial and complicated biological processes such as photosynthesis, biological electron transfer, and cellular respiration take place and undergo in water, electrolytes, or buffers. The measurements of dry samples do not reflect real activities in those kinds of systems. To deeply understand them, TERS in solution/liquid is needed to be developed. The first TERS experiment in solution/liquid is successfully performed in 2009. After that time, TERS in solution/liquid has gradually been developed. It shows a potential to study structural changes of biomembranes, opening the world of dynamic living cells. TERS is combined with electrochemical techniques, establishing electrochemical TERS (EC-TERS) in 2015. EC-TERS creates an interesting path to fulfil the knowledge about electrochemical-related reactions or processes. TERS tip can be functionalized with sensitive molecules to act as a "surface-enhanced Raman scattering (SERS) at tip" for investigating distinct properties of systems in solution/liquid e.g., pH and electron transfer mechanism. TERS setup is continuously under developing. Versatile geometry of the setup and a guideline of a systematic implementation for a setup of TERS in solution/liquid are proposed. New style of setup is also reported for TERS imaging in solution/liquid. From all of these, TERS in solution/liquid will expand a nano-scaled exploration into solution/liquid systems of various fields e.g., energy storages, catalysts, electronic devices, medicines, alternative energy sources, and build a next step of nanoscience and nanotechnology.

Electrochemical pesticide detection with AutoDip--a portable platform for automation of crude sample analyses.

PubMed

Drechsel, Lisa; Schulz, Martin; von Stetten, Felix; Moldovan, Carmen; Zengerle, Roland; Paust, Nils

2015-02-07

Lab-on-a-chip devices hold promise for automation of complex workflows from sample to answer with minimal consumption of reagents in portable devices. However, complex, inhomogeneous samples as they occur in environmental or food analysis may block microchannels and thus often cause malfunction of the system. Here we present the novel AutoDip platform which is based on the movement of a solid phase through the reagents and sample instead of transporting a sequence of reagents through a fixed solid phase. A ball-pen mechanism operated by an external actuator automates unit operations such as incubation and washing by consecutively dipping the solid phase into the corresponding liquids. The platform is applied to electrochemical detection of organophosphorus pesticides in real food samples using an acetylcholinesterase (AChE) biosensor. Minimal sample preparation and an integrated reagent pre-storage module hold promise for easy handling of the assay. Detection of the pesticide chlorpyrifos-oxon (CPO) spiked into apple samples at concentrations of 10(-7) M has been demonstrated. This concentration is below the maximum residue level for chlorpyrifos in apples defined by the European Commission.

Lithium insertion in graphite from ternary ionic liquid-lithium salt electrolytes. I. Electrochemical characterization of the electrolytes

NASA Astrophysics Data System (ADS)

Appetecchi, Giovanni B.; Montanino, Maria; Balducci, Andrea; Lux, Simon F.; Winterb, Martin; Passerini, Stefano

In this paper we report the results of chemical-physical investigation performed on ternary room temperature ionic liquid-lithium salt mixtures as electrolytes for lithium-ion battery systems. The ternary electrolytes were made by mixing N-methyl- N-propyl pyrrolidinium bis(fluorosulfonyl) imide (PYR 13FSI) and N-butyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR 14TFSI) ionic liquids with lithium hexafluorophosphate (LiPF 6) or lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The mixtures were developed based on preliminary results on the cyclability of graphite electrodes in the IL-LiX binary electrolytes. The results clearly show the beneficial synergic effect of the two ionic liquids on the electrochemical properties of the mixtures.

Applications of KPFM-Based Approaches for Surface Potential and Electrochemical Measurements in Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, Liam F.; Weber, Stefan A. L.; Rodriguez, Brian

Kelvin probe force microscopy (KPFM) has been widely used to map nanoscale surface potentials of materials in ambient and ultra-high vacuum environments. However, to study and ultimately understand charge-related processes, e.g., in biological systems or to further improve energy storage devices such as electrochemical batteries, nanoscale surface potential measurements in liquid environments are required. Here, we describe the various implementations of KPFM-based approaches for measuring surface potentials in liquid environments. We provide practical guidelines for surface potential measurements and describe what other information can be obtained. Finally, we discuss potential applications and limitations of existing approaches and present possible solutionsmore » for the successful implementation of liquid KPFM.« less

Liquid electrode

DOEpatents

Ekechukwu, A.A.

1994-07-05

A dropping electrolyte electrode is described for use in electrochemical analysis of non-polar sample solutions, such as benzene or cyclohexane. The liquid electrode, preferably an aqueous salt solution immiscible in the sample solution, is introduced into the solution in dropwise fashion from a capillary. The electrolyte is introduced at a known rate, thus, the droplets each have the same volume and surface area. The electrode is used in making standard electrochemical measurements in order to determine properties of non-polar sample solutions. 2 figures.

Cation effect on small phosphonium based ionic liquid electrolytes with high concentrations of lithium salt

NASA Astrophysics Data System (ADS)

Chen, Fangfang; Kerr, Robert; Forsyth, Maria

2018-05-01

Ionic liquid electrolytes with high alkali salt concentrations have displayed some excellent electrochemical properties, thus opening up the field for further improvements to liquid electrolytes for lithium or sodium batteries. Fundamental computational investigations into these high concentration systems are required in order to gain a better understanding of these systems, yet they remain lacking. Small phosphonium-based ionic liquids with high concentrations of alkali metal ions have recently shown many promising results in experimental studies, thereby prompting us to conduct further theoretical exploration of these materials. Here, we conducted a molecular dynamics simulation on four small phosphonium-based ionic liquids with 50 mol. % LiFSI salt, focusing on the effect of cation structure on local structuring and ion diffusional and rotational dynamics—which are closely related to the electrochemical properties of these materials.

Wide electrochemical window solvents for use in electrochemical devices and electrolyte solutions incorporating such solvents

DOEpatents

Angell, Charles Austen; Zhang, Sheng-Shui; Xu, Kang

1998-01-01

The present invention relates to electrolyte solvents for use in liquid or rubbery electrolyte solutions. Specifically, this invention is directed to boron-containing electrolyte solvents and boron-containing electrolyte solutions.

Ionic liquids as electrolytes for Li-ion batteries-An overview of electrochemical studies

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Świderska-Mocek, Agnieszka

The paper reviews properties of room temperature ionic liquids (RTILs) as electrolytes for lithium and lithium-ion batteries. It has been shown that the formation of the solid electrolyte interface (SEI) on the anode surface is critical to the correct operation of secondary lithium-ion batteries, including those working with ionic liquids as electrolytes. The SEI layer may be formed by electrochemical transformation of (i) a molecular additive, (ii) RTIL cations or (iii) RTIL anions. Such properties of RTIL electrolytes as viscosity, conductivity, vapour pressure and lithium-ion transport numbers are also discussed from the point of view of their influence on battery performance.

Morphology controlled synthesis of platinum nanoparticles performed on the surface of graphene oxide using a gas-liquid interfacial reaction and its application for high-performance electrochemical sensing.

PubMed

Bai, Wushuang; Sheng, Qinglin; Zheng, Jianbin

2016-07-21

In this paper, we report a novel morphology-controlled synthetic method. Platinum (Pt) nanoparticles with three kinds of morphology (aggregation-like, cube-like and globular) were grown on the surface of graphene oxide (GO) using a simple gas-liquid interfacial reaction and Pt/GO nanocomposites were obtained successfully. According to the experimental results, the morphology of the Pt nanoparticles can be controlled by adjusting the reaction temperature with the protection of chitosan. The obtained Pt/GO nanocomposites were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FTIR). Then the Pt/GO nanocomposites with the three kinds of morphology were all used to fabricate electrochemical sensors. The electrochemical experimental results indicated that compared with various reported electrochemical sensors, the Pt/GO modified sensors in this work exhibit a low detection limit, high sensitivity and an extra wide linear range for the detection of nitrite. In addition, the synthesis of Pt particles based on a gas-liquid interfacial reaction provides a new platform for the controllable synthesis of nanomaterials.

Ionic liquid electrolytes for Li-air batteries: lithium metal cycling.

PubMed

Grande, Lorenzo; Paillard, Elie; Kim, Guk-Tae; Monaco, Simone; Passerini, Stefano

2014-05-08

In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li-air cells.

Ionic Liquid Electrolytes for Li–Air Batteries: Lithium Metal Cycling

PubMed Central

Grande, Lorenzo; Paillard, Elie; Kim, Guk-Tae; Monaco, Simone; Passerini, Stefano

2014-01-01

In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li–air cells. PMID:24815072

Sensitive electrochemical detection of dopamine with a DNA/graphene bi-layer modified carbon ionic liquid electrode.

PubMed

Wang, Xiaofeng; You, Zheng; Sha, Hailiang; Cheng, Yong; Zhu, Huanhuan; Sun, Wei

2014-10-01

A DNA and graphene (GR) bi-layer modified carbon ionic liquid electrode (CILE) was fabricated by an electrodeposition method. GR nanosheets were electrodeposited on the surface of CILE at the potential of -1.3 V and then DNA was further deposited at the potential of +0.5 V on GR modified CILE. Electrochemical performances of the fabricated DNA/GR/CILE were carefully investigated. Then electrochemical behaviors of dopamine (DA) on the modified electrode were studied with the calculated electrochemical parameters. Under the optimized conditions, a linear relationship between the oxidation peak current and the concentration of DA was obtained in the range from 0.1 μmol/L to 1.0 mmol/L with a detection limit of 0.027 μmol/L (3σ). The modified electrode exhibited excellent reproducibility, repeatability, stability, validation and robustness for the electrochemical detection of DA. The proposed method was further applied to the DA injection solution and human urine samples determination with satisfactory results. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis of ionic liquids

DOEpatents

Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN

2008-09-09

Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic liqand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

Synthesis of ionic liquids

DOEpatents

Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN

2011-11-01

Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic ligand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

Method for improving the durability of ion insertion materials

DOEpatents

Lee, Se-Hee; Tracy, C. Edwin; Cheong, Hyeonsik M.

2002-01-01

The invention provides a method of protecting an ion insertion material from the degradative effects of a liquid or gel-type electrolyte material by disposing a protective, solid ion conducting, electrically insulating, layer between the ion insertion layer and the liquid or gel-type electrolyte material. The invention further provides liquid or gel-type electrochemical cells having improved durability having a pair of electrodes, a pair of ion insertion layers sandwiched between the pair of electrodes, a pair of solid ion conducting layers sandwiched between the ion insertion layers, and a liquid or gel-type electrolyte material disposed between the solid ion conducting layers, where the solid ion conducting layer minimizes or prevents degradation of the faces of the ion insertion materials facing the liquid or gel-type electrolyte material. Electrochemical cells of this invention having increased durability include secondary lithium batteries and electrochromic devices.

Embedding covalency into metal catalysts for efficient electrochemical conversion of CO2.

PubMed

Lim, Hyung-Kyu; Shin, Hyeyoung; Goddard, William A; Hwang, Yun Jeong; Min, Byoung Koun; Kim, Hyungjun

2014-08-13

CO2 conversion is an essential technology to develop a sustainable carbon economy for the present and the future. Many studies have focused extensively on the electrochemical conversion of CO2 into various useful chemicals. However, there is not yet a solution of sufficiently high enough efficiency and stability to demonstrate practical applicability. In this work, we use first-principles-based high-throughput screening to propose silver-based catalysts for efficient electrochemical reduction of CO2 to CO while decreasing the overpotential by 0.4-0.5 V. We discovered the covalency-aided electrochemical reaction (CAER) mechanism in which p-block dopants have a major effect on the modulating reaction energetics by imposing partial covalency into the metal catalysts, thereby enhancing their catalytic activity well beyond modulations arising from d-block dopants. In particular, sulfur or arsenic doping can effectively minimize the overpotential with good structural and electrochemical stability. We expect this work to provide useful insights to guide the development of a feasible strategy to overcome the limitations of current technology for electrochemical CO2 conversion.

Portable system and method combining chromatography and array of electrochemical sensors

DOEpatents

Zaromb, Solomon; Stetter, Joseph R.

1989-01-01

A portable system for analyzing a fluid sample includes a small, portable, low-pressure and low-power chromatographic analyzer and a chemical parameter spectrometry monitor including an array of sensors for detecting, identifying and measuring the concentrations of a variety of components in the eluent from the chromatographic analyzer. The monitor includes one or more operating condition controllers which may be used to change one or more of the operating conditions during exposure of the sensors to the eluent from the chromatography analyzer to form a response pattern which is then compared with a library of previously established patterns. Gas and liquid chromatographic embodiments are disclosed. In the gas embodiment, the operating condition controllers include heated filaments which may convert electrochemically inactive components to electrochemically active products. In the liquid chromatography embodiment, low-power, liquid-phase equivalents of heated filaments are used with appropriate sensors. The library response patterns may be divided into subsets and the formed pattern may be assigned for comparison only with the patterns of a particular subset.

Electrodeposition of Si from an Ionic Liquid Bath at Room Temperature in the Presence of Water.

PubMed

Shah, Nisarg K; Pati, Ranjan Kumar; Ray, Abhijit; Mukhopadhyay, Indrajit

2017-02-21

The electrochemical deposition of Si has been carried out in an ionic liquid medium in the presence of water in a limited dry nitrogen environment on highly oriented pyrolytic graphite (HOPG) at room temperature. It has been found that the presence of water in ionic liquids does not affect the available effective potential window to a large extent. Silicon has been successfully deposited electrochemically in the overpotential regime in two different ionic liquids, namely, BMImTf 2 N and BMImPF 6 , in the presence of water. Although a Si thin film has been obtained from BMImTf 2 N; only distinguished Si crystals protected in ionic liquid droplets have been observed from BMImPF 6 . The most important observation of the present investigation is that the Si precursor, SiCl 4 , instead of undergoing hydrolysis, even in the presence of water, coexisted with ionic liquids, and elemental Si has been successfully electrodeposited.

Viscosity, conductivity, and electrochemical property of dicyanamide ionic liquids

NASA Astrophysics Data System (ADS)

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-03-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands.

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

PubMed Central

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-01-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands. PMID:29600245

Electrochemical Energy Storage for an Orbiting Space Station

NASA Technical Reports Server (NTRS)

Martin, R. E.

1981-01-01

The system weight of a multi hundred kilowatt fuel cell electrolysis cell energy storage system based upon alkaline electrochemical cell technology for use in a future orbiting space station in low Earth orbit (LEO) was studied. Preliminary system conceptual design, fuel cell module performance characteristics, subsystem and system weights, and overall system efficiency are identified. The impact of fuel cell module operating temperature and efficiency upon energy storage system weight is investigated. The weight of an advanced technology system featuring high strength filament wound reactant tanks and a fuel cell module employing lightweight graphite electrolyte reservoir plates is defined.

High Frequency Electromechanical Imaging of Ferroelectrics in a Liquid Environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jesse, Stephen; Chu, Ying-Hao; Kalinin, Sergei V

The coupling between electrical and mechanical phenomena is a ubiquitous feature of many information and energy storage materials and devices. In addition to involvement in performance and degradation mechanisms, electromechanical effects underpin a broad spectrum of nanoscale imaging and spectroscopies including piezoresponse force and electrochemical strain microscopies. Traditionally, these studies are conducted under ambient conditions. However, applications related to imaging energy storage and electrophysiological phenomena require operation in a liquid phase and therefore the development of electromechanical probing techniques suitable to liquid environments. Due to the relative high conductivity of most liquids and liquid decomposition at low voltages, the transfermore » of characterization techniques from ambient to liquid is not straightforward. Here we present a detailed study of ferroelectric domain imaging and manipulation in thin film BiFeO{sub 3} using piezoresponse force microscopy in liquid environments as model systems for electromechanical phenomena in general. We explore the use of contact resonance enhancement and the application of multifrequency excitation and detection principles to overcome the experimental problems introduced by a liquid environment. Understanding electromechanical sample characterization in liquid is a key aspect not only for ferroelectric oxides but also for biological and electrochemical sample systems.« less

Electrochemical kinetics and dimensional considerations, at the nanoscale

NASA Astrophysics Data System (ADS)

Yamada, H.; Bandaru, P. R.

2016-06-01

It is shown that the consideration of the density of states variation in nanoscale electrochemical systems yields modulations in the rate constant and concomitant electrical currents. The proposed models extend the utility of Marcus-Hush-Chidsey (MHC) kinetics to a larger class of materials and could be used as a test of dimensional character. The implications of the study are of much significance to an understanding and modulation of charge transfer nanostructured electrodes.

Polymers for new battery technologies.

NASA Astrophysics Data System (ADS)

Singh, Mohit

2009-03-01

The chemical and electrochemical reactivity of the components comprising today's lithium batteries has severely limited their lifetime and stability, and attempts to push the limits on energy density have exacerbated these stability issues. The weakest link in terms of safety and stability of Li ion systems is the organic liquid electrolyte that facilitates the Li^+ ion transport between the electrodes. The electrolyte is flammable and electrochemically unstable against the graphitic anode. It is the continuous electrochemical degradation of the electrolyte at the electrodes that leads to poor cycle life of the batteries, and in some cases runaway reactions that lead to explosions. Dry polymer electrolytes alleviate the electrochemical stability problem by offering a stable electrode-electrolyte interface. The absence of flammable liquids prevents runaway reactions. The main hurdle that has prevented dry polymer electrolytes from being commercialized is low ionic conductivity, and challenges in interfacing with the electrode materials. We demonstrate a novel approach towards addressing these challenges that renders batteries with excellent cycle lives, and thermal stability.

Electrochemically Initiated Tagging of Thiols Using an Electrospray Ionization-Based Liquid Microjunction Surface Sampling Probe Two-Electrode Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Berkel, Gary J; Kertesz, Vilmos

2009-01-01

This paper reports on the conversion of a liquid microjunction surface sampling probe (LMJ-SSP) into a two electrode electrochemical cell using a conductive sample surface and the probe as the two electrodes with an appropriate battery powered circuit. With this LMJ-SSP, two-electrode cell arrangement, tagging of analyte thiol functionalities (in this case peptide cysteine residues) with hydroquinone tags was initiated electrochemically using a hydroquinone doped solution when the analyte either was initially in solution or was sampled from a surface. Efficient tagging (~90%), at flow rates of 5-10 L/min, could be achieved for up to at least two cysteines onmore » a peptide. The high tagging efficiency observed was explained with a simple kinetic model. In general, the incorporation of a two-electrode electrochemical cell, or other multiple electrode arrangement, into the LMJ-SSP is expected to add to the versatility of this approach for surface sampling and ionization coupled with mass spectrometric detection.« less

Ultramicroelectrode voltammetry and scanning electrochemical microscopy in room-temperature ionic liquid electrolytes.

PubMed

Walsh, Darren A; Lovelock, Kevin R J; Licence, Peter

2010-11-01

The high viscosity and unusual properties of room temperature ionic liquids (RTILs) present a number of challenges when performing steady-state voltammetry and scanning electrochemical microscopy in RTILs. These include difficulties in recording steady-state currents at ultramicroelectrode surfaces due to low diffusion coefficients of redox species and problems associated with unequal diffusion coefficients of oxidised and reduced species in RTILs. In this tutorial review, we highlight the recent progress in the use of RTILs as electrolytes for ultramicroelectrode voltammetry and SECM. We describe the basic principles of ultramicroelectrode voltammetry and SECM and, using examples from the recent literature, we discuss the conditions that must be met to perform steady-state voltammetry and SECM measurements in RTILs. Finally, we briefly discuss the electrochemical insights that can be obtained from such measurements.

Construction of a carbon ionic liquid paste electrode based on multi-walled carbon nanotubes-synthesized Schiff base composite for trace electrochemical detection of cadmium.

PubMed

Afkhami, Abbas; Khoshsafar, Hosein; Bagheri, Hasan; Madrakian, Tayyebeh

2014-02-01

A simple, highly sensitive and selective carbon nanocomposite electrode has been developed for the electrochemical trace determination of cadmium. This sensor was designed by incorporation of multi-walled carbon nanotubes (MWCNTs) and a new synthesized Schiff base into the carbon paste ionic liquid electrode (CPE(IL)) which provides remarkably improved sensitivity and selectivity for the electrochemical stripping assay of Cd(II). The detection limit of the method was found to be 0.08 μg L(-1) (S/N=3) that is lower than the maximum contaminant level of Cd(II) allowed by the Environmental Protection Agency (EPA) in standard drinking waters. The proposed electrode exhibits good applicability for monitoring Cd(II) in various real samples. © 2013.

Strain Engineering to Modify the Electrochemistry of Energy Storage Electrodes

PubMed Central

Muralidharan, Nitin; Carter, Rachel; Oakes, Landon; Cohn, Adam P.; Pint, Cary L.

2016-01-01

Strain engineering has been a critical aspect of device design in semiconductor manufacturing for the past decade, but remains relatively unexplored for other applications, such as energy storage. Using mechanical strain as an input parameter to modulate electrochemical potentials of metal oxides opens new opportunities intersecting fields of electrochemistry and mechanics. Here we demonstrate that less than 0.1% strain on a Ni-Ti-O based metal-oxide formed on superelastic shape memory NiTi alloys leads to anodic and cathodic peak potential shifts by up to ~30 mV in an electrochemical cell. Moreover, using the superelastic properties of NiTi to enable strain recovery also recovers the electrochemical potential of the metal oxide, providing mechanistic evidence of strain-modified electrochemistry. These results indicate that mechanical energy can be coupled with electrochemical systems to efficiently design and optimize a new class of strain-modulated energy storage materials. PMID:27283872

Application of graphene-ionic liquid-chitosan composite-modified carbon molecular wire electrode for the sensitive determination of adenosine-5'-monophosphate.

PubMed

Shi, Fan; Gong, Shixing; Xu, Li; Zhu, Huanhuan; Sun, Zhenfan; Sun, Wei

2013-12-01

In this paper, a graphene (GR) ionic liquid (IL) 1-octyl-3-methylimidazolium hexafluorophosphate and chitosan composite-modified carbon molecular wire electrode (CMWE) was fabricated by a drop-casting method and further applied to the sensitive electrochemical detection of adenosine-5'-monophosphate (AMP). CMWE was prepared with diphenylacetylene (DPA) as the modifier and the binder. The properties of modified electrode were examined by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Electrochemical behaviors of AMP was carefully investigated with enhanced responses appeared, which was due to the presence of GR-IL composite on the electrode surface with excellent electrocatalytic ability. A well-defined oxidation peak of AMP appeared at 1.314 V and the electrochemical parameters were calculated by electrochemical methods. Under the selected conditions, the oxidation peak current of AMP was proportional to its concentration in the range from 0.01 μM to 80.0 μM with the detection limit as 3.42 nM (3σ) by differential pulse voltammetry. The proposed method exhibited good selectivity and was applied to the detection of vidarabine monophosphate injection samples with satisfactory results. © 2013.

Controllable Synthesis of Formaldehyde Modified Manganese Oxide Based on Gas-Liquid Interfacial Reaction and Its Application of Electrochemical Sensing.

PubMed

Bai, Wushuang; Sheng, Qinglin; Nie, Fei; Zheng, Jianbin

2015-12-30

Controllable synthesis of manganese oxides was performed via a simple one-step synthetic method. Then obtained manganese oxides which exhibit flower-like, cloud-like, hexagon-like, and rod-like morphologies were modified by formaldehyde based on a simple self-made gas-liquid reaction device respectively and the modified manganese oxides with coral-like, scallop-like and rod-like morphology were synthesized accordingly. The obtained materials were characterized and the formation mechanism was also researched. Then the modified manganese oxides were used to fabricate electrochemical sensors to detect H2O2. Comparison of electrochemical properties between three kinds of modified manganese oxides was investigated and the best one has been successfully employed as H2O2 sensor which shows a low detection limit of 0.01 μM, high sensitivity of 162.69 μA mM(-1) cm(-2), and wide linear range of 0.05 μM-12.78 mM. The study provides a new method for controllable synthesis of metal oxides, and electrochemical application of formaldehyde modified manganese oxides will provides a new strategy for electrochemical sensing with high performance, low cost, and simple fabrication.

Electropolymerized polyazulene as active material in flexible supercapacitors

NASA Astrophysics Data System (ADS)

Suominen, Milla; Lehtimäki, Suvi; Yewale, Rahul; Damlin, Pia; Tuukkanen, Sampo; Kvarnström, Carita

2017-07-01

We report the capacitive behavior of electrochemically polymerized polyazulene films in different ionic liquids. The ionic liquids in this study represent conventional imidazolium based ionic liquids with tetrafluoroborate and bis(trifluoromethylsulfonyl)imide anions as well as an unconventional choline based ionic liquid. The effect of different ionic liquids on the polymerization and capacitive performance of polyazulene films is demonstrated by cyclic voltammetry and electrochemical impedance spectroscopy in a 3-electrode cell configuration. The films exhibit the highest capacitances in the lowest viscosity ionic liquid (92 mF cm-2), while synthesis in high viscosity ionic liquid shortens the conjugation length and results in lower electroactivity (25 mF cm-2). The obtained films also show good cycling stabilities retaining over 90% of their initial capacitance over 1200 p-doping cycles. We also demonstrate, for the first time, flexible polyazulene supercapacitors of symmetric and asymmetric configurations using the choline based ionic liquid as electrolyte. In asymmetric configuration, capacitance of 55 mF (27 mF cm-2) with an equivalent series resistance of 19 Ω is obtained at operating voltage of 1.5 V. Upon increasing the operating voltage up to 2.4 V, the capacitance increases to 72 mF (36 mF cm-2).

Integration of electrochemistry with ultra-performance liquid chromatography/mass spectrometry.

PubMed

Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A; Chen, Hao

2015-01-01

This study presents the development of ultra-performance liquid chromatography (UPLC) mass spectrometry (MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of proteins/peptides that contain disulfide bonds. In our approach, a protein/peptide mixture sample undergoes a fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and tandem mass spectrometry (MS/MS) analyses. The electrochemical cell is coupled to the mass spectrometer using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, peptides that contain disulfide bonds can be differentiated from those without disulfide bonds, as the former are electroactive and reducible. MS/MS analysis of the disulfide-reduced peptide ions provides increased information on the sequence and disulfide-linkage pattern. In a reactive DESI- MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which will be useful in top- down protein structure MS analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1(~)2 orders of magnitude by using UPLC for the liquid chromatography (LC)/EC/MS platform, in comparison to the previously used high- performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion, and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis.

Ultra-large optical modulation of electrochromic porous WO3 film and the local monitoring of redox activity† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc03727a

PubMed Central

Cai, Guofa; Cui, Mengqi; Kumar, Vipin; Darmawan, Peter; Wang, Jiangxin; Wang, Xu; Lee-Sie Eh, Alice; Qian, Kai

2016-01-01

Porous WO3 films with ultra-high transmittance modulation were successfully fabricated on different substrates by a novel, facile and economical pulsed electrochemical deposited method with 1.1 s interval time between each pulse. The near ideal optical modulation (97.7% at 633 nm), fast switching speed (6 and 2.7 s), high coloration efficiency (118.3 cm2 C–1), and excellent cycling stability are achieved by the porous WO3 on ITO-coated glass. The outstanding electrochromic performances of the porous WO3 film were mainly attributed to the porous structure, which facilitates the charge-transfer, promotes the electrolyte infiltration and alleviates the expansion of the WO3 during H+ insertion compared to that of the compact structure. In addition, the relationships between the structural and electrochemical activity of the electrochromic WO3 films were further explored by the scanning electrochemical microscopy. These results testify that the porous structure can promote the infiltration of electrolyte and reduce the diffusion path, which consequently enhance the electrochemical activity. PMID:29910894

X-ray and Electrochemical Impedance Spectroscopy Diagnostic Investigations of Liquid Water in Polymer Electrolyte Membrane Fuel Cell Gas Diffusion Layers

NASA Astrophysics Data System (ADS)

Antonacci, Patrick

In this thesis, electrochemical impedance spectroscopy (EIS) and synchrotron x-ray radiography were utilized to characterize the impact of liquid water distributions in polymer electrolyte membrane fuel cell (PEMFC) gas diffusion layers (GDLs) on fuel cell performance. These diagnostic techniques were used to quantify the effects of liquid water visualized on equivalent resistances measured through EIS. The effects of varying the thickness of the microporous layer (MPL) of GDLs were studied using these diagnostic techniques. In a first study on the feasibility of this methodology, two fuel cell cases with a 100 microm-thick and a 150 microm-thick MPL were compared under constant current density operation. In a second study with 10, 30, 50, and 100 microm-thick MPLs, the liquid water in the cathode substrate was demonstrated to affect mass transport resistance, while the liquid water content in the anode (from back diffusion) affected membrane hydration, evidenced through ohmic resistance measurements.

Silica-grafted ionic liquids for revealing the respective charging behaviors of cations and anions in supercapacitors.

PubMed

Dou, Qingyun; Liu, Lingyang; Yang, Bingjun; Lang, Junwei; Yan, Xingbin

2017-12-19

Supercapacitors based on activated carbon electrodes and ionic liquids as electrolytes are capable of storing charge through the electrosorption of ions on porous carbons and represent important energy storage devices with high power delivery/uptake. Various computational and instrumental methods have been developed to understand the ion storage behavior, however, techniques that can probe various cations and anions of ionic liquids separately remain lacking. Here, we report an approach to monitoring cations and anions independently by using silica nanoparticle-grafted ionic liquids, in which ions attaching to silica nanoparticle cannot access activated carbon pores upon charging, whereas free counter-ions can. Aided by this strategy, conventional electrochemical characterizations allow the direct measurement of the respective capacitance contributions and acting potential windows of different ions. Moreover, coupled with electrochemical quartz crystal microbalance, this method can provide unprecedented insight into the underlying electrochemistry.

2,4-Toluene Diisocyanate Detection in Liquid and Gas Environments through Electrochemical Oxidation in an Ionic Liquid

PubMed Central

Lin, Lu; Rehman, Abdul; Chi, Xiaowei; Zeng, Xiangqun

2016-01-01

The electrochemical oxidation of 2,4-toluene diisocyanate (2,4-TDI) in an ionic liquid (IL) has been systematically characterized to determine plausible electrochemical and chemical reaction mechanisms and to define the optimal detection methods for such a highly significant analyte. It has been found that the use of an IL as the electrolyte allows the oxidation of 2,4-TDI to occur at a less positive anodic potential with no side reactions as compared to traditional acetonitrile based electrolytes. UV-Vis, FT-IR, Cyclic Voltammetry and Electrochemical Impedance Spectroscopy (EIS) studies have revealed the unique mechanisms of dimerization of 2,4-TDI at the electrode interface by self-addition reactions, which can be utilized to improve the selectivity of detection. The study of 2,4-TDI redox chemistry further facilitates the development of a robust amperometric sensing methodology by selecting a hydrophobic IL ([C4mpy][NTf2]) and by restricting the potential window to only include the oxidation process. Thus, this innovative electrochemical sensor is capable of avoiding the two most ubiquitous interferents in ambient conditions (i.e. humidity and oxygen), thereby enhancing the sensor performance and reliability for real world applications. The method was established to detect 2,4–TDI in both liquid and gas phases. The limits of detection (LOD) values were 130.2 ppm and 0.7862 ppm, respectively, for the two phases, and are comparable to the safety standards reported by NIOSH. The as-developed 2.4-TDI amperometric sensor exhibits a sensitivity of 1.939 μA/ppm. Moreover, due to the simplicity of design and the use of an IL both as a solvent and non-volatile electrolyte, the sensor has the potential to be miniaturized for smart sensing protocols in distributed sensor applications. PMID:26763507

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE PAGES

Guardado, Jesus O.; Salleo, Alberto

2017-07-17

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Hierarchical and Well-Ordered Porous Copper for Liquid Transport Properties Control.

PubMed

Pham, Quang N; Shao, Bowen; Kim, Yongsung; Won, Yoonjin

2018-05-09

Liquid delivery through interconnected pore network is essential for various interfacial transport applications ranging from energy storage to evaporative cooling. The liquid transport performance in porous media can be significantly improved through the use of hierarchical morphology that leverages transport phenomena at different length scales. Traditional surface engineering techniques using chemical or thermal reactions often show nonuniform surface nanostructuring within three-dimensional pore network due to uncontrollable diffusion and reactivity in geometrically complex porous structures. Here, we demonstrate hierarchical architectures on the basis of crystalline copper inverse opals using an electrochemistry approach, which offers volumetric controllability of structural and surface properties within the complex porous metal. The electrochemical process sequentially combines subtractive and additive steps-electrochemical polishing and electrochemical oxidation-to improve surface wetting properties without sacrificing structural permeability. We report the transport performance of the hierarchical inverse opals by measuring the capillary-driven liquid rise. The capillary performance parameter of hierarchically engineered inverse opal ( K/ R eff = ∼5 × 10 -3 μm) is shown to be higher than that of a typical crystalline inverse opal ( K/ R eff = ∼1 × 10 -3 μm) owing to the enhancement in fluid permeable and hydrophilic pathways. The new surface engineering method presented in this work provides a rational approach in designing hierarchical porous copper for transport performance enhancements.

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guardado, Jesus O.; Salleo, Alberto

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Chemical and Electrochemical Studies in Ionic Liquids

DTIC Science & Technology

1990-01-12

Electrochemistry and Witchcraft ", Gordon Research Conference on Electrochemistry", Santa Barbara, CA, January, 1985. OR. A. Osteryoung, ’An Introduction to...Temperature Chloroaluminate Ionic Liquids: Chemistry, Electrochemistry and Witchcraft ", Chemistry Department Colloquium, University of Alabama...Tuscaloosa, Alabama, December 1, 1988. OR. A. Osteryoung, "Ambient Temperature Chloroaluminate Ionic Liquids: Chemistry, Electrochemistry and Witchcraft

A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction

PubMed Central

Dickey, Michael D.

2016-01-01

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where interfacial tension is a dominant force. A variety of methods exist for controlling the interfacial tension of aqueous and organic liquids on this scale; however, these techniques have limited utility for liquid metals due to their large interfacial tension. Liquid metals can form soft, stretchable, and shape-reconfigurable components in electronic and electromagnetic devices. Although it is possible to manipulate these fluids via mechanical methods (e.g., pumping), electrical methods are easier to miniaturize, control, and implement. However, most electrical techniques have their own constraints: electrowetting-on-dielectric requires large (kV) potentials for modest actuation, electrocapillarity can affect relatively small changes in the interfacial tension, and continuous electrowetting is limited to plugs of the liquid metal in capillaries. Here, we present a method for actuating gallium and gallium-based liquid metal alloys via an electrochemical surface reaction. Controlling the electrochemical potential on the surface of the liquid metal in electrolyte rapidly and reversibly changes the interfacial tension by over two orders of magnitude (~500 mN/m to near zero). Furthermore, this method requires only a very modest potential (< 1 V) applied relative to a counter electrode. The resulting change in tension is due primarily to the electrochemical deposition of a surface oxide layer, which acts as a surfactant; removal of the oxide increases the interfacial tension, and vice versa. This technique can be applied in a wide variety of electrolytes and is independent of the substrate on which it rests. PMID:26863045

Thermally responsive polymer electrolytes for inherently safe electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kelly, Jesse C.

Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in electrochemical energy storage devices, while preserving the performance, lifetimes, and versatility that large-format systems require. Initial work focused on the development of a model system that demonstrated the concept of RPEs in an electrochemical device. Aqueous electrolyte solutions of polymers exhibiting properties that change in response to temperature were developed for applications in EDLCs and supercapacitors. These "smart materials" provide a means to control electrochemical systems where polymer phase separation at high temperatures affects electrolyte properties and inhibits device performance. Aqueous RPEs were synthesized using N-isopropylacrylamide, which governs the thermal properties, and fractions of acrylic acid or vinyl sulfonic acids, which provide ions to the solution. The molecular properties of these aqueous RPEs, specifically the ionic composition, were shown to influence the temperature-dependent electrolyte properties and the extent to which these electrolytes control the energy storage characteristics of a supercapacitor device. Materials with high ionic content provided the highest room temperature conductivity and electrochemical activity; however, RPEs with low ionic content provided the highest "on-off" ratio in electrochemical activity at elevated temperatures. Overall, solution pH and conductivity were altered by an order of magnitude and device performance (ability to store charge) decreased by over 70%. After demonstration of a model responsive electrolyte in an aqueous system, ionic liquid (IL) based electrolytes were developed as a means of controlling the electrochemical performance in the non-aqueous environments that batteries, specifically Li-ion, require. Here, two systems were developed: (1) an electrolyte comprising poly(ethylene oxide) (PEO), the IL, [EMIM][BF4], and a lithium salt and (2) an electrolyte comprising poly(benzyl methacrylate) (PBzMA), the IL, [EMIM][TFSI], and a lithium salt. In each system, the polymer-IL phase separation inhibited device operation at elevated temperatures. For the PEO/IL electrolyte, the thermally induced liquid-liquid phase separation was shown to decrease the ionic conductivity, thereby affecting the concentration of ions at the electrode. Additionally, an increasing charge transfer resistance associated with the phase separated polymer coating the porous electrode was shown to limit electrochemical activity significantly. For the PBzMA/IL electrolyte, the solid-liquid phase separation did not show a change in conductivity, but did cause a drastic increase in charge transfer resistance, effectively shutting off Li-ion battery operation at high temperatures. Such responsive mixtures provide a transformative approach to regulating electrochemical processes, which is necessary to achieve inherently safe operation in large format energy storage with EDLCs, supercapacitors and Li-ion batteries.

Formulation of ionic liquid electrolyte to expand the voltage window of supercapacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury

We report an effective method to expand the operating potential window (OPW) of electrochemical capacitors based on formulating the ionic liquid (IL) electrolytes. Moreover, using model electrochemical cells based on two identical onion like carbon (OLC) electrodes and two different IL electrolytes and their mixtures, it was shown that the asymmetric behavior of the electrolyte’s cation and anion toward the two electrodes limits the OPW of the cell and therefore its energy density. Additionally, a general solution to this problem is proposed by formulating the IL electrolyte mixtures to balance the capacitance of electrodes in a symmetric supercapacitor.

Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury

An effective method to expand the operating potential window (OPW) of electrochemical capacitors based on formulating the ionic-liquid (IL) electrolytes is reported. Using model electrochemical cells based on two identical onion-like carbon (OLC) electrodes and two different IL electrolytes and their mixtures, it was shown that the asymmetric behavior of the electrolyte cation and anion toward the two electrodes limits the OPW of the cell and therefore its energy density. Also, a general solution to this problem is proposed by formulating the IL electrolyte mixtures to balance the capacitance of electrodes in a symmetric supercapacitor.

Formulation of ionic liquid electrolyte to expand the voltage window of supercapacitors

DOE PAGES

Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury

2015-03-18

We report an effective method to expand the operating potential window (OPW) of electrochemical capacitors based on formulating the ionic liquid (IL) electrolytes. Moreover, using model electrochemical cells based on two identical onion like carbon (OLC) electrodes and two different IL electrolytes and their mixtures, it was shown that the asymmetric behavior of the electrolyte’s cation and anion toward the two electrodes limits the OPW of the cell and therefore its energy density. Additionally, a general solution to this problem is proposed by formulating the IL electrolyte mixtures to balance the capacitance of electrodes in a symmetric supercapacitor.

Direct liquid-feed fuel cell with membrane electrolyte and manufacturing thereof

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1999-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Improvements in interfacing of the catalyst layer and the membrane and activating catalyst materials are disclosed.

Compact electrochemical sensor system and method for field testing for metals in saliva or other fluids

DOEpatents

Lin, Yuehe; Bennett, Wendy D.; Timchalk, Charles; Thrall, Karla D.

2004-03-02

Microanalytical systems based on a microfluidics/electrochemical detection scheme are described. Individual modules, such as microfabricated piezoelectrically actuated pumps and a microelectrochemical cell were integrated onto portable platforms. This allowed rapid change-out and repair of individual components by incorporating "plug and play" concepts now standard in PC's. Different integration schemes were used for construction of the microanalytical systems based on microfluidics/electrochemical detection. In one scheme, all individual modules were integrated in the surface of the standard microfluidic platform based on a plug-and-play design. Microelectrochemical flow cell which integrated three electrodes based on a wall-jet design was fabricated on polymer substrate. The microelectrochemical flow cell was then plugged directly into the microfluidic platform. Another integration scheme was based on a multilayer lamination method utilizing stacking modules with different functionality to achieve a compact microanalytical device. Application of the microanalytical system for detection of lead in, for example, river water and saliva samples using stripping voltammetry is described.

Electrochemical Polishing Applications and EIS of a Vitamin B{sub 4}-Based Ionic Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-01-01

Modern particle accelerators require minimal interior surface roughness for Niobium superconducting radio frequency (SRF) cavities. Polishing of the Nb is currently achieved via electrochemical polishing with concentrated mixtures of sulfuric and hydrofluoric acids. This acid-based approach is effective at reducing the surface roughness to acceptable levels for SRF use, but due to acid-related hazards and extra costs (including safe disposal of used polishing solutions), an acid-free method would be preferable. This study focuses on an alternative electrochemical polishing method for Nb, using a novel ionic liquid solution containing choline chloride, also known as Vitamin B{sub 4} (VB{sub 4}). Potentiostatic electrochemicalmore » impedance spectroscopy (EIS) was also performed on the VB4-based system. Nb polished using the VB4-based method was found to have a final surface roughness comparable to that achieved via the acid-based method, as assessed by atomic force microscopy (AFM). These findings indicate that acid-free VB{sub 4}-based electrochemical polishing of Nb represents a promising replacement for acid-based methods of SRF cavity preparation.« less

Determination of organic acids by high-performance liquid chromatography with electrochemical detection during wine brewing.

PubMed

Kotani, Akira; Miyaguchi, Yuji; Tomita, Eiji; Takamura, Kiyoko; Kusu, Fumiyo

2004-03-24

Voltammetric determination of acids by means of the electrochemical reduction of quinone was applied to high-performance liquid chromatography (HPLC) with electrochemical detection (ED) for determining organic acids in fruit wines. A two-channel HPLC-ED system was fabricated by use of an ion-exclusion column and an electrochemical detector with a glassy carbon working electrode. Aqueous solution of 0.1 mM HClO(4) and ethanol containing 2-methyl-1,4-naphthoquinone served as a mobile phase and reagent solution, respectively. Determination of acetic, citric, lactic, malic, succinic, and tartaric acids was made by measuring the peak areas of the flow signals due to the reduction current of quinone caused by the eluted acids. The peak area was found to be linearly related to the acid amount ranging from 0.1 to 40 nmol per 20 microL injection. The present method was characterized by reproducibility with the simple and rapid procedure without derivatization of analytes. The method was shown as an effective means for following acid contents in fruit juices during fermentation with wine yeast.

Reliability and engineering sciences area. Materials research: Single junction thin film

NASA Technical Reports Server (NTRS)

1986-01-01

A test bench was designed and fabricated for the purpose of improving control of hot-spot test accuracy. Electrochemical corrosion research focused on corrosion mechanisms to which both crystalline and a-Si modules may be subjected in central station applications. A variety of cells and several designs were subjected to accelerated stress tests. Humiditiy degradation rates were determined and key electrochemical failure mechanisms were identified. Software was developed for the prediction of power loss resulting from open circuits in an array field of a-Si modules. Failure analysis was continued on the four ARCO Solar Genesis modules. The interactions of water on the silicon module was examined. An autocatalytic photooxidation model was proposed. The reliability and durability of bonding materials and electrical insulation were also studied.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2003-11-04

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. Fuses and various electrical and electromechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Liquid Catholyte Molecules for Nonaqueous Redox Flow Batteries

DOE PAGES

Huang, Jinhua; Cheng, Lei; Assary, Rajeev S.; ...

2014-11-25

In this study, a series of dimethoxybenzene-based catholyte molecules, which are electrochemically reversible at high potential (4.0 V vs Li/Li +) and in the form of liquid, is developed. The liquid nature offers the molecules the possibility of being a solo or co-solvent for nonaqueous redox flow batteries. This could dramatically improve the energy density.

Engineering the electrochemical capacitive properties of graphene sheets in ionic-liquid electrolytes by correct selection of anions.

PubMed

Shi, Minjie; Kou, Shengzhong; Yan, Xingbin

2014-11-01

Graphene sheet (GS)-ionic liquid (IL) supercapacitors are receiving intense interest because their specific energy density far exceeds that of GS-aqueous electrolytes supercapacitors. The electrochemical properties of ILs mainly depend on their diverse ions, especially anions. Therefore, identifying suitable IL electrolytes for GSs is currently one of the most important tasks. The electrochemical behavior of GSs in a series of ILs composed of 1-ethyl-3-methylimidazolium cation (EMIM(+)) with different anions is systematically studied. Combined with the formula derivation and building models, it is shown that the viscosity, ion size, and molecular weight of ILs affect the electrical conductivity of ILs, and thus, determine the electrochemical performances of GSs. Because the EMIM-dicyanamide IL has the lowest viscosity, ion size, and molecular weight, GSs in it exhibit the highest specific capacitance, smallest resistance, and best rate capability. In addition, because the tetrafluoroborate anion (BF4(-)) has the best electrochemical stability, the GS-[EMIM][BF4] supercapacitor has the widest potential window, and thus, displays the largest energy density. These results may provide valuable information for selecting appropriate ILs and designing high-performance GS-IL supercapacitors to meet different needs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a spectro-electrochemical cell for soft X-ray photon-in photon-out spectroscopy

NASA Astrophysics Data System (ADS)

Ishihara, Tomoko; Tokushima, Takashi; Horikawa, Yuka; Kato, Masaru; Yagi, Ichizo

2017-10-01

We developed a spectro-electrochemical cell for X-ray absorption and X-ray emission spectroscopy, which are element-specific methods to study local electronic structures in the soft X-ray region. In the usual electrochemical measurement setup, the electrode is placed in solution, and the surface/interface region of the electrode is not normally accessible by soft X-rays that have low penetration depth in liquids. To realize soft X-ray observation of electrochemical reactions, a 15-nm-thick Pt layer was deposited on a 150-nm-thick film window with an adhesive 3-nm-thick Ti layer for use as both the working electrode and the separator window between vacuum and a sample liquid under atmospheric pressure. The designed three-electrode electrochemical cell consists of a Pt film on a SiC window, a platinized Pt wire, and a commercial Ag|AgCl electrode as the working, counter, and reference electrodes, respectively. The functionality of the cell was tested by cyclic voltammetry and X-ray absorption and emission spectroscopy. As a demonstration, the electroplating of Pb on the Pt/SiC membrane window was measured by X-ray absorption and real-time monitoring of fluorescence intensity at the O 1s excitation.

Electrochemically stable electrolytes

DOEpatents

Angell, Charles Austen; Zhang, Sheng-Shui; Xu, Kang

1999-01-01

This invention relates generally to inorganic ionic liquids which function as electrolytes and do not crystallize at ambient temperature. More specifically, this invention is directed to quasi-salt inorganic ionic liquids which comprise the reaction product of a strong Lewis acid with an inorganic halide-donating molecule. This invention is further directed to quasi-salt inorganic ionic liquid mixtures which comprise combinations of electrolyte additives and quasi-salt inorganic ionic liquids. These quasi-salt inorganic ionic liquid mixtures are useful electrolytes.

Electrochemically stable electrolytes

DOEpatents

Angell, C.A.; Zhang, S.S.; Xu, K.

1999-01-05

This invention relates generally to inorganic ionic liquids which function as electrolytes and do not crystallize at ambient temperature. More specifically, this invention is directed to quasi-salt inorganic ionic liquids which comprise the reaction product of a strong Lewis acid with an inorganic halide-donating molecule. This invention is further directed to quasi-salt inorganic ionic liquid mixtures which comprise combinations of electrolyte additives and quasi-salt inorganic ionic liquids. These quasi-salt inorganic ionic liquid mixtures are useful electrolytes. 16 figs.

Promoting Effect of Layered Titanium Phosphate on the Electrochemical and Photovoltaic Performance of Dye-Sensitized Solar Cells

PubMed Central

2010-01-01

We reported a composite electrolyte prepared by incorporating layered α-titanium phosphate (α-TiP) into an iodide-based electrolyte using 1-ethyl-3-methylimidazolium tetrafluoroborate(EmimBF4) ionic liquid as solvent. The obtained composite electrolyte exhibited excellent electrochemical and photovoltaic properties compared to pure ionic liquid electrolyte. Both the diffusion coefficient of triiodide (I3−) in the electrolyte and the charge-transfer reaction at the electrode/electrolyte interface were improved markedly. The mechanism for the enhanced electrochemical properties of the composite electrolyte was discussed. The highest conversion efficiency of dye-sensitized solar cell (DSSC) was obtained for the composite electrolyte containing 1wt% α-TiP, with an improvement of 58% in the conversion efficiency than the blank one, which offered a broad prospect for the fabrication of stable DSSCs with a high conversion efficiency. PMID:20676195

Electrochemical study of the anticancer drug daunorubicin at a water/oil interface: drug lipophilicity and quantification.

PubMed

Ribeiro, José A; Silva, F; Pereira, Carlos M

2013-02-05

In this work, the ion transfer mechanism of the anticancer drug daunorubicin (DNR) at a liquid/liquid interface has been studied for the first time. This study was carried out using electrochemical techniques, namely cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The lipophilicity of DNR was investigated at the water/1,6-dichlorohexane (DCH) interface, and the results obtained were presented in the form of an ionic partition diagram. The partition coefficients of both neutral and ionic forms of the drug were determined. The analytical parameter for the detection of DNR was also investigated in this work. An electrochemical DNR sensor is proposed by means of simple ion transfer at the water/DCH interface, using DPV as the quantification technique. Experimental conditions for the analytical determination of DNR were established, and a detection limit of 0.80 μM was obtained.

An electrochemical fungicide pyrimethanil sensor based on carbon nanotubes/ionic-liquid construction modified electrode.

PubMed

Yang, Jichun; Wang, Qiong; Zhang, Minhui; Zhang, Shuming; Zhang, Lei

2015-11-15

In this study, a simple, rapid, sensitive and environmentally friendly electroanalytical detection method for pyrimethanil (PMT) was developed, which was based on multi-walled carbon nanotubes (MWCNTs) and ionic liquids (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) modified glassy carbon electrode (GCE). MWCNTs-IL modified electrode significantly enhanced the oxidation peak current of PMT by combining the excellent electrochemical properties of MWCNTs and IL, suggesting that the modified electrode can remarkably improve the sensitivity of PMT detection. Under the optimum conditions, this electrochemical sensor exhibited a linear concentration range for PMT of 1.0 × 10(-7)-1.0 × 10(-4) mol L(-1) and the detection limit was 1.6 × 10(-8) mol L(-1) (S/N = 3). The fabricated electrode showed good reproducibility, stability and anti-interference, and also it was successfully employed to detect PMT in real samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

New frontiers in materials science opened by ionic liquids.

PubMed

Torimoto, Tsukasa; Tsuda, Tetsuya; Okazaki, Ken-ichi; Kuwabata, Susumu

2010-03-19

Ionic liquids (ILs) including ambient-temperature molten salts, which exist in the liquid state even at room temperature, have a long research history. However, their applications were once limited because ILs were considered as highly moisture-sensitive solvents that should be handled in a glove box. After the first synthesis of moisture-stable ILs in 1992, their unique physicochemical properties became known in all scientific fields. ILs are composed solely of ions and exhibit several specific liquid-like properties, e.g., some ILs enable dissolution of insoluble bio-related materials and the use as tailor-made lubricants in industrial applications under extreme physicochemical conditions. Hybridization of ILs and other materials provides quasi-solid materials, which can be used to fabricate highly functional devices. ILs are also used as reaction media for electrochemical and chemical synthesis of nanomaterials. In addition, the negligible vapor pressure of ILs allows the fabrication of electrochemical devices that are operated under ambient conditions, and many liquid-vacuum technologies, such as X-ray photoelectron spectroscopy (XPS) analysis of liquids, electron microscopy of liquids, and sputtering and physical vapor deposition onto liquids. In this article, we review recent studies on ILs that are employed as functional advanced materials, advanced mediums for materials production, and components for preparing highly functional materials.

Modulation of nitrogen vacancy charge state and fluorescence in nanodiamonds using electrochemical potential

PubMed Central

Karaveli, Sinan; Gaathon, Ophir; Wolcott, Abraham; Sakakibara, Reyu; Shemesh, Or A.; Peterka, Darcy S.; Boyden, Edward S.; Owen, Jonathan S.; Yuste, Rafael; Englund, Dirk

2016-01-01

The negatively charged nitrogen vacancy (NV−) center in diamond has attracted strong interest for a wide range of sensing and quantum information processing applications. To this end, recent work has focused on controlling the NV charge state, whose stability strongly depends on its electrostatic environment. Here, we demonstrate that the charge state and fluorescence dynamics of single NV centers in nanodiamonds with different surface terminations can be controlled by an externally applied potential difference in an electrochemical cell. The voltage dependence of the NV charge state can be used to stabilize the NV− state for spin-based sensing protocols and provides a method of charge state-dependent fluorescence sensing of electrochemical potentials. We detect clear NV fluorescence modulation for voltage changes down to 100 mV, with a single NV and down to 20 mV with multiple NV centers in a wide-field imaging mode. These results suggest that NV centers in nanodiamonds could enable parallel optical detection of biologically relevant electrochemical potentials. PMID:27035935

Modulation of nitrogen vacancy charge state and fluorescence in nanodiamonds using electrochemical potential.

PubMed

Karaveli, Sinan; Gaathon, Ophir; Wolcott, Abraham; Sakakibara, Reyu; Shemesh, Or A; Peterka, Darcy S; Boyden, Edward S; Owen, Jonathan S; Yuste, Rafael; Englund, Dirk

2016-04-12

The negatively charged nitrogen vacancy (NV(-)) center in diamond has attracted strong interest for a wide range of sensing and quantum information processing applications. To this end, recent work has focused on controlling the NV charge state, whose stability strongly depends on its electrostatic environment. Here, we demonstrate that the charge state and fluorescence dynamics of single NV centers in nanodiamonds with different surface terminations can be controlled by an externally applied potential difference in an electrochemical cell. The voltage dependence of the NV charge state can be used to stabilize the NV(-) state for spin-based sensing protocols and provides a method of charge state-dependent fluorescence sensing of electrochemical potentials. We detect clear NV fluorescence modulation for voltage changes down to 100 mV, with a single NV and down to 20 mV with multiple NV centers in a wide-field imaging mode. These results suggest that NV centers in nanodiamonds could enable parallel optical detection of biologically relevant electrochemical potentials.

Modulation of nitrogen vacancy charge state and fluorescence in nanodiamonds using electrochemical potential

NASA Astrophysics Data System (ADS)

Karaveli, Sinan; Gaathon, Ophir; Wolcott, Abraham; Sakakibara, Reyu; Shemesh, Or A.; Peterka, Darcy S.; Boyden, Edward S.; Owen, Jonathan S.; Yuste, Rafael; Englund, Dirk

2016-04-01

The negatively charged nitrogen vacancy (NV-) center in diamond has attracted strong interest for a wide range of sensing and quantum information processing applications. To this end, recent work has focused on controlling the NV charge state, whose stability strongly depends on its electrostatic environment. Here, we demonstrate that the charge state and fluorescence dynamics of single NV centers in nanodiamonds with different surface terminations can be controlled by an externally applied potential difference in an electrochemical cell. The voltage dependence of the NV charge state can be used to stabilize the NV- state for spin-based sensing protocols and provides a method of charge state-dependent fluorescence sensing of electrochemical potentials. We detect clear NV fluorescence modulation for voltage changes down to 100 mV, with a single NV and down to 20 mV with multiple NV centers in a wide-field imaging mode. These results suggest that NV centers in nanodiamonds could enable parallel optical detection of biologically relevant electrochemical potentials.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2004-09-28

An electrochemical energy storage device includes a number of solid-state thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics.

PubMed

Drüschler, Marcel; Borisenko, Natalia; Wallauer, Jens; Winter, Christian; Huber, Benedikt; Endres, Frank; Roling, Bernhard

2012-04-21

Ionic liquids are of high interest for the development of safe electrolytes in modern electrochemical cells, such as batteries, supercapacitors and dye-sensitised solar cells. However, electrochemical applications of ionic liquids are still hindered by the limited understanding of the interface between electrode materials and ionic liquids. In this article, we first review the state of the art in both experiment and theory. Then we illustrate some general trends by taking the interface between the extremely pure ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and an Au(111) electrode as an example. For the study of this interface, electrochemical impedance spectroscopy was combined with in situ STM and in situ AFM techniques. In addition, we present new results for the temperature dependence of the interfacial capacitance and dynamics. Since the interfacial dynamics are characterised by different processes taking place on different time scales, the temperature dependence of the dynamics can only be reliably studied by recording and carefully analysing broadband capacitance spectra. Single-frequency experiments may lead to artefacts in the temperature dependence of the interfacial capacitance. We demonstrate that the fast capacitive process exhibits a Vogel-Fulcher-Tamman temperature dependence, since its time scale is governed by the ionic conductivity of the ionic liquid. In contrast, the slower capacitive process appears to be Arrhenius activated. This suggests that the time scale of this process is determined by a temperature-independent barrier, which may be related to structural reorganisations of the Au surface and/or to charge redistributions in the strongly bound innermost ion layer. This journal is © the Owner Societies 2012

Electrochemical detection of DNA damage induced by acrylamide and its metabolite at the graphene-ionic liquid-Nafion modified pyrolytic graphite electrode.

PubMed

Qiu, Yanyan; Qu, Xiangjin; Dong, Jing; Ai, Shiyun; Han, Ruixia

2011-06-15

A new electrochemical biosensor for directly detecting DNA damage induced by acrylamide (AA) and its metabolite was presented in this work. The graphene-ionic liquid-Nafion modified pyrolytic graphite electrode (PGE) was prepared, and then horseradish peroxidase (HRP) and natural double-stranded DNA were alternately assembled on the modified electrode by the layer-by-layer method. The PGE/graphene-ionic liquid-Nafion and the construction of the (HRP/DNA)(n) film were characterized by electrochemical impedance spectroscopy. With the guanine signal in DNA as an indicator, the damage of DNA was detected by differential pulse voltammetry after PGE/graphene-ionic liquid-Nafion/(HRP/DNA)(n) was incubated in AA solution or AA+H(2)O(2) solution at 37°C. This method provides a new model to mimic and directly detect DNA damage induced by chemical pollutants and their metabolites in vitro. The results indicated that, in the presence of H(2)O(2), HRP was activated and catalyzed the transformation of AA to glycidamide, which could form DNA adducts and induce more serious damage of DNA than AA. In order to further verify these results, UV-vis spectrophotometry was also used to investigate DNA damage induced by AA and its metabolites in solution and the similar results were obtained. Copyright © 2011 Elsevier B.V. All rights reserved.

Electrochemical biosensor based on immobilized enzymes and redox polymers

DOEpatents

Skotheim, Terje A.; Okamoto, Yoshiyuki; Hale, Paul D.

1992-01-01

The present invention relates to an electrochemical enzyme biosensor for use in liquid mixtures of components for detecting the presence of, or measuring the amount of, one or more select components. The enzyme electrode of the present invention is comprised of an enzyme, an artificial redox compound covalently bound to a flexible polymer backbone and an electron collector.

Electrochemical and/or microbiological treatment of pyrolysis wastewater.

PubMed

Silva, José R O; Santos, Dara S; Santos, Ubiratan R; Eguiluz, Katlin I B; Salazar-Banda, Giancarlo R; Schneider, Jaderson K; Krause, Laiza C; López, Jorge A; Hernández-Macedo, Maria L

2017-10-01

Electrochemical oxidation may be used as treatment to decompose partially or completely organic pollutants (wastewater) from industrial processes such as pyrolysis. Pyrolysis is a thermochemical process used to obtain bio-oil from biomasses, generating a liquid waste rich in organic compounds including aldehydes and phenols, which can be submitted to biological and electrochemical treatments in order to minimize its environmental impact. Thus, electrochemical systems employing dimensionally stable anodes (DSAs) have been proposed to enable biodegradation processes in subsurface environments. In order to investigate the organic compound degradation from residual coconut pyrolysis wastewater, ternary DSAs containing ruthenium, iridium and cerium synthetized by the 'ionic liquid method' at different calcination temperatures (500, 550, 600 and 700 °C) for the pretreatment of these compounds, were developed in order to allow posterior degradation by Pseudomonas sp., Bacillus sp. or Acinetobacter sp. bacteria. The electrode synthesized applying 500 °C displayed the highest voltammetric charge and was used in the pretreatment of pyrolysis effluent prior to microbial treatment. Regarding biological treatment, the Pseudomonas sp. exhibited high furfural degradation in wastewater samples electrochemically pretreated at 2.0 V. On the other hand, the use of Acinetobacter efficiently degraded phenolic compounds such as phenol, 4-methylphenol, 2,5-methylphenol, 4-ethylphenol and 3,5-methylphenol in both wastewater samples, with and without electrochemical pretreatment. Overall, the results indicate that the combination of both processes used in this study is relevant for the treatment of pyrolysis wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of dapsone in serum and saliva using reversed-phase high-performance liquid chromatography with ultraviolet or electrochemical detection.

PubMed

Moncrieff, J

1994-03-18

A simple, extractionless method for the determination of dapsone in serum and saliva is described. Reversed-phase high-performance liquid chromatography is used with UV detection at 295 nm or electrochemical detection at 0.7 V. Diazoxide in buffer is the internal standard for UV detection and practolol for electrochemical detection. Sample preparation is minimal with protein precipitation of serum samples whilst saliva samples are simply diluted with addition of an internal standard. Low-level serum and saliva samples are front-cut on-line with a 3 cm laboratory-made precolumn in the loop position on a standard Valco injection valve. Isocratic separation is achieved on a 250 mm x 4.6 mm I.D. stainless-steel Spherisorb S5 ODS-1 column. The mobile phase for high levels of dapsone is acetonitrile-elution buffer (12:88, v/v) at 2 ml/min and a column temperature of 40 degrees C for both serum and saliva separations. For the low-level assays using electrochemical detection and solid-phase clean-up, the mobile phase is acetonitrile-methanol-elution buffer (9:4:87, v/v/v). The UV and electrochemical detection limits are 25 ng/ml and 200 pg/ml, respectively, in both serum and saliva. This simple method is applicable to the routine monitoring of dapsone levels in serum from leprotic patients and electrochemical detection gives a simple, reliable method for the monitoring of trough values in subjects on anti-malarial prophylaxis.

Continuous synthesis of peralkylated imidazoles and their transformation into ionic liquids with improved (electro)chemical stabilities.

PubMed

Maton, Cedric; De Vos, Nils; Roman, Bart I; Vanecht, Evert; Brooks, Neil R; Binnemans, Koen; Schaltin, Stijn; Fransaer, Jan; Stevens, Christian V

2012-09-17

A versatile and efficient method to synthesize tetrasubstituted imidazoles via a one-pot modified Debus-Radziszewski reaction and their subsequent transformation into the corresponding imidazolium ionic liquids is reported. The tetrasubstituted imidazoles were also synthesized by means of a continuous flow process. This straightforward synthetic procedure allows for a fast and selective synthesis of tetrasubstituted imidazoles on a large scale. The completely substituted imidazolium dicyanamide and bis(trifluoromethylsulfonyl)imide salts were obtained via a metathesis reaction of the imidazolium iodide salts. The melting points and viscosities are of the same order of magnitude as for their non-substituted analogues. In addition to the superior chemical stability of these novel ionic liquids, which allows them to be applied in strong alkaline media, the improved thermal and electrochemical stabilities of these compounds compared with conventional imidazolium ionic liquids is also demonstrated by thermogravimetrical analysis (TGA) and cyclic voltammetry (CV). Although increased substitution of the ionic liquids does not further increase thermal stability, a definite increase in cathodic stability is observable. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance of Multi Walled Carbon Nanotubes Grown on Conductive Substrates as Supercapacitors Electrodes using Organic and Ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Winchester, Andrew; Ghosh, Sujoy; Turner, Ben; Zhang, X. F.; Talapatra, Saikat

2012-02-01

In this work we will present the use of Multi Walled Carbon Nanotubes (MWNT) directly grown on inconel substrates via chemical vapor deposition, as electrode materials for electrochemical double layer capacitors (EDLC). The performance of the MWNT EDLC electrodes were investigated using two electrolytes, an organic electrolyte, tetraethylammonium tetrafluoroborate in propylene carbonate (Et4NBF4 in PC), and a room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6). Cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy measurements to obtain values for the capacitance and internal resistance of these devices will be presented and compared.

ECLSS Sustaining Metal Materials Compatibility Final Report, Electrochemical and Crevice Corrosion Test Results

NASA Technical Reports Server (NTRS)

Lee, R. E.

2015-01-01

Electrochemical test results are presented for six noble metals evaluated in two acidic test solutions which are representative of waste liquids processed in the Environmental Control and Life Support System (ECLSS) aboard the International Space Station (ISS). The two test solutions consisted of fresh waste liquid which had been modified with a proposed or alternate pretreatment formulation and its associated brine concentrate. The six test metals included three titanium grades, (Commercially Pure, 6Al-4V alloy and 6Al-4V Low Interstitial alloy), two nickel-chromium alloys (Inconel® 625 and Hastelloy® C276), and one high tier stainless steel (Cronidur® 30).

Highly Safe Ionic Liquid Electrolytes for Sodium-Ion Battery: Wide Electrochemical Window and Good Thermal Stability.

PubMed

Wu, Feng; Zhu, Na; Bai, Ying; Liu, Libin; Zhou, Hang; Wu, Chuan

2016-08-24

Novel ionic liquid (IL) electrolytes are prepared by mixing 1-ethyl-3-methylimidazolium-bis-tetrafluoroborate (EMIBF4) with different concentrations of sodium salt (NaBF4). The as-prepared IL electrolytes display wide electrochemical windows of ∼4 V (1-5 V), which are consistent with the quantum chemical theoretical calculation. The IL electrolyte with 0.1 M NaBF4 shows excellent ionic conductivity, namely, 9.833 × 10(-3) S cm(-1) at 20 °C. In addition, nonflammability and good thermal stability are exhibited by combustion test and thermogravimetric analysis (TGA), which indicate the high safety of the IL electrolyte.

Gas-Phase Functionalization of Macroscopic Carbon Nanotube Fiber Assemblies: Reaction Control, Electrochemical Properties, and Use for Flexible Supercapacitors.

PubMed

Iglesias, Daniel; Senokos, Evgeny; Alemán, Belén; Cabana, Laura; Navío, Cristina; Marcilla, Rebeca; Prato, Maurizio; Vilatela, Juan J; Marchesan, Silvia

2018-02-14

The assembly of aligned carbon nanotubes (CNTs) into fibers (CNTFs) is a convenient approach to exploit and apply the unique physico-chemical properties of CNTs in many fields. CNT functionalization has been extensively used for its implementation into composites and devices. However, CNTF functionalization is still in its infancy because of the challenges associated with preservation of CNTF morphology. Here, we report a thorough study of the gas-phase functionalization of CNTF assemblies using ozone which was generated in situ from a UV source. In contrast with liquid-based oxidation methods, this gas-phase approach preserves CNTF morphology, while notably increasing its hydrophilicity. The functionalized material is thoroughly characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. Its newly acquired hydrophilicity enables CNTF electrochemical characterization in aqueous media, which was not possible for the pristine material. Through comparison of electrochemical measurements in aqueous electrolytes and ionic liquids, we decouple the effects of functionalization on pseudocapacitive reactions and quantum capacitance. The functionalized CNTF assembly is successfully used as an active material and a current collector in all-solid supercapacitor flexible devices with an ionic liquid-based polymer electrolyte.

Electrochemical performance of solid oxide fuel cells having electrolytes made by suspension and solution precursor plasma spraying

NASA Astrophysics Data System (ADS)

Marr, M.; Kuhn, J.; Metcalfe, C.; Harris, J.; Kesler, O.

2014-01-01

Yttria-stabilized zirconia (YSZ) electrolytes were deposited by suspension plasma spraying (SPS) and solution precursor plasma spraying (SPPS). The electrolytes were evaluated for permeability, microstructure, and electrochemical performance. With SPS, three different suspensions were tested to explore the influence of powder size distribution and liquid properties. Electrolytes made from suspensions of a powder with d50 = 2.6 μm were more gas-tight than those made from suspensions of a powder with d50 = 0.6 μm. A peak open circuit voltage of 1.00 V was measured at 750 °C with a cell with an electrolyte made from a suspension of d50 = 2.6 μm powder. The use of a flammable suspension liquid was beneficial for improving electrolyte conductivity when using lower energy plasmas, but the choice of liquid was less important when using higher energy plasmas. With SPPS, peak electrolyte conductivities were comparable to the peak conductivities of the SPS electrolytes. However, leak rates through the SPPS electrolytes were higher than those through the electrolytes made from suspensions of d50 = 2.6 μm powder. The electrochemical test data on SPPS electrolytes are the first reported in the literature.

Electrochemical Quartz Crystal Microbalance with Dissipation Real-Time Hydrodynamic Spectroscopy of Porous Solids in Contact with Liquids.

PubMed

Sigalov, Sergey; Shpigel, Netanel; Levi, Mikhael D; Feldberg, Moshe; Daikhin, Leonid; Aurbach, Doron

2016-10-18

Using multiharmonic electrochemical quartz crystal microbalance with dissipation (EQCM-D) monitoring, a new method of characterization of porous solids in contact with liquids has been developed. The dynamic gravimetric information on the growing, dissolving, or stationary stored solid deposits is supplemented by their precise in-operando porous structure characterization on a mesoscopic scale. We present a very powerful method of quartz-crystal admittance modeling of hydrodynamic solid-liquid interactions in order to extract the porous structure parameters of solids during their formation in real time, using different deposition modes. The unique hydrodynamic spectroscopic characterization of electrolytic and rf-sputtered solid Cu coatings that we use for our "proof of concept" provides a new strategy for probing various electrochemically active thin and thick solid deposits, thereby offering inexpensive, noninvasive, and highly efficient quantitative control over their properties. A broad spectrum of applications of our method is proposed, from various metal electroplating and finishing technologies to deeper insight into dynamic build-up and subsequent development of solid-electrolyte interfaces in the operation of Li-battery electrodes, as well as monitoring hydrodynamic consequences of metal corrosion, and growth of biomass coatings (biofouling) on different solid surfaces in seawater.

Electrochemical attosyringe.

PubMed

Laforge, François O; Carpino, James; Rotenberg, Susan A; Mirkin, Michael V

2007-07-17

The ability to manipulate ultrasmall volumes of liquids is essential in such diverse fields as cell biology, microfluidics, capillary chromatography, and nanolithography. In cell biology, it is often necessary to inject material of high molecular weight (e.g., DNA, proteins) into living cells because their membranes are impermeable to such molecules. All techniques currently used for microinjection are plagued by two common problems: the relatively large injector size and volume of injected fluid, and poor control of the amount of injected material. Here we demonstrate the possibility of electrochemical control of the fluid motion that allows one to sample and dispense attoliter-to-picoliter (10(-18) to 10(-12) liter) volumes of either aqueous or nonaqueous solutions. By changing the voltage applied across the liquid/liquid interface, one can produce a sufficient force to draw solution inside a nanopipette and then inject it into an immobilized biological cell. A high success rate was achieved in injections of fluorescent dyes into cultured human breast cells. The injection of femtoliter-range volumes can be monitored by video microscopy, and current/resistance-based approaches can be used to control injections from very small pipettes. Other potential applications of the electrochemical syringe include fluid dispensing in nanolithography and pumping in microfluidic systems.

Electrochemical attosyringe

PubMed Central

Laforge, François O.; Carpino, James; Rotenberg, Susan A.; Mirkin, Michael V.

2007-01-01

The ability to manipulate ultrasmall volumes of liquids is essential in such diverse fields as cell biology, microfluidics, capillary chromatography, and nanolithography. In cell biology, it is often necessary to inject material of high molecular weight (e.g., DNA, proteins) into living cells because their membranes are impermeable to such molecules. All techniques currently used for microinjection are plagued by two common problems: the relatively large injector size and volume of injected fluid, and poor control of the amount of injected material. Here we demonstrate the possibility of electrochemical control of the fluid motion that allows one to sample and dispense attoliter-to-picoliter (10−18 to 10−12 liter) volumes of either aqueous or nonaqueous solutions. By changing the voltage applied across the liquid/liquid interface, one can produce a sufficient force to draw solution inside a nanopipette and then inject it into an immobilized biological cell. A high success rate was achieved in injections of fluorescent dyes into cultured human breast cells. The injection of femtoliter-range volumes can be monitored by video microscopy, and current/resistance-based approaches can be used to control injections from very small pipettes. Other potential applications of the electrochemical syringe include fluid dispensing in nanolithography and pumping in microfluidic systems. PMID:17620612

Ab Initio Simulations and Electronic Structure of Lithium-Doped Ionic Liquids: Structure, Transport, and Electrochemical Stability.

PubMed

Haskins, Justin B; Bauschlicher, Charles W; Lawson, John W

2015-11-19

Density functional theory (DFT), density functional theory molecular dynamics (DFT-MD), and classical molecular dynamics using polarizable force fields (PFF-MD) are employed to evaluate the influence of Li(+) on the structure, transport, and electrochemical stability of three potential ionic liquid electrolytes: N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([pyr14][TFSI]), N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]). We characterize the Li(+) solvation shell through DFT computations of [Li(Anion)n]((n-1)-) clusters, DFT-MD simulations of isolated Li(+) in small ionic liquid systems, and PFF-MD simulations with high Li-doping levels in large ionic liquid systems. At low levels of Li-salt doping, highly stable solvation shells having two to three anions are seen in both [pyr14][TFSI] and [pyr13][FSI], whereas solvation shells with four anions dominate in [EMIM][BF4]. At higher levels of doping, we find the formation of complex Li-network structures that increase the frequency of four anion-coordinated solvation shells. A comparison of computational and experimental Raman spectra for a wide range of [Li(Anion)n]((n-1)-) clusters shows that our proposed structures are consistent with experiment. We then compute the ion diffusion coefficients and find measures from small-cell DFT-MD simulations to be the correct order of magnitude, but influenced by small system size and short simulation length. Correcting for these errors with complementary PFF-MD simulations, we find DFT-MD measures to be in close agreement with experiment. Finally, we compute electrochemical windows from DFT computations on isolated ions, interacting cation/anion pairs, and liquid-phase systems with Li-doping. For the molecular-level computations, we generally find the difference between ionization energy and electron affinity from isolated ions and interacting cation/anion pairs to provide upper and lower bounds, respectively, to experiment. In the liquid phase, we find the difference between the lowest unoccupied and highest occupied electronic levels in pure and hybrid functionals to provide lower and upper bounds, respectively, to experiment. Li-doping in the liquid-phase systems results in electrochemical windows little changed from the neat systems.

Electrochemical characterisation of a lithium-ion battery electrolyte based on mixtures of carbonates with a ferrocene-functionalised imidazolium electroactive ionic liquid.

PubMed

Forgie, John C; El Khakani, Soumia; MacNeil, Dean D; Rochefort, Dominic

2013-05-28

Electrolytic solutions of lithium-ion batteries can be modified with additives to improve their stability and safety. Electroactive molecules can be used as such additives to act as an electron (redox) shuttle between the two electrodes to prevent overcharging. The electroactive ionic liquid, 1-ferrocenylmethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (TFSI), was synthesised and its electrochemical properties were investigated when diluted with ethylene carbonate-diethyl carbonate solvent at various concentrations. Cyclic voltammetry data were gathered to determine the redox potential, diffusion coefficient and heterogeneous rate constants of the electroactive imidazolium TFSI ionic liquid in the carbonate solution. The properties of this molecule as an additive in lithium battery electrolytes were studied in standard coin cells with a metallic Li anode and a Li4Ti5O12 cathode.

Ordered mesoporous carbon modified carbon ionic liquid electrode for the electrochemical detection of double-stranded DNA.

PubMed

Zhu, Zhihong; Li, Xia; Zeng, Yan; Sun, Wei

2010-06-15

In this paper the direct electrochemistry of double-stranded DNA (dsDNA) was investigated on ordered mesoporous carbon (OMC) modified carbon ionic liquid electrode (CILE). CILE was prepared by mixing graphite powder with 1-ethyl-3-methylimidazolium ethylsulphate ([EMIM]EtOSO(3)) and liquid paraffin. A stable OMC film was formed on the surface of CILE with the help of Nafion to get a modified electrode denoted as Nafion-OMC/CILE. Due to the specific characteristics of OMC and IL present on the electrode surface, the fabricated electrode showed good electrochemical performances to different electroactive molecules. The electrochemical responses of dsDNA were carefully investigated on this electrode with two irreversible oxidation peak appeared at +1.250 V and +0.921 V (vs. SCE), which was corresponding to the oxidation of adenine and guanine residues in dsDNA structure. The electrochemical behaviors of dsDNA were carefully investigated on the Nafion-OMC/CILE. Experimental results indicated that the electron transfer rate was promoted with the increase of the oxidation peak current and the decrease of the oxidation peak potential, which was due to the electrocatalytic ability of OMC on the electrode surface. Under the optimal conditions the oxidation peak current increased with dsDNA concentration in the range of 10.0-600.0 microg mL(-1) by differential pulse voltammetry (DPV) with the detection limit of 1.2 microg mL(-1) (3sigma). Copyright 2010 Elsevier B.V. All rights reserved.

A solvated electron lithium electrode for secondary batteries

NASA Astrophysics Data System (ADS)

Sammells, A. F.; Semkow, K. W.

1986-09-01

Attention is given to a novel method for the achievement of high electro-chemical reversibility in Li-based nonaqueous cells, using a liquid negative electrode that consists of Li dissolved in liquid ammonia as a solvated electron Li electrode. The containment of this liquid negative active material from direct contact to a liquid nonaqueous electrolyte in the positive electrode compartment was realized through the use of a Li-intercalated, electronically conducting ceramic membrane.

Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes

PubMed Central

2018-01-01

Electrodeposition is a widely practiced method for creating metal, colloidal, and polymer coatings on conductive substrates. In the Newtonian liquid electrolytes typically used, the process is fundamentally unstable. The underlying instabilities have been linked to failure of microcircuits, dendrite formation on battery electrodes, and overlimiting conductance in ion-selective membranes. We report that viscoelastic electrolytes composed of semidilute solutions of very high–molecular weight neutral polymers suppress these instabilities by multiple mechanisms. The voltage window ΔV in which a liquid electrolyte can operate free of electroconvective instabilities is shown to be markedly extended in viscoelastic electrolytes and is a power-law function, ΔV : η1/4, of electrolyte viscosity, η. This power-law relation is replicated in the resistance to ion transport at liquid/solid interfaces. We discuss consequences of our observations and show that viscoelastic electrolytes enable stable electrodeposition of many metals, with the most profound effects observed for reactive metals, such as sodium and lithium. This finding is of contemporary interest for high-energy electrochemical energy storage. PMID:29582017

Exceptionally High Electric Double Layer Capacitances of Oligomeric Ionic Liquids.

PubMed

Matsumoto, Michio; Shimizu, Sunao; Sotoike, Rina; Watanabe, Masayoshi; Iwasa, Yoshihiro; Itoh, Yoshimitsu; Aida, Takuzo

2017-11-15

Electric double layer (EDL) capacitors are promising as next-generation energy accumulators if their capacitances and operation voltages are both high. However, only few electrolytes can simultaneously fulfill these two requisites. Here we report that an oligomeric ionic liquid such as IL4 TFSI with four imidazolium ion units in its structure provides a wide electrochemical window of ∼5.0 V, similar to monomeric ionic liquids. Furthermore, electrochemical impedance measurements using Au working electrodes demonstrated that IL4 TFSI exhibits an exceptionally high EDL capacitance of ∼66 μF/cm 2 , which is ∼6 times as high as those of monomeric ionic liquids so far reported. We also found that an EDL-based field effect transistor (FET) using IL4 TFSI as a gate dielectric material and SrTiO 3 as a channel material displays a very sharp transfer curve with an enhanced carrier accumulation capability of ∼64 μF/cm 2 , as determined by Hall-effect measurements.

Ambient-Pressure X-ray Photoelectron Spectroscopy to Characterize the Solid/Liquid Interface: Probing the Electrochemical Double Layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Favaro, Marco; Liu, Zhi; Crumlin, Ethan J.

Ambient-pressure X-ray photoelectron spectroscopy (APXPS) has contributed greatly to a wide range of research fields, including environmental science, catalysis, and electrochemistry, to name a few. The use of this technique at synchrotron facilities primarily focused on probing the solid/gas interface; however, it quickly advanced to the probing of liquid/vapor interfaces and solid/liquid interfaces through an X-ray-transparent window. Most recently, combining APXPS with “Tender” X-rays (~2.5 keV to 8 keV) on beamline 9.3.1 at the Advanced Light Source in Lawrence Berkeley National Laboratory (which can generate photoelectrons with much longer inelastic mean free paths) has enabled us to probe the solid/liquidmore » interface without needing a window. This innovation allows us to probe interfacial chemistries of electrochemically controlled solid/liquid interfaces undergoing charge transfer reactions. Lastly, these advancements have transitioned APXPS from a traditional surface science tool to an essential interface science technique.« less

Ambient-Pressure X-ray Photoelectron Spectroscopy to Characterize the Solid/Liquid Interface: Probing the Electrochemical Double Layer

DOE PAGES

Favaro, Marco; Liu, Zhi; Crumlin, Ethan J.

2017-03-31

Ambient-pressure X-ray photoelectron spectroscopy (APXPS) has contributed greatly to a wide range of research fields, including environmental science, catalysis, and electrochemistry, to name a few. The use of this technique at synchrotron facilities primarily focused on probing the solid/gas interface; however, it quickly advanced to the probing of liquid/vapor interfaces and solid/liquid interfaces through an X-ray-transparent window. Most recently, combining APXPS with “Tender” X-rays (~2.5 keV to 8 keV) on beamline 9.3.1 at the Advanced Light Source in Lawrence Berkeley National Laboratory (which can generate photoelectrons with much longer inelastic mean free paths) has enabled us to probe the solid/liquidmore » interface without needing a window. This innovation allows us to probe interfacial chemistries of electrochemically controlled solid/liquid interfaces undergoing charge transfer reactions. Lastly, these advancements have transitioned APXPS from a traditional surface science tool to an essential interface science technique.« less

High flow rate nozzle system with production of uniform size droplets

DOEpatents

Stockel, I.H.

1990-10-16

Method steps for production of substantially uniform size droplets from a flow of liquid include forming the flow of liquid, periodically modulating the momentum of the flow of liquid in the flow direction at controlled frequency, generating a cross flow direction component of momentum and modulation of the cross flow momentum of liquid at substantially the same frequency and phase as the modulation of flow direction momentum, and spraying the so formed modulated flow through a first nozzle outlet to form a desired spray configuration. A second modulated flow through a second nozzle outlet is formed according to the same steps, and the first and second modulated flows impinge upon each other generating a liquid sheet. Nozzle apparatus for modulating each flow includes rotating valving plates interposed in the annular flow of liquid. The plates are formed with radial slots. Rotation of the rotating plates is separably controlled at differential angular velocities for a selected modulating frequency to achieve the target droplet size and production rate for a given flow. The counter rotating plates are spaced to achieve a desired amplitude of modulation in the flow direction, and the angular velocity of the downstream rotating plate is controlled to achieve the desired amplitude of modulation of momentum in the cross flow direction. Amplitude of modulation is set according to liquid viscosity. 5 figs.

High flow rate nozzle system with production of uniform size droplets

DOEpatents

Stockel, Ivar H.

1990-01-01

Method steps for production of substantially uniform size droplets from a flow of liquid include forming the flow of liquid, periodically modulating the momentum of the flow of liquid in the flow direction at controlled frequency, generating a cross flow direction component of momentum and modulation of the cross flow momentum of liquid at substantially the same frequency and phase as the modulation of flow direction momentum, and spraying the so formed modulated flow through a first nozzle outlet to form a desired spray configuration. A second modulated flow through a second nozzle outlet is formed according to the same steps, and the first and second modulated flows impinge upon each other generating a liquid sheet. Nozzle apparatus for modulating each flow includes rotating valving plates interposed in the annular flow of liquid. The plates are formed with radial slots. Rotation of the rotating plates is separably controlled at differential angular velocities for a selected modulating frequency to achieve the target droplet size and production rate for a given flow. The counter rotating plates are spaced to achieve a desired amplitude of modulation in the flow direction, and the angular velocity of the downstream rotating plate is controlled to achieve the desired amplitude of modulation of momentum in the cross flow direction. Amplitude of modulation is set according to liquid viscosity.

Ionic liquid electrolytes for dye-sensitized solar cells.

PubMed

Gorlov, Mikhail; Kloo, Lars

2008-05-28

The potential of room-temperature molten salts (ionic liquids) as solvents for electrolytes for dye-sensitized solar cells has been investigated during the last decade. The non-volatility, good solvent properties and high electrochemical stability of ionic liquids make them attractive solvents in contrast to volatile organic solvents. Despite this, the relatively high viscosity of ionic liquids leads to mass-transport limitations. Here we review recent developments in the application of different ionic liquids as solvents or components of liquid and quasi-solid electrolytes for dye-sensitized solar cells.

On the diffusion of ferrocenemethanol in room-temperature ionic liquids: an electrochemical study.

PubMed

Lovelock, Kevin R J; Ejigu, Andinet; Loh, Sook Fun; Men, Shuang; Licence, Peter; Walsh, Darren A

2011-06-07

The electrochemical behaviour of ferrocenemethanol (FcMeOH) has been studied in a range of room-temperature ionic liquids (RTILs) using cyclic voltammetry, chronoamperomery and scanning electrochemical microscopy (SECM). The diffusion coefficient of FcMeOH, measured using chronoamperometry, decreased with increasing RTIL viscosity. Analysis of the mass transport properties of the RTILs revealed that the Stokes-Einstein equation did not apply to our data. The "correlation length" was estimated from diffusion coefficient data and corresponded well to the average size of holes (voids) in the liquid, suggesting that a model in which the diffusing species jumps between holes in the liquid is appropriate in these liquids. Cyclic voltammetry at ultramicroelectrodes demonstrated that the ability to record steady-state voltammograms during ferrocenemethanol oxidation depended on the voltammetric scan rate, the electrode dimensions and the RTIL viscosity. Similarly, the ability to record steady-state SECM feedback approach curves depended on the RTIL viscosity, the SECM tip radius and the tip approach speed. Using 1.3 μm Pt SECM tips, steady-state SECM feedback approach curves were obtained in RTILs, provided that the tip approach speed was low enough to maintain steady-state diffusion at the SECM tip. In the case where tip-induced convection contributed significantly to the SECM tip current, this effect could be accounted for theoretically using mass transport equations that include diffusive and convective terms. Finally, the rate of heterogeneous electron transfer across the electrode/RTIL interface during ferrocenemethanol oxidation was estimated using SECM, and k(0) was at least 0.1 cm s(-1) in one of the least viscous RTILs studied.

Demonstration of an electrochemical liquid cell for operando transmission electron microscopy observation of the lithiation/delithiation behavior of Si nanowire battery anodes.

PubMed

Gu, Meng; Parent, Lucas R; Mehdi, B Layla; Unocic, Raymond R; McDowell, Matthew T; Sacci, Robert L; Xu, Wu; Connell, Justin Grant; Xu, Pinghong; Abellan, Patricia; Chen, Xilin; Zhang, Yaohui; Perea, Daniel E; Evans, James E; Lauhon, Lincoln J; Zhang, Ji-Guang; Liu, Jun; Browning, Nigel D; Cui, Yi; Arslan, Ilke; Wang, Chong-Min

2013-01-01

Over the past few years, in situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration-the dynamics of the electrolyte and, potentially, a future quantitative characterization of the solid electrolyte interphase layer formation and structural and chemical evolution.

In-situ electrochemical transmission electron microscopy for battery research.

PubMed

Mehdi, B Layla; Gu, Meng; Parent, Lucas R; Xu, Wu; Nasybulin, Eduard N; Chen, Xilin; Unocic, Raymond R; Xu, Pinghong; Welch, David A; Abellan, Patricia; Zhang, Ji-Guang; Liu, Jun; Wang, Chong-Min; Arslan, Ilke; Evans, James; Browning, Nigel D

2014-04-01

The recent development of in-situ liquid stages for (scanning) transmission electron microscopes now makes it possible for us to study the details of electrochemical processes under operando conditions. As electrochemical processes are complex, care must be taken to calibrate the system before any in-situ/operando observations. In addition, as the electron beam can cause effects that look similar to electrochemical processes at the electrolyte/electrode interface, an understanding of the role of the electron beam in modifying the operando observations must also be understood. In this paper we describe the design, assembly, and operation of an in-situ electrochemical cell, paying particular attention to the method for controlling and quantifying the experimental parameters. The use of this system is then demonstrated for the lithiation/delithiation of silicon nanowires.

The possibility of multi-layer nanofabrication via atomic force microscope-based pulse electrochemical nanopatterning

NASA Astrophysics Data System (ADS)

Kim, Uk Su; Morita, Noboru; Lee, Deug Woo; Jun, Martin; Park, Jeong Woo

2017-05-01

Pulse electrochemical nanopatterning, a non-contact scanning probe lithography process using ultrashort voltage pulses, is based primarily on an electrochemical machining process using localized electrochemical oxidation between a sharp tool tip and the sample surface. In this study, nanoscale oxide patterns were formed on silicon Si (100) wafer surfaces via electrochemical surface nanopatterning, by supplying external pulsed currents through non-contact atomic force microscopy. Nanoscale oxide width and height were controlled by modulating the applied pulse duration. Additionally, protruding nanoscale oxides were removed completely by simple chemical etching, showing a depressed pattern on the sample substrate surface. Nanoscale two-dimensional oxides, prepared by a localized electrochemical reaction, can be defined easily by controlling physical and electrical variables, before proceeding further to a layer-by-layer nanofabrication process.

Development of a system for treatment of coconut industry wastewater using electrochemical processes followed by Fenton reaction.

PubMed

Gomes, Lúcio de Moura; Duarte, José Leandro da Silva; Pereira, Nathalia Marcelino; Martínez-Huitle, Carlos A; Tonholo, Josealdo; Zanta, Carmen Lúcia de Paiva E Silva

2014-01-01

The coconut processing industry generates a significant amount of liquid waste. New technologies targeting the treatment of industrial effluents have emerged, including advanced oxidation processes, the Fenton reaction, and electrochemical processes, which produce strong oxidizing species to remove organic matter. In this study we combined the Fenton reaction and electrochemical process to treat wastewater generated by the coconut industry. We prepared a synthetic wastewater consisting of a mixture of coconut milk and water and assessed how the Fenton reagents' concentration, the cathode material, the current density, and the implementation of associated technologies affect its treatment. Electrochemical treatment followed by the Fenton reaction diminished turbidity and chemical oxygen demand (COD) by 85 and 95%, respectively. The Fenton reaction followed by the electrochemical process reduced turbidity and COD by 93 and 85%, respectively. Therefore, a combination of the Fenton and electrochemical technologies can effectively treat the effluent from the coconut processing industry.

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

PubMed Central

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; Yano, Junko; Hussain, Zahid; Liu, Zhi; Crumlin, Ethan J.

2016-01-01

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzing the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential. PMID:27576762

Electric and Hydraulic Properties of Carbon Felt Immersed in Different Dielectric Liquids

PubMed Central

Kossenko, Alexey; Lugovskoy, Svetlana

2018-01-01

Electroconductive carbon felt (CF) material, having a permeable structure and significant electroconductive surface, is widely used for electrodes in numerous electrochemical applications such as redox flow batteries, fuel cells, electrochemical desalination apparatus, etc. The internal structure of CF is composed of different lengths of carbon filaments bonded together. This structure creates a large number of stochastically oriented and stochastically linked channels that have different lengths and cross sections. Therefore, the CF hydraulic permeability is similar to that of porous media and is determined by the internal empty volume and arrangement of carbon fibers. Its electroconductivity is ensured by the conductivity of the carbon filaments and by the electrical interconnections between fibers. Both of these properties (permeability and electrical conductivity) are extremely important for the efficient functioning of electrochemical devices. However, their influences counter each other during CF compressing. Increasing the stress on a felt element provides supplementary electrical contacts of carbon filaments, which lead to improved electrical conductivity. Thus, the active surface of the felt electrode is increased, which also boosts redox chemical reactions. On the other hand, compressed felt possesses reduced hydrodynamic permeability as a result of a diminished free volume of porous media and intrinsic channels. This causes increasing hydrodynamic expenditures of electrolyte pumping through electrodes and lessened cell (battery) efficiency. The designer of specific electrochemical systems has to take into account both of these properties when selecting the optimal construction for a cell. This article presents the results of measurements and novel approximating expressions of electrical and hydraulic characteristics of a CF during its compression. Since electrical conductivity plays a determining role in providing electrochemical reactions, it was measured in dry conditions and when the CF was immersed in several non-conductive liquids. The choice of such liquids prevented side effects of electrolyte ionic conductivity impact on electrical resistivity of the CF. This gave an opportunity to determine the influences of dielectric parameters of electrolytes to increase or decrease the density of interconnectivity of carbon fibers either between themselves or between them and electrodes. The experiments showed the influence of liquid permittivity on the conductivity of CF, probably by changing the density of fiber interconnections inside the felt. PMID:29690636

Electric and Hydraulic Properties of Carbon Felt Immersed in Different Dielectric Liquids.

PubMed

Kossenko, Alexey; Lugovskoy, Svetlana; Averbukh, Moshe

2018-04-23

Electroconductive carbon felt (CF) material, having a permeable structure and significant electroconductive surface, is widely used for electrodes in numerous electrochemical applications such as redox flow batteries, fuel cells, electrochemical desalination apparatus, etc. The internal structure of CF is composed of different lengths of carbon filaments bonded together. This structure creates a large number of stochastically oriented and stochastically linked channels that have different lengths and cross sections. Therefore, the CF hydraulic permeability is similar to that of porous media and is determined by the internal empty volume and arrangement of carbon fibers. Its electroconductivity is ensured by the conductivity of the carbon filaments and by the electrical interconnections between fibers. Both of these properties (permeability and electrical conductivity) are extremely important for the efficient functioning of electrochemical devices. However, their influences counter each other during CF compressing. Increasing the stress on a felt element provides supplementary electrical contacts of carbon filaments, which lead to improved electrical conductivity. Thus, the active surface of the felt electrode is increased, which also boosts redox chemical reactions. On the other hand, compressed felt possesses reduced hydrodynamic permeability as a result of a diminished free volume of porous media and intrinsic channels. This causes increasing hydrodynamic expenditures of electrolyte pumping through electrodes and lessened cell (battery) efficiency. The designer of specific electrochemical systems has to take into account both of these properties when selecting the optimal construction for a cell. This article presents the results of measurements and novel approximating expressions of electrical and hydraulic characteristics of a CF during its compression. Since electrical conductivity plays a determining role in providing electrochemical reactions, it was measured in dry conditions and when the CF was immersed in several non-conductive liquids. The choice of such liquids prevented side effects of electrolyte ionic conductivity impact on electrical resistivity of the CF. This gave an opportunity to determine the influences of dielectric parameters of electrolytes to increase or decrease the density of interconnectivity of carbon fibers either between themselves or between them and electrodes. The experiments showed the influence of liquid permittivity on the conductivity of CF, probably by changing the density of fiber interconnections inside the felt.

Self-Organization of Ions at the Interface between Graphene and Ionic Liquid DEME-TFSI.

PubMed

Hu, Guangliang; Pandey, Gaind P; Liu, Qingfeng; Anaredy, Radhika S; Ma, Chunrui; Liu, Ming; Li, Jun; Shaw, Scott K; Wu, Judy

2017-10-11

Electrochemical effects manifest as nonlinear responses to an applied electric field in electrochemical devices, and are linked intimately to the molecular orientation of ions in the electric double layer (EDL). Herein, we probe the origin of the electrochemical effect using a double-gate graphene field effect transistor (GFET) of ionic liquid N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEME-TFSI) top-gate, paired with a ferroelectric Pb 0.92 La 0.08 Zr 0.52 Ti 0.48 O 3 (PLZT) back-gate of compatible gating efficiency. The orientation of the interfacial molecular ions can be extracted by measuring the GFET Dirac point shift, and their dynamic response to ultraviolet-visible light and a gate electric field was quantified. We have observed that the strong electrochemical effect is due to the TFSI anions self-organizing on a treated GFET surface. Moreover, a reversible order-disorder transition of TFSI anions self-organized on the GFET surface can be triggered by illuminating the interface with ultraviolet-visible light, revealing that it is a useful method to control the surface ion configuration and the overall performance of the device.

Electrochemically exfoliated graphene anodes with enhanced biocurrent production in single-chamber air-breathing microbial fuel cells.

PubMed

Najafabadi, Amin Taheri; Ng, Norvin; Gyenge, Előd

2016-07-15

Microbial fuel cells (MFCs) present promising options for environmentally sustainable power generation especially in conjunction with waste water treatment. However, major challenges remain including low power density, difficult scale-up, and durability of the cell components. This study reports enhanced biocurrent production in a membrane-free MFC, using graphene microsheets (GNs) as anode and MnOx catalyzed air cathode. The GNs are produced by ionic liquid assisted simultaneous anodic and cathodic electrochemical exfoliation of iso-molded graphite electrodes. The GNs produced by anodic exfoliation increase the MFC peak power density by over 300% compared to plain carbon cloth (i.e., 2.85Wm(-2) vs 0.66Wm(-2), respectively), and by 90% compared to conventional carbon black (i.e., Vulcan XC-72) anode. These results exceed previously reported power densities for graphene-containing MFC anodes. The fuel cell polarization results are corroborated by electrochemical impedance spectroscopy indicating three times lower charge transfer resistance for the GN anode. Material characterizations suggest that the best performing GN samples were of relatively smaller size (~500nm), with higher levels of ionic liquid induced surface functionalization during the electrochemical exfoliation process. Copyright © 2016 Elsevier B.V. All rights reserved.

GaN light-emitting device based on ionic liquid electrolyte

NASA Astrophysics Data System (ADS)

Hirai, Tomoaki; Sakanoue, Tomo; Takenobu, Taishi

2018-06-01

Ionic liquids (ILs) are attractive materials for fabricating unique hybrid devices based on electronics and electrochemistry; thus, IL-gated transistors and organic light-emitting devices of light-emitting electrochemical cells (LECs) are investigated for future low-voltage and high-performance devices. In LECs, voltage application induces the formation of electrochemically doped p–n homojunctions owing to ion rearrangements in composites of semiconductors and electrolytes, and achieves electron–hole recombination for light emission at the homojunctions. In this work, we applied this concept of IL-induced electrochemical doping to the fabrication of GaN-based light-emitting devices. We found that voltage application to the layered IL/GaN structure accumulated electrons on the GaN surface owing to ion rearrangements and improved the conductivity of GaN. The ion rearrangement also enabled holes to be injected by the strong electric field of electric double layers on hole injection contacts. This simultaneous injection of holes and electrons into GaN mediated by ions achieves light emission at a low voltage of around 3.4 V. The light emission from the simple IL/GaN structure indicates the usefulness of an electrochemical technique in generating light emission with great ease of fabrication.

Innovative oxide materials for electrochemical energy conversion and oxygen separation

NASA Astrophysics Data System (ADS)

Belousov, V. V.

2017-10-01

Ion-conducting solid metal oxides are widely used in high-temperature electrochemical devices for energy conversion and oxygen separation. However, liquid metal oxides possessing unique electrochemical properties still remain of limited use. The review demonstrates the potential for practical applications of molten oxides. The transport properties of molten oxide materials are discussed. The emphasis is placed on the chemical diffusion of oxygen in the molten oxide membrane materials for electrochemical energy conversion and oxygen separation. The thermodynamics of these materials is considered. The dynamic polymer chain model developed to describe the oxygen ion transport in molten oxides is discussed. Prospects for further research into molten oxide materials are outlined. The bibliography includes 145 references.

Exploration of two-dimensional bio-functionalized phosphorene nanosheets (black phosphorous) for label free haptoglobin electro-immunosensing applications

NASA Astrophysics Data System (ADS)

Tuteja, Satish K.; Neethirajan, Suresh

2018-04-01

We report on the development of an antibody-functionalized interface based on electrochemically active liquid-exfoliated two-dimensional phosphorene (Ph) nanosheets—also known as black phosphorous nanosheets—for the label-free electrochemical immunosensing of a haptoglobin (Hp) biomarker, a clinical marker of severe inflammation. The electrodeposition has been achieved over the screen-printed electrode (SPE) using liquid-assisted ultrasonically exfoliated black phosphorus nanosheets. Subsequently, Ph-SPEs bioconjugated with Hp antibodies (Ab), using electrostatic interactions via a poly-L-lysine linker for biointerface development. Electrochemical analysis demonstrates that the Ab-modified Ph-SPEs (Ab@Ph-SPE) exhibit enhanced electroconducting behavior as compared to the pristine electrodes. This Ab-functionalized phosphorene-based electrochemical immunosensor platform has demonstrated remarkable sensitivity and specificity, having a dynamic linear response range from 0.01-10 mg ml-1 for Hp in standard and serum samples with a low detection limit (˜0.011 mg ml-1) using the label-free electrochemical technique. The sensor electrodes were also studied with other closely relative interferents to investigate cross reactivity and specificity. This strategy opens up avenues to POC (point-of-care) and on-farm livestock disease monitoring technologies for multiplexed diagnosis in complex biological samples such as serum. The technique is simple in fabrication and provides an analytical response in less than 60 s.

Liquid metal embrittlement. [crack propagation in metals with liquid metal in crack space

NASA Technical Reports Server (NTRS)

Tiller, W. A.

1973-01-01

Crack propagation is discussed for metals with liquid metal in the crack space. The change in electrochemical potential of an electron in a metal due to changes in stress level along the crack surface was investigated along with the change in local chemistry, and interfacial energy due to atomic redistribution in the liquid. Coupled elastic-elastrostatic equations, stress effects on electron energy states, and crack propagation via surface roughening are discussed.

Characterization of a non-approved selective androgen receptor modulator drug candidate sold via the Internet and identification of in vitro generated phase-I metabolites for human sports drug testing.

PubMed

Thevis, Mario; Lagojda, Andreas; Kuehne, Dirk; Thomas, Andreas; Dib, Josef; Hansson, Annelie; Hedeland, Mikael; Bondesson, Ulf; Wigger, Tina; Karst, Uwe; Schänzer, Wilhelm

2015-06-15

Potentially performance-enhancing agents, particularly anabolic agents, are advertised and distributed by Internet-based suppliers to a substantial extent. Among these anabolic agents, a substance referred to as LGD-4033 has been made available, comprising the core structure of a class of selective androgen receptor modulators (SARMs). In order to provide comprehensive analytical data for doping controls, the substance was obtained and characterized by nuclear magnetic resonance spectroscopy (NMR) and liquid chromatography/electrospray ionization high resolution/high accuracy tandem mass spectrometry (LC/ESI-HRMS). Following the identification of 4-(2-(2,2,2-trifluoro-1-hydroxyethyl)pyrrolidin-1-yl)-2-(trifluoromethyl)benzonitrile, the substance was subjected to in vitro metabolism studies employing human liver microsomes and Cunninghamella elegans (C. elegans) preparations as well as electrochemical metabolism simulations. By means of LC/ESI-HRMS, five main phase-I metabolites were identified as products of liver microsomal preparations including three monohydroxylated and two bishydroxylated species. The two most abundant metabolites (one mono- and one bishydroxylated product) were structurally confirmed by LC/ESI-HRMS and NMR. Comparing the metabolic conversion of 4-(2-(2,2,2-trifluoro-1-hydroxyethyl)pyrrolidin-1-yl)-2-(trifluoromethyl)benzonitrile observed in human liver microsomes with C. elegans and electrochemically derived metabolites, one monohydroxylated product was found to be predominantly formed in all three methodologies. The implementation of the intact SARM-like compound and its presumed urinary phase-I metabolites into routine doping controls is suggested to expand and complement existing sports drug testing methods. Copyright © 2015 John Wiley & Sons, Ltd.

Methods of producing sulfate salts of cations from heteroatomic compounds and dialkyl sulfates and uses thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2015-09-29

Methods of preparing sulfate salts of heteroatomic compounds using dialkyl sulfates as a primary reactant are disclosed. Also disclosed are methods of making ionic liquids from the sulfate salts of the heteroatomic compound, and electrochemical cells comprising the ionic liquids.

Detection of ricin contamination in liquid egg by electrochemiluminescence immunosorbent assay

USDA-ARS?s Scientific Manuscript database

A monoclonal antibody-based electrochemical luminescence (ECL) method was developed for detecting and quantifying ricin in liquid egg, with a limit of detection of 0.2 ng/mL. Because this highly toxic protein, present in the seeds of Ricinus communis (castor), has been used for intentional poisoning...

Electrochemical Supercapacitor Electrodes from Sponge-like Graphene Nanoarchitectures with Ultrahigh Power Density.

PubMed

Xu, Zhanwei; Li, Zhi; Holt, Chris M B; Tan, Xuehai; Wang, Huanlei; Amirkhiz, Babak Shalchi; Stephenson, Tyler; Mitlin, David

2012-10-18

We employed a microwave synthesis process of cobalt phthalocyanine molecules templated by acid-functionalized multiwalled carbon nanotubes to create three-dimensional sponge-like graphene nanoarchitectures suited for ionic liquid-based electrochemical capacitor electrodes that operate at very high scan rates. The sequential "bottom-up" molecular synthesis and subsequent carbonization process took less than 20 min to complete. The 3D nanoarchitectures are able to deliver an energy density of 7.1 W·h kg(-1) even at an extra high power density of 48 000 W kg(-1). In addition, the ionic liquid supercapacitor based on this material works very well at room temperature due to its fully opened structures, which is ideal for the high-power energy application requiring more tolerance to temperature variation. Moreover, the structures are stable in both ionic liquids and 1 M H2SO4, retaining 90 and 98% capacitance after 10 000 cycles, respectively.

Switchable silver mirrors with long memory effects.

PubMed

Park, Chihyun; Seo, Seogjae; Shin, Haijin; Sarwade, Bhimrao D; Na, Jongbeom; Kim, Eunkyoung

2015-01-01

An electrochemically stable and bistable switchable mirror was achieved for the first time by introducing (1) a thiol-modified indium tin oxide (ITO) electrode for the stabilization of the metallic film and (2) ionic liquids as an anion-blocking layer, to achieve a long memory effect. The growth of the metallic film was denser and faster at the thiol-modified ITO electrode than at a bare ITO electrode. The electrochemical stability of the metallic film on the thiol-modified ITO was enhanced, maintaining the metallic state without rupture. In the voltage-off state, the metal film maintained bistability for a long period (>2 h) when ionic liquids were introduced as electrolytes for the switchable mirror. The electrical double layer in the highly viscous ionic liquid electrolyte seemed to effectively form a barrier to the bromide ions, to protect the metal thin film from them when in the voltage-off state.

Electrical double layer modulation of hybrid room temperature ionic liquid/aqueous buffer interface for enhanced sweat based biosensing.

PubMed

Jagannath, Badrinath; Muthukumar, Sriram; Prasad, Shalini

2018-08-03

We have investigated the role of kosmotropic anionic moieties and chaotropic cationic moieties of room temperature hydrophilic ionic liquids in enhancing the biosensing performance of affinity based immunochemical biosensors in human sweat. Two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM[BF 4 ]) and choline dihydrogen phosphate (Choline[DHP]) were investigated in this study with Choline[DHP] being more kosmotropic in nature having a more protein stabilizing effect based on the hofmeister series. Non-faradaic interfacial charge transfer has been employed as the mechanism for evaluating the formation and the biosensing of capture probe antibodies in room temperature ionic liquids (RTILs)/aqueous human sweat interface. The charge of the ionic moieties were utilized to form compact electrical double layers around the antibodies for enhancing the stability of the antibody capture probes, which was evaluated through zeta potential measurements. The zeta potential measurements indicated stability of antibodies due to electrostatic repulsion of the RTIL charged moieties encompassing the antibodies, thus preventing any aggregation. Here, we report for the first time of non-faradaic electrochemical impedance spectroscopy equivalent circuit model analysis for analyzing and interpreting affinity based biosensing at hybrid electrode/ionic liquid-aqueous sweat buffer interface guided by the choice of the ionic liquid. Interleukin-6 (IL-6) and cortisol two commonly occurring biomarkers in human sweat were evaluated using this method. The limit of detection (LOD) obtained using both ionic liquids for IL-6 was 0.2 pg mL -1 with cross-reactivity studies indicating better performance of IL-6 detection using Choline[DHP] and no response to cross-reactive molecule. The LOD of 0.1 ng/mL was achieved for cortisol and the cross-reactivity studies indicated that cortisol antibody in BMIM[BF 4 ] did not show any signal response to cross-reactive molecules. Furthermore, improved sensitivity and LOD was achieved using ionic liquids as compared to capture probes in aqueous buffer. Copyright © 2018 Elsevier B.V. All rights reserved.

Calculating the Maximum Density of the Surface Packing of Ions in Ionic Liquids

NASA Astrophysics Data System (ADS)

Kislenko, S. A.; Moroz, Yu. O.; Karu, K.; Ivaništšev, V. B.; Fedorov, M. V.

2018-05-01

The maximum density of monolayer packing on a graphene surface is calculated by means of molecular dynamics (MD) for ions of characteristic size and symmetry: 1-butyl-3-methylimidazolium [BMIM]+, tetrabutylammonium [TBA]+, tetrafluoroborate [BF4]-, dicyanamide [DCA]-, and bis(trifluoromethane) sulfonimide [TFSI]-. The characteristic orientations of ions in a closely packed monolayer are found. It is shown that the formation of a closely packed monolayer is possible for [DCA]- and [BF4]- anions only at surface charges that exceed the limit of the electrochemical stability of the corresponding ionic liquids. For the [TBA]+ cation, a monolayer structure can be observed at the charge of nearly 30 μC/cm2 attainable in electrochemical experiment.

Optically transparent FTO-free cathode for dye-sensitized solar cells.

PubMed

Kavan, Ladislav; Liska, Paul; Zakeeruddin, Shaik M; Grätzel, Michael

2014-12-24

The woven fabric containing electrochemically platinized tungsten wire is an affordable flexible cathode for liquid-junction dye-sensitized solar cells with the I3(-)/I(-) redox mediator and electrolyte solution consisting of ionic liquids and propionitrile. The fabric-based electrode outperforms the thermally platinized FTO in serial ohmic resistance and charge-transfer resistance for triiodide reduction, and it offers comparable or better optical transparency in the visible and particularly in the near-IR spectral region. The electrode exhibits good stability during electrochemical loading and storage at open circuit. The dye-sensitized solar cells with a C101-sensitized titania photoanode and either Pt-W/PEN or Pt-FTO cathodes show a comparable performance.

Electrochemical air revitalization system optimization investigation

NASA Technical Reports Server (NTRS)

Woods, R. R.; Schubert, F. H.; Hallick, T. M.

1975-01-01

A program to characterize a Breadboard of an Electrochemical Air Revitalization System (BEARS) was successfully completed. The BEARS is composed of three components: (1) a water vapor electrolysis module (WVEM) for O2 production and partial humidity control, (2) an electrochemical depolarized carbon dioxide concentrator module (EDCM) for CO2 control, and (3) a power-sharing controller, designed to utilize the power produced by the EDCM to partially offset the WVEM power requirements. It is concluded from the results of this work that the concept of electrochemical air revitalization with power-sharing is a viable solution to the problem of providing a localized topping force for O2 generation, CO2 removal and partial humidity control aboard manned spacecraft. Continued development of the EARS concept is recommended, applying the operational experience and limits identified during the BEARS program to testing of a one-man capacity system and toward the development of advanced system controls to optimize EARS operation for given interfaces and requirements. Successful completion of this development will produce timely technology necessary to plan future advanced environmental control and life support system programs and experiments.

A method for determining the actual rate of orientation switching of DNA self-assembled monolayers using optical and electrochemical frequency response analysis.

PubMed

Casanova-Moreno, J; Bizzotto, D

2015-02-17

Electrostatic control of the orientation of fluorophore-labeled DNA strands immobilized on an electrode surface has been shown to be an effective bioanalytical tool. Modulation techniques and later time-resolved measurements were used to evaluate the kinetics of the switching between lying and standing DNA conformations. These measurements, however, are the result of a convolution between the DNA "switching" response time and the other frequency limited responses in the measurement. In this work, a method for analyzing the response of a potential driven DNA sensor is presented by calculating the potential effectively dropped across the electrode interface (using electrochemical impedance spectroscopy) as opposed to the potential applied to the electrochemical cell. This effectively deconvolutes the effect of the charging time on the observed frequency response. The corrected response shows that DNA is able to switch conformation faster than previously reported using modulation techniques. This approach will ensure accurate measurements independent of the electrochemical system, removing the uncertainty in the analysis of the switching response, enabling comparison between samples and measurement systems.

Refurbishment of one-person regenerative air revitalization system

NASA Technical Reports Server (NTRS)

Powell, Ferolyn T.

1989-01-01

Regenerative processes for the revitalization of spacecraft atmospheres and reclamation of waste waters are essential for making long-term manned space missions a reality. Processes studied include: static feed water electrolysis for oxygen generation, Bosch carbon dioxide reduction, electrochemical carbon dioxide concentration, vapor compression distillation water recovery, and iodine monitoring. The objectives were to: provide engineering support to Marshall Space Flight Center personnel throughout all phases of the test program, e.g., planning through data analysis; fabricate, test, and deliver to Marshall Space Flight Center an electrochemical carbon dioxide module and test stand; fabricate and deliver an iodine monitor; evaluate the electrochemical carbon dioxide concentrator subsystem configuration and its ability to ensure safe utilization of hydrogen gas; evaluate techniques for recovering oxygen from a product oxygen and carbon dioxide stream; and evaluate the performance of an electrochemical carbon dioxide concentrator module to operate without hydrogen as a method of safe haven operation. Each of the tasks were related in that all focused on providing a better understanding of the function, operation, and performance of developmental pieces of environmental control and life support system hardware.

Effects of pH on the electrochemical behaviour of titanium alloys for implant applications.

PubMed

Souza, Maria E P; Lima, Lonetá; Lima, Carmo R P; Zavaglia, Cecília A C; Freire, Célia M A

2009-02-01

The electrochemical behaviour of two commercial titanium alloys Ti-6Al-4 V (ASTM F136) and Ti-13Nb-13Zr (ASTM F1713) was investigated in Ringer physiological solution at two pH values (5.5 and 7.0). The corrosion properties were examined by using electrochemical techniques: Potentiodynamic anodic polarization, cyclic polarization and electrochemical impedance spectroscopy (EIS). The electrochemical corrosion properties of both alloys at different conditions were measured in terms of corrosion potential (E (corr)), corrosion current density (i (corr)) and passivation current density (i (pass)). Equivalent electrical circuits were used to modulate EIS data, in order to characterize alloys surface and better understanding the pH effect on the interface alloy/solution.

Role of density modulation in the spatially resolved dynamics of strongly confined liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saw, Shibu, E-mail: shibu.saw@sydney.edu.au; Dasgupta, Chandan, E-mail: cdgupta@physics.iisc.ernet.in

Confinement by walls usually produces a strong modulation in the density of dense liquids near the walls. Using molecular dynamics simulations, we examine the effects of the density modulation on the spatially resolved dynamics of a liquid confined between two parallel walls, using a resolution of a fraction of the interparticle distance in the liquid. The local dynamics is quantified by the relaxation time associated with the temporal autocorrelation function of the local density. We find that this local relaxation time varies in phase with the density modulation. The amplitude of the spatial modulation of the relaxation time can bemore » quite large, depending on the characteristics of the wall and thermodynamic parameters of the liquid. To disentangle the effects of confinement and density modulation on the spatially resolved dynamics, we compare the dynamics of a confined liquid with that of an unconfined one in which a similar density modulation is induced by an external potential. We find several differences indicating that density modulation alone cannot account for all the features seen in the spatially resolved dynamics of confined liquids. We also examine how the dynamics near a wall depends on the separation between the two walls and show that the features seen in our simulations persist in the limit of large wall separation.« less

Improved Performance of Ionic Liquid Supercapacitors by using Tetracyanoborate Anions.

PubMed

Martins, Vitor L; Rennie, Anthony J R; Sanchez-Ramirez, Nedher; Torresi, Roberto M; Hall, Peter J

2018-02-01

Supercapacitors are energy storage devices designed to operate at higher power densities than conventional batteries, but their energy density is still too low for many applications. Efforts are made to design new electrolytes with wider electrochemical windows than aqueous or conventional organic electrolytes in order to increase energy density. Ionic liquids (ILs) with wide electrochemical stability windows are excellent candidates to be employed as supercapacitor electrolytes. ILs containing tetracyanoborate anions [B(CN) 4 ] offer wider electrochemical stability than conventional electrolytes and maintain a high ionic conductivity (6.9 mS cm -1 ). Herein, we report the use of ILs containing the [B(CN) 4 ] anion for such an application. They presented a high maximum operating voltage of 3.7 V, and two-electrode devices demonstrate high specific capacitances even when operating at relatively high rates (ca. 20 F g -1 @ 15 A g -1 ). This supercapacitor stored more energy and operated at a higher power at all rates studied when compared with cells using a commonly studied ILs.

Electrochemical and in-situ X-ray diffraction studies of Ti 3C 2T x MXene in ionic liquid electrolyte

DOE PAGES

Lin, Zifeng; Rozier, Patrick; Duployer, Benjamin; ...

2016-08-26

2D titanium carbide (Ti 3C 2T x MXene) showed good capacitance in both organic and neat ionic liquid electrolytes, but its charge storage mechanism is still not fully understood. Here, electrochemical characteristics of Ti 3C 2T x electrode were studied in neat EMI-TFSI electrolyte. A capacitive behavior was observed within a large electrochemical potential range (from – 1.5 to 1.5 V vs. Ag). Intercalation and de-intercalation of EMI + cations and/or TFSI– anions were investigated by in-situ X-ray diffraction. Interlayer spacing of Ti 3C 2T x flakes decreases during positive polarization, which can be ascribed to either electrostatic attraction effectmore » between intercalated TFSI– anions and positively charged Ti 3C 2T x nanosheets or steric effect caused by de-intercalation of EMI + cations. In conclusion, the expansion of interlayer spacing when polarized to negative potentials is explained by steric effect of cation intercalation.« less

Electrochemical Impedance Spectroscopic Study on Eu 2+ and Sr 2+ Using Liquid Metal Cathodes in Molten Chlorides

NASA Astrophysics Data System (ADS)

Matsumiya, Masahiko; Takagi, Ryuzo

2000-08-01

For the pyrochemical reprocessing of spent metallic nuclear fuels in molten salt baths it is important to investigate the behavior of the electrochemically negative elements Eu and Sr, which are significant fission products. Voltammetric and chronopotentiometric studies have shown that the reduction of Eu 2+ and Sr 2+ on liquid Pb cathodes in molten chloride baths at 1073 K follows the alloy formation reaction: Eu 2+ + 2e- + 3Pb → EuPb 3 and Sr 2+ + 2e- + 3Pb → SrPb 3 . In the present work these alloy formation reactions were studiedby electrochemical impedance spectroscopy. Analysis of the spectra showed that the electronic exchange of Eu 2+ /Eu and Sr 2+ /Sr is quasi-re-versible. Moreover, the experimental results allowed the determination of the kinetic parameters of EU 2+ /EU and Sr 2+ /Sr, the diffusion coefficients of these species in molten chloride baths, and also the diffusion layer thickness.

Chip-based generation of carbon nanodots via electrochemical oxidation of screen printed carbon electrodes and the applications for efficient cell imaging and electrochemiluminescence enhancement

NASA Astrophysics Data System (ADS)

Xu, Yuanhong; Liu, Jingquan; Zhang, Jizhen; Zong, Xidan; Jia, Xiaofang; Li, Dan; Wang, Erkang

2015-05-01

A portable lab-on-a-chip methodology to generate ionic liquid-functionalized carbon nanodots (CNDs) was developed via electrochemical oxidation of screen printed carbon electrodes. The CNDs can be successfully applied for efficient cell imaging and solid-state electrochemiluminescence sensor fabrication on the paper-based chips.A portable lab-on-a-chip methodology to generate ionic liquid-functionalized carbon nanodots (CNDs) was developed via electrochemical oxidation of screen printed carbon electrodes. The CNDs can be successfully applied for efficient cell imaging and solid-state electrochemiluminescence sensor fabrication on the paper-based chips. Electronic supplementary information (ESI) available: Experimental section; Fig. S1. XPS spectra of the as-prepared CNDs after being dialyzed for 72 hours; Fig. S2. LSCM images showing time-dependent fluorescence signals of HeLa cells treated by the as-prepared CNDs; Tripropylamine analysis using the Nafion/CNDs modified ECL sensor. See DOI: 10.1039/c5nr01765c

Miniaturized Planar Room Temperature Ionic Liquid Electrochemical Gas Sensor for Rapid Multiple Gas Pollutants Monitoring.

PubMed

Wan, Hao; Yin, Heyu; Lin, Lu; Zeng, Xiangqun; Mason, Andrew J

2018-02-01

The growing impact of airborne pollutants and explosive gases on human health and occupational safety has escalated the demand of sensors to monitor hazardous gases. This paper presents a new miniaturized planar electrochemical gas sensor for rapid measurement of multiple gaseous hazards. The gas sensor features a porous polytetrafluoroethylene substrate that enables fast gas diffusion and room temperature ionic liquid as the electrolyte. Metal sputtering was utilized for platinum electrodes fabrication to enhance adhesion between the electrodes and the substrate. Together with carefully selected electrochemical methods, the miniaturized gas sensor is capable of measuring multiple gases including oxygen, methane, ozone and sulfur dioxide that are important to human health and safety. Compared to its manually-assembled Clark-cell predecessor, this sensor provides better sensitivity, linearity and repeatability, as validated for oxygen monitoring. With solid performance, fast response and miniaturized size, this sensor is promising for deployment in wearable devices for real-time point-of-exposure gas pollutant monitoring.

Specialist gelator for ionic liquids.

PubMed

Hanabusa, Kenji; Fukui, Hiroaki; Suzuki, Masahiro; Shirai, Hirofusa

2005-11-08

Cyclo(l-beta-3,7-dimethyloctylasparaginyl-L-phenylalanyl) (1) and cyclo(L-beta-2-ethylhexylasparaginyl-L-phenylalanyl) (2), prepared from L-asparaginyl-L-phenylalanine methyl ester, have been found to be specialist gelators for ionic liquids. They can gel a wide variety of ionic liquids, including imizazolium, pyridinium, pyrazolidinium, piperidinium, morpholinium, and ammonium salts. The mean minimum gel concentrations (MGCs) necessary to make gels at 25 degrees C were determined for ionic liquids. The gel strength increased at a rate nearly proportional to the concentration of added gelator. The strength of the transparent gel of 1-butylpyridinium tetrafluoroborate ([C(4)py]BF(4)), prepared at a concentration of 60 g L(-1) (gelator 1/[C(4)py]BF(4)), was ca. 1500 g cm(-2). FT-IR spectroscopy indicated that a driving force for gelation was intermolecular hydrogen bonding between amides and that the phase transition from gel to liquid upon heating was brought about by the collapse of hydrogen bonding. The gels formed from ionic liquids were very thermally stable; no melting occurs up to 140 degrees C when the gels were prepared at a concentration of 70 g L(-1) (gelator/ionic liquid). The ionic conductivities of the gels were nearly the same as those of pure ionic liquids. The gelator had electrochemical stability and a wide electrochemical window. When the gels were prepared from ionic liquids containing propylene carbonate, the ionic conductivities of the resulting gels increased to levels rather higher than those of pure ionic liquids. The gelators also gelled ionic liquids containing supporting electrolytes.

Ionic liquids as an electrolyte for the electro synthesis of organic compounds.

PubMed

Kathiresan, Murugavel; Velayutham, David

2015-12-25

The use of ionic liquids (ILs) as a solvent and an electrolyte for electro organic synthesis has been reviewed. To date several ILs exist, however the ILs based on tetraalkylammonium, pyrrolidinium, piperidinium and imidazolium cations with BF4(-), PF6(-), and TFSI anions have been widely used and explored the most. Electro organic synthesis in ionic liquid media leading to the synthesis of a wide range of organic compounds has been discussed. Anodic oxidation or cathodic reduction will generate radical cation or anion intermediates, respectively. These radicals can undergo self coupling or coupling with other molecules yielding organic compounds of interest. The cation of the IL is known to stabilize the radical anion extensively. This stabilization effect has a specific impact on the electrochemical CO2 reduction and coupling to various organics. The relative stability of the intermediates in IL leads to the formation of specific products in higher yields. Electrochemical reduction of imidazolium or thiazolium based ILs generates N-heterocyclic carbenes that have been shown to catalyze a wide range of base or nucleophile catalyzed organic reactions in IL media, an aspect that falls into the category of organocatalysis. Electrochemical fluorination or selective electrochemical fluorination is another fascinating area that delivers selectively fluorinated organic products in Et3N·nHF or Et4NF·nHF adducts (IL) via anodic oxidation. Oxidative polymerization in ILs has been explored the most; although morphological changes were observed compared to the conventional methods, polymers were obtained in good yields and in some cases ILs were used as dopants to improve the desired properties.

Surface phenomenon in Electrochemical Systems

NASA Astrophysics Data System (ADS)

Gupta, Tanya

Interfaces play a critical role in the performance of electrochemical systems. This thesis focusses on interfaces in batteries and covers aspects of interfacial morphologies of metal anodes, including Silicon, Lithium and Zinc. Growth and cycling of electrochemically grown Lithium and Zinc metal structures is investigated. A new morphology of Zinc, called Hyper Dendritic Zinc is introduced. It is cycled against Prussian Blue Analogues and is shown to improve the performance of this couple significantly. Characterization of materials is done using various electron microscopy techniques ranging from Low Energy Electron Microscope (LEEM), to high energy Transmission Electron Microscope (TEM). LEEM is used for capturing subtle surface phenomenon occurring during epitaxial process of electrolyte on anode. The system studied is Silicon (100) during Chemical Vapor Deposition of Ethylene Carbonate. A strain driven relaxation theory is modeled to explain the unusual restructuring of Si substrate. The other extreme, TEM, is often used to study electrochemical processes, without clear understanding of how the high-energy electron beam can influence the sample under investigation. Here, we study the radiolysis in liquid cell TEM and emphasize on the enhancement of radiation dose at interfaces of the liquid due to generation of secondary and backscattered electrons from adjoining materials. It is shown that this effect is localized in a 10 nm region around the interface and can play a dominating role if there is an interface of liquid with heavy metals like Gold and Platinum which are frequently used as electrode materials. This analysis can be used to establish guidelines for experimentalists to follow, for accurate interpretation of their results.

Poly(methylene blue) functionalized graphene modified carbon ionic liquid electrode for the electrochemical detection of dopamine.

PubMed

Sun, Wei; Wang, Yuhua; Zhang, Yuanyuan; Ju, Xiaomei; Li, Guangjiu; Sun, Zhenfan

2012-11-02

An ionic liquid 1-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) was used as the substrate electrode and a poly(methylene blue) (PMB) functionalized graphene (GR) composite film was co-electrodeposited on CILE surface by cyclic voltammetry. The PMB-GR/CILE exhibited better electrochemical performances with higher conductivity and lower electron transfer resistance. Electrochemical behavior of dopamine (DA) was further investigated by cyclic voltammetry and a pair of well-defined redox peaks appeared with the peak-to-peak separation (ΔE(p)) as 0.058V in 0.1 mol L(-1) pH 6.0 phosphate buffer solution, which proved a fast quasi-reversible electron transfer process on the modified electrode. Electrochemical parameters of DA on PMB-GR/CILE were calculated with the electron transfer number as 1.83, the charge transfer coefficients as 0.70, the apparent heterogeneous electron transfer rate constant as 1.72 s(-1) and the diffusional coefficient (D) as 3.45×10(-4) cm(2) s(-1), respectively. Under the optimal conditions with differential pulse voltammetric measurement, the linear relationship between the oxidation peak current of DA and its concentration was obtained in the range from 0.02 to 800.0 μmol L(-1) with the detection limit as 5.6 nmol L(-1) (3σ). The coexisting substances exhibited no interference and PMB-GR/CILE was applied to the detection of DA injection samples and human urine samples with satisfactory results. Copyright © 2012 Elsevier B.V. All rights reserved.

Integration of Electrochemistry with Ultra Performance Liquid Chromatography/Mass Spectrometry (UPLC/MS)

PubMed Central

Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A.; Chen, Hao

2015-01-01

This study presents the development of ultra-performance liquid chromatography/mass spectrometry (UPLC/MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of disulfide bond-containing proteins/peptides. In our approach, a protein/peptide mixture sample undergoes fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and MS/MS analyses. The electrochemical cell is coupled to MS using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, disulfide bond-containing peptides can be differentiated from those without disulfide bonds as the former are electroactive and reducible. Tandem MS analysis of the disulfide-reduced peptide ions provides increased sequence and disulfide linkage pattern information. In a reactive DESI-MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which would be useful in top-down protein structure analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1~2 orders of magnitude by using UPLC for the LC/EC/MS platform, in comparison to the previously used high performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis. PMID:26307715

Vibrational Sum Frequency Study of the Influence of Water-Ionic Liquid Mixtures in the CO2 Electroreduction on Silver Electrodes

NASA Astrophysics Data System (ADS)

Garcia Rey, Natalia; Dlott, Dana

2015-06-01

Understand the molecular dynamics on buried electrodes under electrochemical transformations is of significant interest. There is a big gap of knowledge in the CO2 electroreduction mechanism due to the limitations to access and probe the liquid-metal interfaces [1,2]. Vibrational Sum Frequency Spectroscopy (VSFS) is a non-invasive and surface sensitive technique, with molecular level detection that can be used to probe electrochemical reactions occurring on the electrolyte-electrode interface [2]. We observed the CO2 electroreduction to CO in ionic liquids (ILs) on poly Ag using VSFS synchronized with cyclic voltammetry. In order to follow the CO2 reaction in situ on the ionic liquid-Ag interface; the CO, CO2 and imidazolium vibrational modes (resonant SFS) were monitored as a function of potential. We identified at which potential the CO was produced and how the EMIM-BF4 played an important role in the electron transfer to the CO2, lowering the CO2- energy barrier. A new approach to reveal the double layer dynamics to the electrostatic environment is presented by the study of the nonresonant sum frequency intensity as a function of the applied potential. By this method, we studied the influence of water-ionic liquid mixtures in the CO2 electroreduction on Ag electrode. We observed a shift to lower potentials in the CO2 electroreduction in water-ILs electrolyte. Previous studies in gas diffusion fuel cells have shown the CO2 electroreduction in a water-imidazolium-based ILs on Ag nanoparticles at lower overpotential [3]. Our VSFS study helps to understand the fundamental electrochemical mechanism, showing how the ILs structural transition influences the CO2 electroreduction. [1] Polyansky, D. E.; Electroreduction of Carbon Dioxide, 2014, Encyclopedia of Applied Electrochemistry, Springer New York, pag 431-437. [2] Bain, C. D.; J. Chem. Soc., Faraday Trans., 1995, 91, 1281. [3] Rosen, B. A. et al; Science, 2011, 334 (6056), 643. Rosen, B. A. et al.; J. electrochem. Soc., 2013, 160 (2), H138.

HPLC/EC (High Pressure Liquid Chromatography/Electrochemical Detection) Studies of Selected Explosive Components, Nitroanilines, and Nitrophenols with Dual Electrode Electrochemical Detection.

DTIC Science & Technology

1985-09-01

advantage of HPLC/EC for the separation and detection of electroactive species is well documented in the literature (1-5). It has been demonstrated that...Zorbax, Alltech Spherisorb or BAS Biophase columns. The injection valve was a Rheodyne Model 7120 fitted with a 20 pL loop and mounted vertically for

Influence of Particle Size Distribution on the Performance of Ionic Liquid-based Electrochemical Double Layer Capacitors

PubMed Central

Rennie, Anthony J. R.; Martins, Vitor L.; Smith, Rachel M.; Hall, Peter J.

2016-01-01

Electrochemical double layer capacitors (EDLCs) employing ionic liquid electrolytes are the subject of much research as they promise increased operating potentials, and hence energy densities, when compared with currently available devices. Herein we report on the influence of the particle size distribution of activated carbon material on the performance of ionic liquid based EDLCs. Mesoporous activated carbon was ball-milled for increasing durations and the resultant powders characterized physically (using laser diffraction, nitrogen sorption and SEM) and investigated electrochemically in the form of composite EDLC electrodes. A bi-modal particle size distribution was found for all materials demonstrating an increasing fraction of smaller particles with increased milling duration. In general, cell capacitance decreased with increased milling duration over a wide range of rates using CV and galvanostatic cycling. Reduced coulombic efficiency is observed at low rates (<25 mVs−1) and the efficiency decreases as the volume fraction of the smaller particles increases. Efficiency loss was attributed to side reactions, particularly electrolyte decomposition, arising from interactions with the smaller particles. The effect of reduced efficiency is confirmed by cycling for over 15,000 cycles, which has the important implication that diminished performance and reduced cycle life is caused by the presence of submicron-sized particles. PMID:26911531

The potential of incorporation of binary salts and ionic liquid in P(VP-co-VAc) gel polymer electrolyte in electrochemical and photovoltaic performances

PubMed Central

Ming, Ng Hon; Ramesh, S.; Ramesh, K.

2016-01-01

In this study, dye-sensitized solar cells (DSSCs) has been assembled with poly(1-vinylpyrrolidone-co-vinyl acetate) (P(VP-co-VAc)) gel polymer electrolytes (GPEs) which have been incorporated with binary salt and an ionic liquid. The potential of this combination was studied and reported. The binary salt system GPEs was having ionic conductivity and power conversion efficiency (PCE) that could reach up to 1.90 × 10−3 S cm−1 and 5.53%, respectively. Interestingly, upon the addition of the ionic liquid, MPII into the binary salt system the ionic conductivity and PCE had risen steadily up to 4.09 × 10−3 S cm−1 and 5.94%, respectively. In order to know more about this phenomenon, the electrochemical impedance studies (EIS) of the GPE samples have been done and reported. Fourier transform infrared studies (FTIR) and thermogravimetric analysis (TGA) have also been studied to understand more on the structural and thermal properties of the GPEs. The Nyquist plot and Bodes plot studies have been done in order to understand the electrochemical properties of the GPE based DSSCs and Tafel polarization studies were done to determine the electrocatalytic activity of the GPE samples. PMID:27273020

A mixture of triethylphosphate and ethylene carbonate as a safe additive for ionic liquid-based electrolytes of lithium ion batteries

NASA Astrophysics Data System (ADS)

Lalia, Boor Singh; Yoshimoto, Nobuko; Egashira, Minato; Morita, Masayuki

A binary mixture of triethylphosphate (TEP) and ethylene carbonate (EC) has been examined as a new non-flammable additive for ionic liquid-based electrolytes for lithium-ion batteries. The optimized electrolyte composition consists of 0.6 mol dm -3 (=M) LiTFSI in PP13TFSI mixed with TEP and EC in volume ratio of 80:10:10, where TFSI and PP13 denote bis(trifluoromethanesulfonyl)imide and N-methyl- N-propylpiperidinium, respectively. The ionic conductivity of PP13TFSI dissolving 0.4 M LiTFSI was improved from 8.2 × 10 -4 S cm -1 to 3.5 × 10 -3 S cm -1 (at 20 °C) with the addition of TEP and EC. The electrochemical behavior of 0.4 M LiTFSI/PP13TFSI with and without TEP and EC was studied by cyclic voltammetry, which showed no deteriorating effect by the addition of TEP and EC on the electrochemical window of PP13TFSI. The flammability of the electrolyte was tested by a direct flame test. The proposed ionic liquid-based electrolyte revealed significant improvements in the electrochemical charge-discharge characteristics for both graphite negative and LiMn 2O 4 positive electrodes.

New electrolytes for aluminum production: Ionic liquids

NASA Astrophysics Data System (ADS)

Zhang, Mingming; Kamavarum, Venkat; Reddy, Ramana G.

2003-11-01

In this article, the reduction, refining/recycling, and electroplating of aluminum from room-temperature molten salts are reviewed. In addition, the characteristics of several non-conventional organic solvents, electrolytes, and molten salts are evaluated, and the applicability of these melts for production of aluminum is discussed with special attention to ionic liquids. Also reviewed are electrochemical processes and conditions for electrodeposition of aluminum using ionic liquids at near room temperatures.

Electrochemical device for syngas and liquid fuels production

DOEpatents

Braun, Robert J.; Becker, William L.; Penev, Michael

2017-04-25

The invention relates to methods for creating high value liquid fuels such as gasoline, diesel, jet and alcohols using carbon dioxide and water as the starting raw materials and a system for using the same. These methods combine a novel solid oxide electrolytic cell (SOEC) for the efficient and clean conversion of carbon dioxide and water to hydrogen and carbon monoxide, uniquely integrated with a gas-to-liquid fuels producing method.

A Designer Fluid for Aluminum Phase Change Devices, Vol. 1 of 3: General Inorganic Aqueous Solution (IAS) Chemistry

DTIC Science & Technology

2016-11-17

region, in which liquid is disconnected with the electrochemical cycle and hydrogen gas will be generated. In addition, with Q increasing, all the...179  5.3.  Importance of a Continuous Liquid Back Flow...used IAS; (c) condensed liquid from the vapor of IAS .................. 49  Figure 25: Contact angle comparison between smooth and IAS treated metal

Pitting Behavior of L415 Pipeline Steel in Simulated Leaching Liquid Environment

NASA Astrophysics Data System (ADS)

Wan, H. X.; Yang, X. J.; Liu, Z. Y.; Song, D. D.; Du, C. W.; Li, X. G.

2017-02-01

The corrosion behavior and laws of the west-east gas pressure pipeline of L415 steel were studied in simulated leaching liquid. The failure of the L415 steel during the pressure testing process was investigated using electrochemical polarization, electrochemical impedance spectroscopy, and immersion test. The corrosion rate of the L415 steel increased with ion concentration in the leaching liquid. This rate reached about 0.8 mm a-1 and belonged to the severe corrosion grade. Pitting corrosion was observed in various simulated solutions with different aggressive species concentrations. The original ion concentration in the leaching liquid (1×) is the key factor influencing pitting initiation and development. Pitting showed easy nucleation, and its growth rate was relatively slow, in the basic simulating solution of the leach liquid (i.e., the ion content is compactable to the real condition in the rust on the inner steel pipe surface). Pitting was also highly sensitive and easily grew in the solution with doubled ion concentration in the basic simulating solution (2×). A uniform corrosion, instead of pitting, mainly occurred when the ion concentration was up to 10× of the basic solution.

Electrochemical activation and inhibition of neuromuscular systems through modulation of ion concentrations with ion-selective membranes

NASA Astrophysics Data System (ADS)

Song, Yong-Ak; Melik, Rohat; Rabie, Amr N.; Ibrahim, Ahmed M. S.; Moses, David; Tan, Ara; Han, Jongyoon; Lin, Samuel J.

2011-12-01

Conventional functional electrical stimulation aims to restore functional motor activity of patients with disabilities resulting from spinal cord injury or neurological disorders. However, intervention with functional electrical stimulation in neurological diseases lacks an effective implantable method that suppresses unwanted nerve signals. We have developed an electrochemical method to activate and inhibit a nerve by electrically modulating ion concentrations in situ along the nerve. Using ion-selective membranes to achieve different excitability states of the nerve, we observe either a reduction of the electrical threshold for stimulation by up to approximately 40%, or voluntary, reversible inhibition of nerve signal propagation. This low-threshold electrochemical stimulation method is applicable in current implantable neuroprosthetic devices, whereas the on-demand nerve-blocking mechanism could offer effective clinical intervention in disease states caused by uncontrolled nerve activation, such as epilepsy and chronic pain syndromes.

Smartphone-based cyclic voltammetry system with graphene modified screen printed electrodes for glucose detection.

PubMed

Ji, Daizong; Liu, Lei; Li, Shuang; Chen, Chen; Lu, Yanli; Wu, Jiajia; Liu, Qingjun

2017-12-15

Smartphone-based electrochemical devices have such advantages as the low price, miniaturization, and obtaining the real-time data. As a popular electrochemical method, cyclic voltammetry (CV) has shown its great practicability for quantitative detection and electrodes modification. In this study, a smartphone-based CV system with a simple method of electrode modification was constructed to perform electrochemical detections. The system was composed of these main portions: modified electrodes, portable electrochemical detector and smartphone. Among them, the detector was comprised of an energy transformation module applying the stimuli signals, and a low-cost potentiostat module for CV measurements with a Bluetooth module for transmitting data and commands. With an Application (App), the smartphone was used as the controller and displayer of the system. Through controlling of different scan rates, the smartphone-based system could perform CV detections for redox couples with test errors less than 3.8% compared to that of commercial electrochemical workstation. Also, the reduced graphene oxide (rGO) and sensitive substance could be modified by the system on the screen printed electrodes for detections. As a demonstration, 3-amino phenylboronic acid (APBA) was used as the sensitive substance to fabricate a glucose sensor. Finally, the experimental data of the system were shown the linear, sensitive, and specific responses to glucose at different doses, even in blood serum as low as about 0.026mM with 3δ/slope calculation. Thus, the system could show great potentials of detection and modification of electrodes in various fields, such as public health, water monitoring, and food quality. Copyright © 2017 Elsevier B.V. All rights reserved.

High energy supercapattery with an ionic liquid solution of LiClO4.

PubMed

Yu, Linpo; Chen, George Z

2016-08-15

A supercapattery combining an ideally polarized capacitor-like electrode and a battery-like electrode is demonstrated theoretically and practically using an ionic liquid electrolyte containing 1-butyl-1-methylpyrrolidinium tri(pentafluoroethyl)trifluorophosphate (BMPyrrFAP), gamma-butyrolactone (γ-GBL) and LiClO4. The electrochemical deposition and dissolution of lithium metal on a platinum and glass carbon electrode were investigated in this ionic liquid solution. The CVs showed that the fresh electrochemically deposited lithium metal was stable in the electrolyte, which encouraged the investigation of this ionic liquid solution in a supercapattery with a lithium battery negative electrode. The active material counted specific energy of the supercapattery based on a lithium negative electrode and an activated carbon (Act-C) positive electrode could reach 230 W h kg(-1) under a galvanostatic charge-discharge current density of 1 mA cm(-2). The positive electrode material (Act-C) was also investigated by CV, AC impedance, SEM and BET. The non-uniform particle size and micropores dominated porous structure of the Act-C enabled its electric double layer capacitor (EDLC) behavior in the ionic liquid solution. The measured specific capacitance of the Act-C in this ionic liquid solution is higher than the same Act-C in aqueous solution, which indicates the Act-C can also perform well in the ionic liquid electrolyte.

Non-aqueous primary cell

NASA Astrophysics Data System (ADS)

James, S. D.; Smith, P. H.; Oneill, K. M.; Wilson, M. H.

1986-05-01

This patent application relates to electrochemical cells and especially to high-energy, liquid cathode, non-aqueous lithium electrochemical cells free from highly toxic materials. A non-aqueous lithium electrochemical cell is described which includes a halocarbon cathode depolarizer which is 1,2-dichloroethane, 1.1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloro-1,1-difluoroethane or mixtures thereof and a cathode catalyst which is copper, rhodium, palladium, cobalt phthalocyanine, nickel phthalocyanine, iron phthalocyanine, a cobalt tetraaza-(14)-annulene, a nickel tetraaza-(14)-annulene, a iron tetraaza-(14)-annulene, a cobalt porphyrin, a nickel porphyrin, a iron porphyrin, or a mixture thereof.

Porous inorganic nanostructures with colloidal dimensions: synthesis and applications in electrochemical energy devices.

PubMed

Tartaj, Pedro; Amarilla, Jose M

2014-02-28

Porous inorganic nanostructures with colloidal dimensions can be considered as ideal components of electrochemical devices that operate on renewable energy sources. They combine nanoscale properties with good accessibility, a high number of active sites, short diffusion distances and good processability. Herein, we review some of the liquid-phase routes that lead to the controlled synthesis of these nanostructures in the form of non-hollow, hollow or yolk-shell configurations. From solar and fuel cells to batteries and supercapacitors, we put special emphasis on showing how these sophisticated structures can enhance the efficiency of electrochemical energy devices.

Studies of electrochemical interfaces by TOF neutron reflectometry at the IBR-2 reactor

NASA Astrophysics Data System (ADS)

Petrenko, V. I.; Gapon, I. V.; Rulev, A. A.; Ushakova, E. E.; Kataev, E. Yu; Yashina, L. V.; Itkis, D. M.; Avdeev, M. V.

2018-03-01

The operation performance of electrochemical energy conversion and storage systems such as supercapacitors and batteries depends on the processes occurring at the electrochemical interfaces, where charge separation and chemical reactions occur. Here, we report about the tests of the neutron reflectometry cells specially designed for operando studies of structural changes at the electrochemical interfaces between solid electrodes and liquid electrolytes. The cells are compatible with anhydrous electrolytes with organic solvents, which are employed today in all lithium ion batteries and most supercapacitors. The sensitivity of neutron reflectometry applied at the time-of-flight (TOF) reflectometer at the pulsed reactor IBR-2 is discussed regarding the effect of solid electrolyte interphase (SEI) formation on metal electrode surface.

Comparison of diffusivity data derived from electrochemical and NMR investigations of the SeCN¯/(SeCN)2/(SeCN)3¯ system in ionic liquids.

PubMed

Solangi, Amber; Bond, Alan M; Burgar, Iko; Hollenkamp, Anthony F; Horne, Michael D; Rüther, Thomas; Zhao, Chuan

2011-06-02

Electrochemical studies in room temperature ionic liquids are often hampered by their relatively high viscosity. However, in some circumstances, fast exchange between participating electroactive species has provided beneficial enhancement of charge transport. The iodide (I¯)/iodine (I(2))/triiodide (I(3)¯) redox system that introduces exchange via the I¯ + I(2) ⇌ I(3)¯ process is a well documented example because it is used as a redox mediator in dye-sensitized solar cells. To provide enhanced understanding of ion movement in RTIL media, a combined electrochemical and NMR study of diffusion in the {SeCN¯-(SeCN)(2)-(SeCN)(3)¯} system has been undertaken in a selection of commonly used RTILs. In this system, each of the Se, C and N nuclei is NMR active. The electrochemical behavior of the pure ionic liquid, [C(4)mim][SeCN], which is synthesized and characterized here for the first time, also has been investigated. Voltammetric studies, which yield readily interpreted diffusion-limited responses under steady-state conditions by means of a Random Assembly of Microdisks (RAM) microelectrode array, have been used to measure electrochemically based diffusion coefficients, while self-diffusion coefficients were measured by pulsed field gradient NMR methods. The diffusivity data, derived from concentration and field gradients respectively, are in good agreement. The NMR data reveal that exchange processes occur between selenocyanate species, but the voltammetric data show the rates of exchange are too slow to enhance charge transfer. Thus, a comparison of the iodide and selenocyanate systems is somewhat paradoxical in that while the latter give RTILs of low viscosity, sluggish exchange kinetics prevent any significant enhancement of charge transfer through direct electron exchange. In contrast, faster exchange between iodide and its oxidation products leads to substantial electron exchange but this effect does not compensate sufficiently for mass transport limitations imposed by the higher viscosity of iodide RTILs.

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI –] anions with smaller [BF 4 –] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less

Amorphizing of Cu Nanoparticles toward Highly Efficient and Robust Electrocatalyst for CO2 Reduction to Liquid Fuels with High Faradaic Efficiencies.

PubMed

Duan, Yan-Xin; Meng, Fan-Lu; Liu, Kai-Hua; Yi, Sha-Sha; Li, Si-Jia; Yan, Jun-Min; Jiang, Qing

2018-04-01

Conversion of carbon dioxide (CO 2 ) into valuable chemicals, especially liquid fuels, through electrochemical reduction driven by sustainable energy sources, is a promising way to get rid of dependence on fossil fuels, wherein developing of highly efficient catalyst is still of paramount importance. In this study, as a proof-of-concept experiment, first a facile while very effective protocol is proposed to synthesize amorphous Cu NPs. Unexpectedly, superior electrochemical performances, including high catalytic activity and selectivity of CO 2 reduction to liquid fuels are achieved, that is, a total Faradaic efficiency of liquid fuels can sum up to the maximum value of 59% at -1.4 V, with formic acid (HCOOH) and ethanol (C 2 H 6 O) account for 37% and 22%, respectively, as well as a desirable long-term stability even up to 12 h. More importantly, this work opens a new avenue for improved electroreduction of CO 2 based on amorphous metal catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of metal nanoelectrodes by interfacial reactions.

PubMed

Zhu, Xinyu; Qiao, Yonghui; Zhang, Xin; Zhang, Sensen; Yin, Xiaohong; Gu, Jing; Chen, Ye; Zhu, Zhiwei; Li, Meixian; Shao, Yuanhua

2014-07-15

Despite great improvements in the past decades, the controllable fabrication of metal nanoelectrodes still remains very challenging. In this work, a simple and general way to fabricate metal nanoelectrodes (Ag, Au, and Pt) is developed. On the basis of interfacial reactions at nano-liquid/liquid interfaces supported at nanopipettes, the nanoparticles can be formed in situ and have been used to block the orifices of pipettes to make nanoelectrodes. The effect of the driving force for interfacial reaction at the liquid/liquid interface, the ratio of redox species in organic and aqueous phases, and the surface charge of the inner wall of a pipette have been studied. The fabricated nanoelectrodes have been characterized by scanning electron microscopy (SEM) and electrochemical techniques. A silver electrode with about 10 nm in radius has been employed as the scanning electrochemical microscopy (SECM) probe to explore the thickness of a water/nitrobenzene (W/NB) interface, and this value is equal to 0.8 ± 0.1 nm (n = 5). This method of fabrication of nanoelectrodes can be extended to other metal or semiconductor electrodes.

Principles and applications of laser-induced liquid-phase jet-chemical etching

NASA Astrophysics Data System (ADS)

Stephen, Andreas; Metev, Simeon; Vollertsen, Frank

2003-11-01

In this treatment method laser radiation, which is guided from a coaxially expanding liquid jet-stream, locally initiates a thermochemical etching reaction on a metal surface, which leads to selective material removal at high resolution and quality of the treated surface as well as low thermal influence on the workpiece. Electrochemical investigations were performed under focused laser irradiation using a cw-Nd:YAG laser with a maximum power of 15 W and a simultaneous impact of the liquid jet-stream consisting of phosphoric acid with a maximum flow rate of 20 m/s. The time resolved measurements of the electrical potential difference against an electrochemical reference electrode were correlated with the specific processing parameters and corresponding etch rates to identify processing conditions for temporally stable and enhanced chemical etching reactions. Applications of laser-induced liquid-phase jet-chemical etching in the field of sensor technology, micromechanics and micrmoulding technology are presented. This includes the microstructuring of thin film systems, cutting of foils of shape memory alloys or the generation of structures with defined shape in bulk material.

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

DOE PAGES

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris; ...

2018-04-19

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI –] anions with smaller [BF 4 –] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less

Analysis of phenolic acids by ionic liquid-in-water microemulsion liquid chromatography coupled with ultraviolet and electrochemical detector.

PubMed

Peng, Li-Qing; Cao, Jun; Du, Li-Jing; Zhang, Qi-Dong; Shi, Yu-Tin; Xu, Jing-Jing

2017-05-26

An environmentally friendly ionic liquid-in-water (IL/W) microemulsion was established and applied as mobile phase in microemulsion liquid chromatography (MELC) with ultraviolet (UV) detection or electrochemical detector (ECD) for analysis of phenolic compounds in real samples. The optimal condition of the method was using the best composition of microemulsion (0.2% w/v [HMIM]PF 6 , 1.0% w/v SDS, 3.0% w/v n-butanol, 95.8% v/v water, pH 2.5) with UV detection. The validation results indicated that the method provided high degree of sensitivity, precision and accuracy with the low limit of detections ranged from 17.9-238ng/mL, satisfactory mean recovery values in the range of 80.1-105% and good linearity (r 2 >0.9994). Additionally, this method exhibited high selectivity and resolution for the analytes and was more eco-friendly compared with traditional MELC method. Consequently, the established IL/W MELC method was successfully applied to simultaneously separate and determine target compounds in Danshen sample and its preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

NASA Tech Briefs, June 2009

NASA Technical Reports Server (NTRS)

2009-01-01

Topics covered include: Device for Measuring Low Flow Speed in a Duct, Measuring Thermal Conductivity of a Small Insulation Sample, Alignment Jig for the Precise Measurement of THz Radiation, Autoignition Chamber for Remote Testing of Pyrotechnic Devices, Microwave Power Combiners for Signals of Arbitrary Amplitude, Synthetic Foveal Imaging Technology, Airborne Antenna System for Minimum-Cycle-Slip GPS Reception, Improved Starting Materials for Back-Illuminated Imagers, Multi-Modulator for Bandwidth-Efficient Communication, Some Improvements in Utilization of Flash Memory Devices, GPS/MEMS IMU/Microprocessor Board for Navigation, T/R Multi-Chip MMIC Modules for 150 GHz, Pneumatic Haptic Interfaces, Device Acquires and Retains Rock or Ice Samples, Cryogenic Feedthrough Test Rig, Improved Assembly for Gas Shielding During Welding or Brazing, Two-Step Plasma Process for Cleaning Indium Bonding Bumps, Tool for Crimping Flexible Circuit Leads, Yb14MnSb11 as a High-Efficiency Thermoelectric Material, Polyimide-Foam/Aerogel Composites for Thermal Insulation, Converting CSV Files to RKSML Files, Service Management Database for DSN Equipment, Chemochromic Hydrogen Leak Detectors, Compatibility of Segments of Thermoelectric Generators, Complementary Barrier Infrared Detector, JPL Greenland Moulin Exploration Probe, Ultra-Lightweight Self-Deployable Nanocomposite Structure for Habitat Applications, and Room-Temperature Ionic Liquids for Electrochemical Capacitors.

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

DOE PAGES

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; ...

2016-08-31

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzingmore » the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential.« less

Escherichia coli Nissle 1917 enhances bioavailability of serotonin in gut tissues through modulation of synthesis and clearance

PubMed Central

Nzakizwanayo, Jonathan; Dedi, Cinzia; Standen, Guy; Macfarlane, Wendy M.; Patel, Bhavik A.; Jones, Brian V.

2015-01-01

Accumulating evidence shows indigenous gut microbes can interact with the human host through modulation of serotonin (5-HT) signaling. Here we investigate the impact of the probiotic Escherichia coli Nissle 1917 (EcN) on 5-HT signalling in gut tissues. Ex-vivo mouse ileal tissue sections were treated with either EcN or the human gut commensal MG1655, and effects on levels of 5-HT, precursors, and metabolites, were evaluated using amperometry and high performance liquid chromatography with electrochemical detection (HPLC-EC). Exposure of tissue to EcN cells, but not MG1655 cells, was found to increase levels of extra-cellular 5-HT. These effects were not observed when tissues were treated with cell-free supernatant from bacterial cultures. In contrast, when supernatant recovered from untreated ileal tissue was pre-incubated with EcN, the derivative cell-free supernatant was able to elevate 5-HT overflow when used to treat fresh ileal tissue. Measurement of 5-HT precursors and metabolites indicated EcN also increases intracellular 5-HTP and reduces 5-HIAA. The former pointed to modulation of tryptophan hydroxylase-1 to enhance 5-HT synthesis, while the latter indicates an impact on clearance into enterocytes through SERT. Taken together, these findings show EcN is able to enhance 5-HT bioavailability in ileal tissues through interaction with compounds secreted from host tissues. PMID:26616662

Electrochemical Capacities of Commercially Available Structural Carbon Fibers, Fabrics, and Papers

DTIC Science & Technology

2008-09-01

Hollingsworth & Vose. A liquid electrolyte of ethylene carbonate: ethyl methyl carbonate (3:7 by weight) with 1.0 M lithium hexafluorophosphate (LiPF6) was...fiber pulp COTS commercial off-the-shelf Da dalton FE-SEM Field Emission Scanning Electron Microscope LiPF6 lithium hexafluorophosphate MWNT...material for anodes in modern technologies, particularly in lithium -ion batteries and electrochemical supercapacitors. Graphitic carbon allows for

Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes.

PubMed

Van Aken, Katherine L; McDonough, John K; Li, Song; Feng, Guang; Chathoth, Suresh M; Mamontov, Eugene; Fulvio, Pasquale F; Cummings, Peter T; Dai, Sheng; Gogotsi, Yury

2014-07-16

While most supercapacitors are limited in their performance by the stability of the electrolyte, using neat ionic liquids (ILs) as the electrolyte can expand the voltage window and temperature range of operation. In this study, ILs with bis(trifluoromethylsulfonyl)imide (Tf2N) as the anion were investigated as the electrolyte in onion-like carbon-based electrochemical capacitors. To probe the influence of cations on the electrochemical performance of supercapacitors, three different cations were used: 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium and 1,6-bis(3-methylimidazolium-1-yl). A series of electrochemical characterization tests was performed using cyclic voltammetry (CV), galvanostatic cycling and electrochemical impedance spectroscopy (EIS). Diffusion coefficients were measured using EIS and correlated with quasielastic neutron scattering and molecular dynamics simulation. These three techniques were used in parallel to confirm a consistent trend between the three ILs. It was found that the IL with the smaller sized cation had a larger diffusion coefficient, leading to a higher capacitance at faster charge-discharge rates. Furthermore, the IL electrolyte performance was correlated with increasing temperature, which limited the voltage stability window and led to the formation of a solid electrolyte interphase on the carbon electrode surface, evident in both the CV and EIS experiments.

In Situ Electrochemical Synthesis of Oriented and Defect-Free AEL Molecular-Sieve Films Using Ionic Liquids.

PubMed

Yu, Tongwen; Chu, Wenling; Cai, Rui; Liu, Yanchun; Yang, Weishen

2015-10-26

Simply preparing oriented and defect-free molecular-sieve films have been a long-standing challenge both in academia and industry. Most of the early works focus on the careful and multiple controls of the seeds layer or synthesis conditions. Herein, we report a one-step in situ electrochemical ionothermal method that combines a controllable electric field with ionic liquids. We demonstrate that an in-plane oriented and defect-free AEL (one molecular-sieve framework type) molecular-sieve film was obtained using an Al electrode as the Al source. The excellent corrosion-resistant performance of the film makes this technology promising in multiple applications, such as anti-corrosion coatings. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asadi, M.; Kim, K.; Liu, C.

2016-07-28

Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform thatmore » concurrently oxidized water in the absence of any external potential.« less

A hybrid nanosensor for TNT vapor detection.

PubMed

Díaz Aguilar, Alvaro; Forzani, Erica S; Leright, Mathew; Tsow, Francis; Cagan, Avi; Iglesias, Rodrigo A; Nagahara, Larry A; Amlani, Islamshah; Tsui, Raymond; Tao, N J

2010-02-10

Real-time detection of trace chemicals, such as explosives, in a complex environment containing various interferents has been a difficult challenge. We describe here a hybrid nanosensor based on the electrochemical reduction of TNT and the interaction of the reduction products with conducting polymer nanojunctions in an ionic liquid. The sensor simultaneously measures the electrochemical current from the reduction of TNT and the conductance change of the polymer nanojunction caused from the reduction product. The hybrid detection mechanism, together with the unique selective preconcentration capability of the ionic liquid, provides a selective, fast, and sensitive detection of TNT. The sensor, in its current form, is capable of detecting parts-per-trillion level TNT in the presence of various interferents within a few minutes.

BF 3-promoted electrochemical properties of quinoxaline in propylene carbonate

DOE PAGES

Carino, Emily V.; Diesendruck, Charles E.; Moore, Jeffrey S.; ...

2015-02-04

Electrochemical and density functional studies demonstrate that coordination of electrolyte constituents to quinoxalines modulates their electrochemical properties. Quinoxalines are shown to be electrochemically inactive in most electrolytes in propylene carbonate, yet the predicted reduction potential is shown to match computational estimates in acetonitrile. We find that in the presence of LiBF 4 and trace water, an adduct is formed between quinoxaline and the Lewis acid BF3, which then displays electrochemical activity at 1–1.5 V higher than prior observations of quinoxaline electrochemistry in non-aqueous media. Direct synthesis and testing of a bis-BF 3 quinoxaline complex further validates the assignment of themore » electrochemically active species, presenting up to a ~26-fold improvement in charging capacity, demonstrating the advantages of this adduct over unmodified quinoxaline in LiBF 4-based electrolyte. The use of Lewis acids to effectively “turn on” the electrochemical activity of organic molecules may lead to the development of new active material classes for energy storage applications.« less

Library of electrocatalytic sites in nano-structured domains: electrocatalysis of hydrogen peroxide.

PubMed

Pandey, Prem C; Singh, Bhupendra

2008-12-01

Electrochemical detection of hydrogen peroxide at eight types of ormosil-modified electrodes, referred as hexacyanoferrate-system; Prussian blue systems (PB-1, PB-2, and PB-3), palladium (Pd-) system, graphite (Gr-) system, gold nanoparticle (AuNPs) system and palladium-gold nanoparticle (Pd-AuNPs) system were studied. The results on electrochemical detection suggested that hydrogen peroxide does not undergo homogeneous electrochemical mediation; however, the presence of redox mediator within nano-structured domains facilitates the electro-analysis of the same via redox electrocatalysis. Four approaches causing manipulation in nano-structured domains are described: (a) increase in the molecular size of the components generating nano-structured domains; (b) modulation via chemical reactivity; (c) modulation by non-reactive moieties and known nanoparticles; and (d) modulation by mixed approaches (a-c), all leading to decrease in a nano-structured domains. The results demonstrated that an increase in the size of nano-structured domains or decrease in micro-porous geometry increases the efficiency of electrocatalysis. The basic reaction protocol adopted in generating nano-structured domains, followed by manipulation protocols, supported the introduction of a library for creating electrocatalytic sites with varying electrocatalytic efficiency within the same basic nano-structured platform.

Bio-inspired materials for electrochemical devices

NASA Astrophysics Data System (ADS)

Pawlicka, A.; Firmino, A.; Sentanin, F.; Sabadini, R. C.; Jimenez, D. E. Q.; Jayme, C. C.; Mindroiu, M.; Zgarian, R. G.; Tihan, G. T.; Rau, I.; Silva, M. M.; Nogueira, A. F.; Kanicki, J.; Kajzar, F.

2015-10-01

Natural macromolecules are very promising row materials to be used in modern technology including security and defense. They are abundant in nature, easy to extract and possess biocompatibility and biodegradability properties. These materials can be modified throughout chemical or physical processes, and can be doped with lithium and rare earth salts, ionic liquids, organic and inorganic acids. In this communication samples of DNA and modified DNA were doped with Prussian Blue (PB), poly(ethylene dioxythiophene) (PEDOT), europium and erbium triflate and organic dyes such as Nile Blue (NB), Disperse Red 1 (DR1) and Disperse Orange 3 (DO3). The colored or colorless membranes were characterized by electrochemical and spectroscopic measurements, and they were applied in electrochromic devices (ECDs) and dye sensitized solar cells (DSSC). ECDs change the color under applied potential, so they can modulate the intensity of transmitted light of 15 to 35%. As the electrochromic materials, WO3 or Prussian blue (PB), are usually blue colored, the color change is from transparent to blue. DNA, and the complexes: DNA-CTMA, DNA-DODA and DNAPEDOT: PSS were also investigated as either hole carrier material (HTM) or polymer electrolyte in dye-sensitized solar cells (DSSC). The DNA-based samples as HTM in small DSSCs revealed a solar energy conversion efficiency of 0.56%. Polymer electrolytes of DNA-CTMA and DNA-DODA, both with 10 wt% of LiI/I2, applied in small DSSC, exhibited the efficiencies of 0.18 and 0.66%, respectively. The obtained results show that natural macromolecules-based membranes are not only environmentally friendly but are also promising materials to be investigated for several electrochemical devices. However, to obtain better performances more research is still needed.

Electrochemical carbon dioxide concentrator subsystem math model. [for manned space station

NASA Technical Reports Server (NTRS)

Marshall, R. D.; Carlson, J. N.; Schubert, F. H.

1974-01-01

A steady state computer simulation model has been developed to describe the performance of a total six man, self-contained electrochemical carbon dioxide concentrator subsystem built for the space station prototype. The math model combines expressions describing the performance of the electrochemical depolarized carbon dioxide concentrator cells and modules previously developed with expressions describing the performance of the other major CS-6 components. The model is capable of accurately predicting CS-6 performance over EDC operating ranges and the computer simulation results agree with experimental data obtained over the prediction range.

SPECIAL ISSUE ON OPTICAL PROCESSING OF INFORMATION: Characteristics of surface-plasmon liquid-crystal light modulators operating under phase modulation conditions

NASA Astrophysics Data System (ADS)

Nazvanov, V. F.; Afonin, O. A.; Grebennikov, A. I.

1995-10-01

Electrically and optically controlled liquid-crystal light modulators based on surface plasmons were developed and investigated in an ellipsometric optical system. The characteristics of these modulators were determined and compared under phase and amplitude modulation conditions.

Tongue Pressure Modulation during Swallowing: Water versus Nectar-Thick Liquids

ERIC Educational Resources Information Center

Steele, Catriona M.; Bailey, Gemma L.; Molfenter, Sonja M.

2010-01-01

Purpose: Evidence of tongue-palate pressure modulation during swallowing between thin and nectar-thick liquids stimuli has been equivocal. This mirrors a lack of clear evidence in the literature of tongue and hyoid movement modulation between nectar-thick and thin liquid swallows. In the current investigation, the authors sought to confirm whether…

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2000-01-01

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. In one embodiment, a sheet of conductive material is processed by employing a known milling, stamping, or chemical etching technique to include a connection pattern which provides for flexible and selective interconnecting of individual electrochemical cells within the housing, which may be a hermetically sealed housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Electroslag Treatment of Liquid Cast Iron

NASA Astrophysics Data System (ADS)

Grachev, V. A.

2018-01-01

The processes that occur in the liquid metal-slag system during electroslag treatment of cast iron are studied from an electrochemical standpoint. The role of electrolysis in the electroslag process is shown, and a method for producing high-strength cast iron with globular graphite using electrolysis of a slag containing magnesium oxides and fluorides is proposed and tested.

High performance ultracapacitors with carbon nanomaterials and ionic liquids

DOEpatents

Lu, Wen; Henry, Kent Douglas

2012-10-09

The present invention is directed to the use of carbon nanotubes and/or electrolyte structures in various electrochemical devices, such as ultracapacitors having an ionic liquid electrolyte. The carbon nanotubes are preferably aligned carbon nanotubes. Compared to randomly entangled carbon nanotubes, aligned carbon nanotubes can have better defined pore structures and higher specific surface areas.

Industrial uses and applications of ionic liquids

NASA Astrophysics Data System (ADS)

Gutowski, Keith E.

2018-02-01

Ionic liquids are salts that melt at low temperatures (usually defined as less than 100 °C) and have a number of interesting properties that make them useful for industrial applications. Typical ionic liquid properties include high thermal stabilities, negligible vapor pressures, wide liquidus ranges, broad electrochemical windows, and unique solvation properties. Furthermore, the potential combinations of cations and anions provide nearly unlimited chemical tunability. This article will describe the diverse industrial uses of ionic liquids and how their unique properties are leveraged, with examples ranging from chemical processing to consumer packaged goods.

Electrical research on solar cells and photovoltaic materials

NASA Technical Reports Server (NTRS)

Orehotsky, J.

1984-01-01

The flat-plate solar cell array program which increases the service lifetime of the photovoltaic modules used for terrestrial energy applications is discussed. The current-voltage response characteristics of the solar cells encapsulated in the modules degrade with service time and this degradation places a limitation on the useful lifetime of the modules. The most desirable flat-plate array system involves solar cells consisting of highly polarizable materials with similar electrochemical potentials where the cells are encapsulated in polymers in which ionic concentrations and mobilities are negligibly small. Another possible mechanism limiting the service lifetime of the photovoltaic modules is the gradual loss of the electrical insulation characteristics of the polymer pottant due to water absorption or due to polymer degradation from light or heat effects. The mechanical properties of various polymer pottant materials and of electrochemical corrosion mechanisms in solar cell material are as follows: (1) electrical and ionic resistivity; (2) water absorption kinetics and water solubility limits; and (3) corrosion characterization of various metallization systems used in solar cell construction.

Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals

NASA Astrophysics Data System (ADS)

Weitzner, Stephen E.; Dabo, Ismaila

2017-11-01

The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.

Liquid crystal television spatial light modulators

NASA Technical Reports Server (NTRS)

Liu, Hua-Kuang; Chao, Tien-Hsin

1989-01-01

The spatial light modulation characteristics and capabilities of the liquid crystal television (LCTV) spatial light modulators (SLMs) are discussed. A comparison of Radio Shack, Epson, and Citizen LCTV SLMs is made.

A reversible conductivity modulation of azobenzene-based ionic liquids in aqueous solutions using UV/vis light.

PubMed

Li, Zhiyong; Yuan, Xiaoqing; Feng, Ying; Chen, Yongkui; Zhao, Yuling; Wang, Huiyong; Xu, Qingli; Wang, Jianji

2018-05-09

Photo-induced conductivity modulation of stimuli-responsive materials is of great importance from the viewpoint of fundamental research and technology. In this work, 5 new kinds of azobenzene-based photo-responsive ionic liquids were synthesized and characterized, and UV/vis light modulation of their conductivity was investigated in an aqueous solution. The factors affecting the conductivity modulation of the photo-responsive fluids, such as photo-isomerization efficiency, photo-regulation aggregation, concentration and chemical structure of the ionic liquids, were examined systematically. It was found that the conductivity of the ionic liquids in water exhibited a significant increase upon UV light irradiation and the ionic liquids with a shorter alkyl spacer in the cation showed a more remarkable photo-induced conductivity enhancement with a maximum increase of 150%. In addition, the solution conductivity was restored (or very close) to the initial value upon an alternative irradiation with visible light. Thus, the solution conductivity can be modulated using alternative irradiation with UV and visible light. Although the reversible photo-isomerization of the azobenzene group under UV/vis irradiation is the origin of the conductivity modulation, the photo-regulated aggregation of the ionic liquid in water is indispensable for the maximum degree of conductivity modulation because UV irradiation can weaken, even break the aggregated cis-isomers of the ionic liquids in an aqueous solution.

Role of carbon nanotubes in electroanalytical chemistry: a review.

PubMed

Agüí, Lourdes; Yáñez-Sedeño, Paloma; Pingarrón, José M

2008-08-01

This review covers recent advances in the development of new designs of electrochemical sensors and biosensors that make use of electrode surfaces modification with carbon nanotubes. Applications based on carbon nanotubes-driven electrocatalytic effects, and the construction and analytical usefulness of new hybrid materials with polymers or other nanomaterials will be treated. Moreover, electrochemical detection using carbon nanotubes-modified electrodes as detecting systems in separation techniques such as high performance liquid chromatography (HPLC) or capillary electrophoresis (CE) will be also considered. Finally, the preparation of electrochemical biosensors, including enzyme electrodes, immunosensors and DNA biosensors, in which carbon nanotubes play a significant role in their sensing performance will be separately considered.

Predicting In-Situ X-ray Diffraction for the SrTiO3/Liquid Interface from First Principles

NASA Astrophysics Data System (ADS)

Letchworth-Weaver, Kendra; Gunceler, Deniz; Sundararaman, Ravishankar; Huang, Xin; Brock, Joel; Arias, T. A.

2013-03-01

Recent advances in experimental techniques, such as in-situ x-ray diffraction, allow researchers to probe the solid-liquid interface in electrochemical systems under operating conditions. These advances offer an unprecedented opportunity for theory to predict properties of electrode materials in aqueous environments and inform the design of energy conversion and storage devices. To compare with experiment, these theoretical studies require microscopic details of both the liquid and the electrode surface. Joint Density Functional Theory (JDFT), a computationally efficient alternative to molecular dynamics, couples a classical density-functional, which captures molecular structure of the liquid, to a quantum-mechanical functional for the electrode surface. We present a JDFT exploration of SrTiO3, which can catalyze solar-driven water splitting, in an electrochemical environment. We determine the geometry of the polar SrTiO3 surface and the equilibrium structure of the contacting liquid, as well as the influence of the liquid upon the electronic structure of the surface. We then predict the effect of the fluid environment on x-ray diffraction patterns and compare our predictions to in-situ measurements performed at the Cornell High Energy Synchrotron Source (CHESS). This material is based upon work supported by the Energy Materials Center at Cornell (EMC2), an Energy Frontier Research Center funded by the U.S. Department of Energy.

Liquid metal actuator driven by electrochemical manipulation of surface tension

NASA Astrophysics Data System (ADS)

Russell, Loren; Wissman, James; Majidi, Carmel

2017-12-01

We examine the electrocapillary properties of a fluidic actuator composed of a liquid metal droplet that is submerged in electrolytic solution and attached to an elastic beam. The beam deflection is controlled by electrochemically driven changes in the surface energy of the droplet. The metal is a eutectic gallium-indium alloy that is liquid at room temperature and forms an nm-thin Ga2O3 skin when oxidized. The effective surface tension of the droplet changes dramatically with oxidation and reduction, which are reversibly controlled by applying low voltage to the electrolytic bath. Wetting the droplet to two copper pads allows for a controllable tensile force to be developed between the opposing surfaces. We demonstrate the ability to reliably control force by changing the applied oxidizing voltage. Actuator forces and droplet geometries are also examined by performing a computational fluid mechanics simulation using Surface Evolver. The theoretical predictions are in qualitative agreement with the experimental measurements and provide additional confirmation that actuation is driven by surface tension.

Trace detection of oxygen--ionic liquids in gas sensor design.

PubMed

Baltes, N; Beyle, F; Freiner, S; Geier, F; Joos, M; Pinkwart, K; Rabenecker, P

2013-11-15

This paper presents a novel electrochemical membrane sensor on basis of ionic liquids for trace analysis of oxygen in gaseous atmospheres. The faradaic response currents for the reduction of oxygen which were obtained by multiple-potential-step-chronoamperometry could be used for real time detection of oxygen down to concentrations of 30 ppm. The theoretical limit of detection was 5 ppm. The simple, non-expensive sensors varied in electrolyte composition and demonstrated a high sensitivity, a rapid response time and an excellent reproducibility at room temperature. Some of them were continuously used for at least one week and first results promise good long term stability. Voltammetric, impedance and oxygen detection studies at temperatures up to 200 °C (in the presence and absence of humidity and CO2) revealed also the limitations of certain ionic liquids for some electrochemical high temperature applications. Application areas of the developed sensors are control and analysis processes of non oxidative and oxygen free atmospheres. Copyright © 2013 Elsevier B.V. All rights reserved.

Mechanochemical synthesis of carbon-based nanocomposites for supercapacitors

NASA Astrophysics Data System (ADS)

Mateyshina, Yuliya G.; Ulihin, Artem S.; Uvarov, Nikolai F.

2014-12-01

New nanoporous carbon-SiO2 composite materials were synthesized from organic raw materials (rice shells) and their electrochemical properties were investigated by cyclic voltammetry in liquid electrolytes (6 M KOH or 1 M H2SO4). A correlation between specific capacitance and specific surface area was observed. Due to high specific capacitance of 90 F/g the carbon materials under study may be regarded as promising electrode materials for electrochemical supercapacitors.

Sheath-flow electrochemical detection of amino acids with a copper wire electrode in capillary electrophoresis.

PubMed

Inoue, Junji; Kaneta, Takashi; Imasaka, Totaro

2012-09-01

Here, we report the detection of native amino acids using a sheath-flow electrochemical detector with a working electrode made of copper wire. A separation capillary that was inserted into a platinum tube in the detector acted as a grounded electrode for electrophoresis and as a flow channel for sheath liquid. Sheath liquid flowed outside the capillary to support the transport of the separated analytes to the working electrode for electrochemical detection. The copper wire electrode was aligned at the outlet of the capillary in a wall-jet configuration. Amino acids injected into the capillary were separated following elution from the end of the capillary and detection by the copper electrode. Three kinds of copper electrodes with different diameters-50, 125, and 300 μm-were examined to investigate the effect of the electrode diameter on sensitivity. The peak widths of the analytes were independent of the diameter of the working electrode, while the 300-μm electrode led to a decrease in the signal-to-noise ratio compared with the 50- and 125-μm electrodes, which showed no significant difference. The flow rate of the sheath liquid was also varied to optimize the detection conditions. The limits of detection for amino acids ranged from 4.4 to 27 μM under optimal conditions. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

DOE PAGES

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu; ...

2017-12-05

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Synergistic gelation of silica nanoparticles and a sorbitol-based molecular gelator to yield highly-conductive free-standing gel electrolytes.

PubMed

Basrur, Veidhes R; Guo, Juchen; Wang, Chunsheng; Raghavan, Srinivasa R

2013-01-23

Lithium-ion batteries have emerged as the preferred type of rechargeable batteries, but there is a need to improve the performance of the electrolytes therein. Specifically, the challenge is to obtain electrolytes with the mechanical rigidity of solids but with liquid-like conductivities. In this study, we report a class of nanostructured gels that are able to offer this unique combination of properties. The gels are prepared by utilizing the synergistic interactions between a molecular gelator, 1,3:2,4-di-O-methyl-benzylidene-d-sorbitol (MDBS), and a nanoscale particulate material, fumed silica (FS). When MDBS and FS are combined in a liquid consisting of propylene carbonate with dissolved lithium perchlorate salt, the liquid electrolyte is converted into a free-standing gel due to the formation of a strong MDBS-FS network. The gels exhibit elastic shear moduli around 1000 kPa and yield stresses around 11 kPa-both values considerably exceed those obtainable by MDBS or FS alone in the same liquid. At the same time, the gel also exhibits electrochemical properties comparable to the parent liquid, including a high ionic conductivity (~5 × 10(-3) S/cm at room temperature) and a wide electrochemical stability window (up to 4.5 V).

Quasi 2D Mesoporous Carbon Microbelts Derived from Fullerene Crystals as an Electrode Material for Electrochemical Supercapacitors.

PubMed

Tang, Qin; Bairi, Partha; Shrestha, Rekha Goswami; Hill, Jonathan P; Ariga, Katsuhiko; Zeng, Haibo; Ji, Qingmin; Shrestha, Lok Kumar

2017-12-27

Fullerene C 60 microbelts were fabricated using the liquid-liquid interfacial precipitation method and converted into quasi 2D mesoporous carbon microbelts by heat treatment at elevated temperatures of 900 and 2000 °C. The carbon microbelts obtained by heat treatment of fullerene C 60 microbelts at 900 °C showed excellent electrochemical supercapacitive performance, exhibiting high specific capacitances ca. 360 F g -1 (at 5 mV s -1 ) and 290 F g -1 (at 1 A g -1 ) because of the enhanced surface area and the robust mesoporous framework structure. Additionally, the heat-treated carbon microbelt showed good rate performance, retaining 49% of capacitance at a high scan rate of 10 A g -1 . The carbon belts exhibit super cyclic stability. Capacity loss was not observed even after 10 000 charge/discharge cycles. These results demonstrate that the quasi 2D mesoporous carbon microbelts derived from a π-electron-rich carbon source, fullerene C 60 crystals, could be used as a new candidate material for electrochemical supercapacitor applications.

Operando characterization of cathodic reactions in a liquid-state lithium-oxygen micro-battery by scanning transmission electron microscopy.

PubMed

Liu, Pan; Han, Jiuhui; Guo, Xianwei; Ito, Yoshikazu; Yang, Chuchu; Ning, Shoucong; Fujita, Takeshi; Hirata, Akihiko; Chen, Mingwei

2018-02-16

Rechargeable non-aqueous lithium-oxygen batteries with a large theoretical capacity are emerging as a high-energy electrochemical device for sustainable energy strategy. Despite many efforts made to understand the fundamental Li-O 2 electrochemistry, the kinetic process of cathodic reactions, associated with the formation and decomposition of a solid Li 2 O 2 phase during charging and discharging, remains debate. Here we report direct visualization of the charge/discharge reactions on a gold cathode in a non-aqueous lithium-oxygen micro-battery using liquid-cell aberration-corrected scanning transmission electron microscopy (STEM) combining with synchronized electrochemical measurements. The real-time and real-space characterization by time-resolved STEM reveals the electrochemical correspondence of discharge/charge overpotentials to the nucleation, growth and decomposition of Li 2 O 2 at a constant current density. The nano-scale operando observations would enrich our knowledge on the underlying reaction mechanisms of lithium-oxygen batteries during round-trip discharging and charging and shed lights on the strategies in improving the performances of lithium-oxygen batteries by tailoring the cathodic reactions.

Fixed Junction Light Emitting Electrochemical Cells based on Polymerizable Ionic Liquids

NASA Astrophysics Data System (ADS)

Brown, Erin; Limanek, Austin; Bauman, James; Leger, Janelle

Organic photovoltaic (OPV) devices are of interest due to ease of fabrication, which increases their cost-effectiveness. OPV devices based on fixed-junction light emitting electrochemical cells (LECs) in particular have shown promising results. LECs are composed of a layer of polymer semiconductor blended with a salt sandwiched between two electrodes. As a forward bias is applied, the ions within the polymer separate, migrate to the electrodes, and enable electrochemical doping, thereby creating a p-n junction analog. In a fixed junction device, the ions are immobilized after the desired distribution has been established, allowing for operation under reverse bias conditions. Fixed junctions can be established using various techniques, including chemically by mixing polymerizable salts that will bond to the polymer under a forward bias. Previously we have demonstrated the use of the polymerizable ionic liquid allyltrioctylammonium allysulfonate (ATOAAS) as an effective means of creating a chemically fixed junction in an LEC. Here we present the application of this approach to the creation of photovoltaic devices. Devices demonstrate higher open circuit voltages, faster charging, and an overall improved device performance over previous chemically-fixed junction PV devices.

Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

PubMed

Byers, Joshua C; Paulose Nadappuram, Binoy; Perry, David; McKelvey, Kim; Colburn, Alex W; Unwin, Patrick R

2015-10-20

Single molecule electrochemical detection (SMED) is an extremely challenging aspect of electroanalytical chemistry, requiring unconventional electrochemical cells and measurements. Here, SMED is reported using a "quad-probe" (four-channel probe) pipet cell, fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barreled pipet and filling the open channels with electrolyte solution, and quasi-reference counter electrodes. A meniscus forms at the end of the probe covering the two working electrodes and is brought into contact with a substrate working electrode surface. In this way, a nanogap cell is produced whereby the two carbon electrodes in the pipet can be used to promote redox cycling of an individual molecule with the substrate. Anticorrelated currents generated at the substrate and tip electrodes, at particular distances (typically tens of nanometers), are consistent with the detection of single molecules. The low background noise realized in this droplet format opens up new opportunities in single molecule electrochemistry, including the use of ionic liquids, as well as aqueous solution, and the quantitative assessment and analysis of factors influencing redox cycling currents, due to a precisely known gap size.

Probing the electrochemical double layer of an ionic liquid using voltammetry and impedance spectroscopy: a comparative study of carbon nanotube and glassy carbon electrodes in [EMIM](+)[EtSO(4)](-).

PubMed

Zheng, J P; Goonetilleke, P C; Pettit, C M; Roy, D

2010-05-15

Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are compared as techniques for analyzing double layer capacitances of ionic liquids (ILs) at the surfaces of two carbon-based electrodes. These systems are relevant for energy storage supercapacitors and often are associated with unconventional electrochemical properties. Certain theoretical and experimental aspects of CV and EIS necessary for quantitative evaluation of the capacitance characteristics of such systems are explored. The experiments use 1-ethyl-3-methyl imidazolium ethylsulfate as a model IL electrolyte in combination with a porous electrode of carbon nanotubes (CNTs). The results are compared with those obtained with a nonporous glassy carbon (GC) electrode. The time is constant, and hence the power delivery characteristics of the experimental cell are affected by the electrolyte resistance and residual faradaic reactions of the IL, as well as by the spatially inhomogeneous electrode surfaces. It is shown that adequate characterization of these IL-electrode systems can be achieved by combining CV with EIS. A phenomenological framework for utilizing this combination is discussed.

Improved Performance of Ionic Liquid Supercapacitors by using Tetracyanoborate Anions

PubMed Central

Martins, Vitor L.; Rennie, Anthony J. R.; Sanchez‐Ramirez, Nedher; Torresi, Roberto M.; Hall, Peter J.

2018-01-01

Abstract Supercapacitors are energy storage devices designed to operate at higher power densities than conventional batteries, but their energy density is still too low for many applications. Efforts are made to design new electrolytes with wider electrochemical windows than aqueous or conventional organic electrolytes in order to increase energy density. Ionic liquids (ILs) with wide electrochemical stability windows are excellent candidates to be employed as supercapacitor electrolytes. ILs containing tetracyanoborate anions [B(CN)4] offer wider electrochemical stability than conventional electrolytes and maintain a high ionic conductivity (6.9 mS cm−1). Herein, we report the use of ILs containing the [B(CN)4] anion for such an application. They presented a high maximum operating voltage of 3.7 V, and two‐electrode devices demonstrate high specific capacitances even when operating at relatively high rates (ca. 20 F g−1 @ 15 A g−1). This supercapacitor stored more energy and operated at a higher power at all rates studied when compared with cells using a commonly studied ILs. PMID:29577008

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid.

PubMed

Asadi, Mohammad; Kim, Kibum; Liu, Cong; Addepalli, Aditya Venkata; Abbasi, Pedram; Yasaei, Poya; Phillips, Patrick; Behranginia, Amirhossein; Cerrato, José M; Haasch, Richard; Zapol, Peter; Kumar, Bijandra; Klie, Robert F; Abiade, Jeremiah; Curtiss, Larry A; Salehi-Khojin, Amin

2016-07-29

Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform that concurrently oxidized water in the absence of any external potential. Copyright © 2016, American Association for the Advancement of Science.

Electrochemical liquid-liquid-solid (ec-LLS) crystal growth: a low-temperature strategy for covalent semiconductor crystal growth.

PubMed

Fahrenkrug, Eli; Maldonado, Stephen

2015-07-21

This Account describes a new electrochemical synthetic strategy for direct growth of crystalline covalent group IV and III-V semiconductor materials at or near ambient temperature conditions. This strategy, which we call "electrochemical liquid-liquid-solid" (ec-LLS) crystal growth, marries the semiconductor solvation properties of liquid metal melts with the utility and simplicity of conventional electrodeposition. A low-temperature liquid metal (i.e., Hg, Ga, or alloy thereof) acts simultaneously as the source of electrons for the heterogeneous reduction of oxidized semiconductor precursors dissolved in an electrolyte as well as the solvent for dissolution of the zero-valent semiconductor. Supersaturation of the semiconductor in the liquid metal triggers eventual crystal nucleation and growth. In this way, the liquid electrolyte-liquid metal-solid crystal phase boundary strongly influences crystal growth. As a synthetic strategy, ec-LLS has several intrinsic features that are attractive for preparing covalent semiconductor crystals. First, ec-LLS does not require high temperatures, toxic precursors, or high-energy-density semiconductor reagents. This largely simplifies equipment complexity and expense. In practice, ec-LLS can be performed with only a beaker filled with electrolyte and an electrical circuit capable of supplying a defined current (e.g., a battery in series with a resistor). By this same token, ec-LLS is compatible with thermally and chemically sensitive substrates (e.g., plastics) that cannot be used as deposition substrates in conventional syntheses of covalent semiconductors. Second, ec-LLS affords control over a host of crystal shapes and sizes through simple changes in common experimental parameters. As described in detail herein, large and small semiconductor crystals can be grown both homogeneously within a liquid metal electrode and heterogeneously at the interface of a liquid metal electrode and a seed substrate, depending on the particular details chosen for ec-LLS. Third, the rate of introduction of zero-valent materials into the liquid metal is precisely gated with a high degree of resolution by the applied potential/current. The intent of this Account is to summarize the key elements of ec-LLS identified to date, first contextualizing this method with respect to other semiconductor crystal growth methods and then highlighting some unique capabilities of ec-LLS. Specifically, we detail ec-LLS as a platform to prepare Ge and Si crystals from bulk- (∼1 cm(3)), micro- (∼10(-10) cm(3)), and nano-sized (∼10(-16) cm(3)) liquid metal electrodes in common solvents at low temperature. In addition, we describe our successes in the preparation of more compositionally complex binary covalent III-V semiconductors.

Immunosensor based on electrodeposition of gold-nanoparticles and ionic liquid composite for detection of Salmonella pullorum.

PubMed

Wang, Dan; Dou, Wenchao; Zhao, Guangying; Chen, Yan

2014-11-01

In order to increase the reproducibility and stability of electrochemical immunosensor, which is a key issue for its application and popularization, an accurate and stable immunosensor for rapid detection of Salmonella pullorum (S. pullorum) was proposed in this study. The immunosensor was fabricated by modifying Screen-printed Carbon Electrode (SPCE) with electrodeposited gold nanoparticles (AuNPs), HRP-labeled anti-S. pullorum and ionic liquids (ILs) (AuNP/HRP/IL). AuNPs are electrodeposited on the working electrode surface to increase the amount of antibodies that bind to the electrode and then modified with ILs to protect the antibodies from being inactivated in the test environment and maintain their biological activity and the stability of the detection electrode. The electrochemical characteristics of the stepwise modified electrodes and the detection of S. pullorum were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). As shown in the results of the experiments, AuNPs with unique electrochemical properties as well as biocompatibility characteristics have been proven to be able to strengthen the antibody combination effectively and to increase the electrochemical response signal. In addition, a crucial assessment regarding implementation of stability and reproducibility analysis of a range of immunosensors is provided. We found that application of AuNPs/ILs in the immune modified electrodes showed obvious improvement when compared with other groups. Given their high levels of reproducibility, stability, target specificity and sensitivity, AuNPs and ILs were considered to be excellent elements for electrode modification. Copyright © 2014 Elsevier B.V. All rights reserved.

A facile electrochemical route to the preparation of uniform and monoatomic copper shells for gold nanoparticles.

PubMed

Gründer, Y; Ramasse, Q M; Dryfe, R A W

2015-02-28

Copper on gold forms a monolayer deposit via underpotential deposition. For gold particles adsorbed at a liquid-liquid interface this results in a uniform one monolayer thick shell. This approach offers a new route for the uniform functionalisation of nanoparticles and presents a way to probe fundamental processes that underlie nanoparticle synthesis.

An Electrochemical NO2 Sensor Based on Ionic Liquid: Influence of the Morphology of the Polymer Electrolyte on Sensor Sensitivity

PubMed Central

Kuberský, Petr; Altšmíd, Jakub; Hamáček, Aleš; Nešpůrek, Stanislav; Zmeškal, Oldřich

2015-01-01

A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE) and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection) were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)2]) showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride) (PVDF) in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf)2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity. PMID:26569248

Application of Ionic Liquids in Hydrometallurgy

PubMed Central

Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

2014-01-01

Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

Electrochemical reduction of carbon dioxide. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

LaConti, A.B.; Molter, T.M.; Zagaja, J.A.

1986-05-01

Many researchers have studied the electrochemical reduction of carbon dioxide and related organic species to form concentrated liquid/gaseous products in laboratory-scale hardware. Hamilton Standard has developed a high pressure SPE electrolysis cell capable of reducing carbon dioxide streams to form pure, concentrated alcohols, carboxylic acids, and other hydrocarbons. The process is unique in that the byproducts of reaction include oxygen and, under some test conditions water. In addition, a relatively simple test system was designed and constructed permitting both batch and semibatch type electrochemical reduction studies. In this study, cathode materials were developed which 1) had a characteristic high hydrogenmore » overvoltage, and 2) possessed the intrinsic affinity for electrochemical reduction of the carbon dioxide species. In addition, suitable anode electrocatalyst materials were identified. Studies involving the electrochemical reduction of carbon dioxide required the ability to identify and quantify reaction products obtained during cell evaluation. Gas chromatographic techniques were developed along with the establishment of ion chromatographic methods permitting the analysis of organic reaction products. Hamilton Standard has evaluated electrochemical carbon dioxide reduction cells under a variety of test conditions.« less

Methylxanthines: properties and determination in various objects

NASA Astrophysics Data System (ADS)

Andreeva, Elena Yu; Dmitrienko, Stanislava G.; Zolotov, Yurii A.

2012-05-01

Published data on the properties and determination of caffeine, theophylline, theobromine and some other methylxanthines in various objects are surveyed and described systematically. Different sample preparation procedures such as liquid extraction from solid matrices and liquid-liquid, supercritical fluid and solid-phase extraction are compared. The key methods of analysis including chromatography, electrophoresis, spectrometry and electrochemical methods are discussed. Examples of methylxanthine determination in plants, food products, energy beverages, pharmaceuticals, biological fluids and natural and waste waters are given. The bibliography includes 393 references.

Assessing the electrochemical performance of a supercapacitor electrode made of copper oxide and activated carbon using liquid phase plasma

NASA Astrophysics Data System (ADS)

Ki, Seo Jin; Lee, Heon; Park, Young-Kwon; Kim, Sun-Jae; An, Kay-Hyeok; Jung, Sang-Chul

2018-07-01

Successful modification of surface properties of a nanocomposite electrode is prerequisite to enhancing the overall performance of electrochemical supercapacitors. The present study was designed to describe the microstructural and electrochemical characteristics of a new composite electrode assembled by activated carbon (AC) powder (as a host) and copper precursor (as a guest) using liquid phase plasma. The fabrication processes were conducted by changing plasma discharge time from 30 to 90 min in the presence and absence of (thermal) oxidation. We observed that merging plasma and oxidation treatments raised the content of copper oxide nanoparticles precipitated (evenly) on the AC surface, along with oxygen. A mixed valence state of copper oxides (in the forms of Cuo, Cu2O, and CuO) was found in different composites with and without oxidation, where CuO and Cuo affected a specific capacitance in positive and negative ways, respectively. This led to the difference of electrochemical stability and resistance among the assembled composites. For instance, the best cycling performance was observed in the plasma-treated composite for 90 min with oxidation, whereas that of 60 min without oxidation recorded the lowest resistance. Therefore, a proper balance between the capacitance and resistance appears to be required for effective fabrication of the supercapacitor electrode, specifically in cases involving copper oxides.

Ionic liquids and oligomer electrolytes based on the B(CN)4(-) anion; ion association, physical and electrochemical properties.

PubMed

Scheers, Johan; Pitawala, Jagath; Thebault, Frederic; Kim, Jae-Kwang; Ahn, Jou-Hyeon; Matic, Aleksandar; Johansson, Patrik; Jacobsson, Per

2011-09-07

The role of B(CN)(4)(-) (Bison) as a component of battery electrolytes is addressed by investigating the ionic conductivity and phase behaviour of ionic liquids (ILs), ion association mechanisms, and the electrochemical stability and cycling properties of LiBison based electrochemical cells. For C(4)mpyrBison and C(2)mimBison ILs, and mixtures thereof, high ionic conductivities (3.4 ≤σ(ion)≤ 18 mS cm(-1)) are measured, which together with the glass transition temperatures (-80 ≤T(g)≤-76 °C) are found to shift systematically for most compositions. Unfortunately, poor solubility of LiBison in these ILs hinders their use as solvents for lithium salts, although good NaBison solubility offers an alternative application in Na(+) conducting electrolytes. The poor IL solubility of LiBison is predicted to be a result of a preferred monodentate ion association, according to first principles modelling, supported by Raman spectroscopy. The solubility is much improved in strongly Li(+) coordinating oligomers, for example polyethylene glycol dimethyl ether (PEGDME), with the practical performance tested in electrochemical cells. The electrolyte is found to be stable in Li/LiFePO(4) coin cells up to 4 V vs. Li and shows promising cycling performance, with a capacity retention of 99% over 22 cycles. This journal is © the Owner Societies 2011

Inkjet printing of nanoporous gold electrode arrays on cellulose membranes for high-sensitive paper-like electrochemical oxygen sensors using ionic liquid electrolytes.

PubMed

Hu, Chengguo; Bai, Xiaoyun; Wang, Yingkai; Jin, Wei; Zhang, Xuan; Hu, Shengshui

2012-04-17

A simple approach to the mass production of nanoporous gold electrode arrays on cellulose membranes for electrochemical sensing of oxygen using ionic liquid (IL) electrolytes was established. The approach, combining the inkjet printing of gold nanoparticle (GNP) patterns with the self-catalytic growth of these patterns into conducting layers, can fabricate hundreds of self-designed gold arrays on cellulose membranes within several hours using an inexpensive inkjet printer. The resulting paper-based gold electrode arrays (PGEAs) had several unique properties as thin-film sensor platforms, including good conductivity, excellent flexibility, high integration, and low cost. The porous nature of PGEAs also allowed the addition of electrolytes from the back cellulose membrane side and controllably produced large three-phase electrolyte/electrode/gas interfaces at the front electrode side. A novel paper-based solid-state electrochemical oxygen (O(2)) sensor was therefore developed using an IL electrolyte, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The sensor looked like a piece of paper but possessed high sensitivity for O(2) in a linear range from 0.054 to 0.177 v/v %, along with a low detection limit of 0.0075% and a short response time of less than 10 s, foreseeing its promising applications in developing cost-effective and environment-friendly paper-based electrochemical gas sensors.

Fabrication and testing of an electrochemical microcell for in situ soft X-ray microspectroscopy measurements

NASA Astrophysics Data System (ADS)

Gianoncelli, A.; Kaulich, B.; Kiskinova, M.; Mele, C.; Prasciolu, M.; Sgura, I.; Bozzini, B.

2013-03-01

In this paper we report on the fabrication and testing of a novel concept of electrochemical microcell for in-situ soft X-ray microspectroscopy in transmission. The microcell, fabricated by electron-beam lithography, implements an improved electrode design, with optimal current density distribution and minimised ohmic drop, allowing the same three-electrode electrochemical control achievable with traditional cells. Moreover standard electroanalytical measurements, such as cyclic voltammetry, can be routinely performed. As far as the electrolyte is concerned, we selected a room-temperature ionic-liquid. Some of the materials belonging to this class, in addition to a broad range of outstanding electrochemical properties, feature two highlights that are crucial for in situ, soft X-ray transmission work: spinnability, enabling accurate thickness control, and stability to UHV, allowing operation of an open cell in the analysis chamber vacuum (10-6 mbar). The cell can, of course, be used also with non-vacuum stable electrolytes in the sealed version developed in previous work in our group. In this study, the microcell designed, fabricated and tested in situ by applying an anodic polarisation to a Au electrode and following the formation of a distribution of corrosion features. This specific material combination presented in this work does not limit the cell concept, that can implement any electrodic material grown by lithography, any liquid electrolyte and any spinnable solid electrolyte.

Corrosion barriers processed by Al electroplating and their resistance against flowing Pb-15.7Li

NASA Astrophysics Data System (ADS)

Krauss, Wolfgang; Konys, Jürgen; Wulf, Sven-Erik

2014-12-01

In the HCLL blanket design, ferritic-martensitic steels are in direct contact with the flowing liquid breeder Pb-15.7Li and have to withstand severe corrosion attack. Beyond corrosion, T-permeation from the breeder into the RAFM-steels is also an important issue and has to be reduced significantly. Earlier work showed that Al-based coatings can act as barriers for both, however, applied processes e.g. HDA or VPS exhibited strong drawbacks in the past. Meanwhile new industrial relevant coating processes, using electroplating technology are under development and called ECA (electrochemical aluminization) and ECX (electrochemical deposition from ionic liquids) process. In this study electrochemically Al-coated and heat-treated Eurofer samples were tested in PICOLO loop for exposure times up to 12,000 h (ECA) and 2000 h (first results ECX) respectively to determine corrosion properties in flowing Pb-15.7Li (550 °C, 0.1 m/s). Cross section analysis afterward corrosion testing proved the ability of thin Al-based barriers made by electrochemical techniques to protect the bare Eurofer from corrosion attack even at exposure times of 12,000 h. Determined radial corrosion rates lay between 10 and 20 μm/a. First results for ECX coated samples (2000 h) revealed more homogeneous corrosion behavior of the barrier layer itself compared to ECA.

Synthesis and characterization of transition metal oxide/sulfide nanostructures for electrochemical applications

NASA Astrophysics Data System (ADS)

Yilmaz, Gamze

This thesis is essentially oriented to develop low-cost nanostructured transition metal (nickel and vanadium) oxides and sulfides with high energy density, power density and electrochemical stability via strategies of structural design, hybridization, functionalization and surface engineering. Metal oxide and metal oxide/sulfide hybrid nanostructures in several designs, including hierarchical porous nanostructures, hollow polyhedrons, nanocubes, nanoframes, octopod nanoframes, and nanocages, were synthesized to study the contribution of structural design, compositional engineering, functionalization and surface engineering to the electrochemical properties of the materials. Modulated compositional and structural features disclosed the opportunities of large accessible active sites, facile ion transport, robustness and enhanced electrical conductivity. The best electrochemical performance with merits of highest energy density (38.9 Wh kg-1), power density (7.4 kW kg-1) and electrochemical stability (90.9% after 10000 cycles) was obtained for nickel cobalt layered double hydroxide/cobalt sulfide (NiCo-LDH/Co9S8) hybrid hollow polyhedron structure.

Probing Ion Transfer across Liquid-Liquid Interfaces by Monitoring Collisions of Single Femtoliter Oil Droplets on Ultramicroelectrodes.

PubMed

Deng, Haiqiang; Dick, Jeffrey E; Kummer, Sina; Kragl, Udo; Strauss, Steven H; Bard, Allen J

2016-08-02

We describe a method of observing collisions of single femtoliter (fL) oil (i.e., toluene) droplets that are dispersed in water on an ultramicroelectrode (UME) to probe the ion transfer across the oil/water interface. The oil-in-water emulsion was stabilized by an ionic liquid, in which the oil droplet trapped a highly hydrophobic redox probe, rubrene. The ionic liquid also functions as the supporting electrolyte in toluene. When the potential of the UME was biased such that rubrene oxidation would be possible when a droplet collided with the electrode, no current spikes were observed. This implies that the rubrene radical cation is not hydrophilic enough to transfer into the aqueous phase. We show that current spikes are observed when tetrabutylammonium trifluoromethanesulfonate or tetrahexylammonium hexafluorophosphate are introduced into the toluene phase and when tetrabutylammonium perchlorate is introduced into the water phase, implying that the ion transfer facilitates electron transfer in the droplet collisions. The current (i)-time (t) behavior was evaluated quantitatively, which indicated the ion transfer is fast and reversible. Furthermore, the size of these emulsion droplets can also be calculated from the electrochemical collision. We further investigated the potential dependence on the electrochemical collision response in the presence of tetrabutylammonium trifluoromethanesulfonate in toluene to obtain the formal ion transfer potential of tetrabutylammonium across the toluene/water interface, which was determined to be 0.754 V in the inner potential scale. The results yield new physical insights into the charge balance mechanism in emulsion droplet collisions and indicate that the electrochemical collision technique can be used to probe formal ion transfer potentials between water and solvents with very low (ε < 5) dielectric constants.

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

PubMed Central

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; Cullen, David A.; Toops, Todd J.; Green, Johney B.; Mench, Matthew M.; Zhang, Feng-Yuan

2016-01-01

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. This discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices. PMID:28138516

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

DOE PAGES

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; ...

2016-11-18

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

Direct imaging of nanobubble Ostwald ripening using graphene liquid cell TEM

NASA Astrophysics Data System (ADS)

Xu, Cong; Chen, Qian; Granick, Steve

We directly image the growth, morphology evolution and interaction dynamics of gas nanobubbles in a thin liquid, which are relevant to many materials and electrochemical processes. Using the recently emergent liquid phase transmission electron microscopy (TEM), we resolve the dynamics of nanobubbles in situ at nm resolution in real time. We find that nanobubbles grow through an Ostwald ripening-like process, where adjacent bubbles stochastically fluctuate to disappear or enlarge. Capability of feature tracking enables us to characterize the motions and shape fluctuations of nanobubbles, providing insights into the gas-liquid interfacial fluctuations explored at the nanoscale.

Electrochemical oxygen intercalation into Sr2IrO4

NASA Astrophysics Data System (ADS)

Fruchter, L.; Brouet, V.; Colson, D.; Moussy, J.-B.; Forget, A.; Li, Z. Z.

2018-01-01

Oxygen was electrochemically intercalated into Sr2IrO4 sintered samples, single crystals and a thin film. We estimate the diffusion length to a few μm and the concentration of the intercalated oxygen to δ ≃ 0.01. The latter is thus much smaller than for the cuprate and nickelate parent compounds, for which δ > 0.1 is obtained, which could be a consequence of larger steric effects. The influence of the oxygen doping state on resistivity is small, indicating also a poor charge transfer to the conduction band. It is shown that electrochemical intercalation of oxygen may also contribute to doping, when gating thin films with ionic liquid in the presence of water.

Principles and Applications of Solid Polymer Electrolyte Reactors for Electrochemical Hydrodehalogenation of Organic Pollutants

NASA Astrophysics Data System (ADS)

Cheng, Hua; Scott, Keith

The ability to re-cycle halogenated liquid wastes, based on electrochemical hydrodehalogenation (EHDH), will provide a significant economic advantage and will reduce the environmental burden in a number of processes. The use of a solid polymer electrolyte (SPE) reactor is very attractive for this purpose. Principles and features of electrochemical HDH technology and SPE EHDH reactors are described. The SPE reactor enables selective dehalogenation of halogenated organic compounds in both aqueous and non-aqueous media with high current efficiency and low energy consumption. The influence of operating conditions, including cathode material, current density, reactant concentration and temperature on the HDH process and its stability are examined.

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2016-07-05

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at least 5 mAh/cm.sup.2 at a C-rate of C/2.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at leastmore » 5 mAh/cm.sup.2 at a C-rate of C/2.« less

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2015-11-10

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at least 5 mAh/cm.sup.2 at a C-rate of C/2.

A study on the involvement of GABA-transaminase in MCT induced pulmonary hypertension.

PubMed

Lingeshwar, Poorella; Kaur, Gurpreet; Singh, Neetu; Singh, Seema; Mishra, Akanksha; Shukla, Shubha; Ramakrishna, Rachumallu; Laxman, Tulsankar Sachin; Bhatta, Rabi Sankar; Siddiqui, Hefazat H; Hanif, Kashif

2016-02-01

Increased sympathetic nervous system (SNS) activity is associated with cardiovascular diseases but its role has not been completely explored in pulmonary hypertension (PH). Increased SNS activity is distinguished by elevated level of norepinephrine (NE) and activity of γ-Amino butyric acid Transminase (GABA-T) which degrades GABA, an inhibitory neurotransmitter within the central and peripheral nervous system. Therefore, we hypothesized that GABA-T may contribute in pathophysiology of PH by modulating level of GABA and NE. The effect of daily oral administration of GABA-T inhibitor, Vigabatrin (GVG, 50 and 75 mg/kg/day, 35 days) was studied following a single subcutaneous administration of monocrotaline (MCT, 60 mg/kg) in male SD rats. The pressure and hypertrophy of right ventricle (RV), oxidative stress, inflammation, pulmonary vascular remodelling were assessed after 35 days in MCT treated rats. The expression of GABA-T and HIF-1α was studied in lung tissue. The levels of plasma NE (by High performance liquid chromatography coupled with electrochemical detector; HPLC-ECD) and lung GABA (by liquid chromatography-mass spectrometry) were also estimated. GVG at both doses significantly attenuated increased in pressure (35.82 ± 4.80 mm Hg, p < 0.001; 28.37 ± 3.32 mm Hg, p < 0.001 respectively) and hypertrophy of RV, pulmonary vascular remodelling, oxidative stress and inflammation in lungs of MCT exposed rats. GVG also reduced the expression of GABA-T and HIF-1α in MCT treated rats. Increased NE level and decreased GABA level was also reversed by GVG in MCT exposed rats. GABA-T plays an important role in PH by modulating SNS activity and may be considered as a therapeutic target in PH. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrochemistry of poly(3,4-ethylenedioxythiophene)-polyaniline/ Prussian blue electrochromic devices containing an ionic liquid based gel electrolyte film.

PubMed

Deepa, Melepurath; Awadhia, Arvind; Bhandari, Shweta

2009-07-21

Electrochromic devices based on poly(3,4-ethylenedioxythiophene) (PEDOT) as the cathodic coloring electrode and polyaniline (PANI) or Prussian blue (PB) as the counter electrode containing a highly conductive, self-supporting, distensible and transparent polymer-gel electrolyte film encapsulating an ionic liquid, 1-butyl-1-methylpyrrolidiniumbis-(trifluoromethylsulfonyl)imide, have been fabricated. Polarization, charge transfer and diffusion processes control the electrochemistry of the functional electrodes during coloration and bleaching and these phenomena differ when PEDOT and PANI/PB were employed alternately as working electrodes. While the electrochemical impedance response shows good similitude for PEDOT and PANI electrodes, the responses of PEDOT and PB were significantly different in the PEDOT-PB device, especially during reduction of PB, wherein the overall amplitude of the impedance response is enormous. Large values of the coloration efficiency maxima of 281 cm2 C(-1) (lambda = 583 nm) and 274 cm2 C(-1) (lambda = 602 nm), achieved at -1.0 and -1.5 V for the PEDOT PANI and PEDOT-PB devices have been correlated to the particularly low magnitude of charge transfer resistance and high polarization capacitance operative at the PEDOT ionic liquid based electrolyte interface at these dc potentials, thus allowing facile ion-transport and consequently resulting in enhanced absorption modulation. Moderately fast switching kinetics and the ability of these devices to sustain about 2500 cycles of clear-to-dark and dark-to-clear without incurring major losses in the optical contrast, along with the ease of construction of these cells in terms of high scalability and reproducibility of the synthetic procedure for fabrication of the electrochromic films and the ionic liquid based gel electrolyte film, are indicators of the promise these devices hold for practical applications like electrochromic windows and displays.

In operando evidence of deoxygenation in ionic liquid gating of YBa2Cu3O7-X

PubMed Central

Perez-Muñoz, Ana M.; Schio, Pedro; Poloni, Roberta; Fernandez-Martinez, Alejandro; Rivera-Calzada, Alberto; Salas-Colera, Eduardo; Kinney, Joseph; Leon, Carlos; Santamaria, Jacobo; Garcia-Barriocanal, Javier; Goldman, Allen M.

2017-01-01

Field-effect experiments on cuprates using ionic liquids have enabled the exploration of their rich phase diagrams [Leng X, et al. (2011) Phys Rev Lett 107(2):027001]. Conventional understanding of the electrostatic doping is in terms of modifications of the charge density to screen the electric field generated at the double layer. However, it has been recently reported that the suppression of the metal to insulator transition induced in VO2 by ionic liquid gating is due to oxygen vacancy formation rather than to electrostatic doping [Jeong J, et al. (2013) Science 339(6126):1402–1405]. These results underscore the debate on the true nature, electrostatic vs. electrochemical, of the doping of cuprates with ionic liquids. Here, we address the doping mechanism of the high-temperature superconductor YBa2Cu3O7-X (YBCO) by simultaneous ionic liquid gating and X-ray absorption experiments. Pronounced spectral changes are observed at the Cu K-edge concomitant with the superconductor-to-insulator transition, evidencing modification of the Cu coordination resulting from the deoxygenation of the CuO chains, as confirmed by first-principles density functional theory (DFT) simulations. Beyond providing evidence of the importance of chemical doping in electric double-layer (EDL) gating experiments with superconducting cuprates, our work shows that interfacing correlated oxides with ionic liquids enables a delicate control of oxygen content, paving the way to novel electrochemical concepts in future oxide electronics. PMID:28028236

In operando evidence of deoxygenation in ionic liquid gating of YBa2Cu3O7-X.

PubMed

Perez-Muñoz, Ana M; Schio, Pedro; Poloni, Roberta; Fernandez-Martinez, Alejandro; Rivera-Calzada, Alberto; Cezar, Julio C; Salas-Colera, Eduardo; Castro, German R; Kinney, Joseph; Leon, Carlos; Santamaria, Jacobo; Garcia-Barriocanal, Javier; Goldman, Allen M

2017-01-10

Field-effect experiments on cuprates using ionic liquids have enabled the exploration of their rich phase diagrams [Leng X, et al. (2011) Phys Rev Lett 107(2):027001]. Conventional understanding of the electrostatic doping is in terms of modifications of the charge density to screen the electric field generated at the double layer. However, it has been recently reported that the suppression of the metal to insulator transition induced in VO 2 by ionic liquid gating is due to oxygen vacancy formation rather than to electrostatic doping [Jeong J, et al. (2013) Science 339(6126):1402-1405]. These results underscore the debate on the true nature, electrostatic vs. electrochemical, of the doping of cuprates with ionic liquids. Here, we address the doping mechanism of the high-temperature superconductor YBa 2 Cu 3 O 7-X (YBCO) by simultaneous ionic liquid gating and X-ray absorption experiments. Pronounced spectral changes are observed at the Cu K-edge concomitant with the superconductor-to-insulator transition, evidencing modification of the Cu coordination resulting from the deoxygenation of the CuO chains, as confirmed by first-principles density functional theory (DFT) simulations. Beyond providing evidence of the importance of chemical doping in electric double-layer (EDL) gating experiments with superconducting cuprates, our work shows that interfacing correlated oxides with ionic liquids enables a delicate control of oxygen content, paving the way to novel electrochemical concepts in future oxide electronics.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-01-23

A method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Advanced double layer capacitors

NASA Technical Reports Server (NTRS)

Sarangapani, S.; Lessner, P.; Forchione, J.; Griffith, A.; Laconti, A. B.

1989-01-01

Work was conducted that could lead to a high energy density electrochemical capacitor, completely free of liquid electrolyte. A three-dimensional RuO sub x-ionomer composite structure has been successfully formed and appears to provide an ionomer ionic linkage throughout the composite structure. Capacitance values of approximately 0.6 F/sq cm were obtained compared with 1 F/sq cm when a liquid electrolyte is used with the same configuration.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-02-13

A system and method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-05-15

A system and method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Electrochemically Reduced Graphene Oxide Multilayer Films as Efficient Counter Electrode for Dye-Sensitized Solar Cells

PubMed Central

Xu, Xiaobao; Huang, Dekang; Cao, Kun; Wang, Mingkui; Zakeeruddin, Shaik M.; Grätzel, Michael

2013-01-01

We report on a new counter electrode for dye-sensitized solar cells (DSCs), which is prepared using layer-by-layer assembly of negatively charged graphene oxide and positively charged poly (diallyldimethylammonium chloride) followed by an electrochemical reduction procedure. The DSC devises using the heteroleptic Ru complex C106TBA as sensitizer and this new counter electrode reach power conversion efficiencies of 9.5% and 7.6% in conjunction with low volatility and solvent free ionic liquid electrolytes, respectively. The new counter electrode exhibits good durability (60°C for 1000 h in a solar simulator, 100 mW cm−2) during the accelerated tests when used in combination with an ionic liquid electrolyte. This work identifies a new class of electro-catalysts with potential for low cost photovoltaic devices. PMID:23508212

Electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-01-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-09-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Ionic liquid-assisted solvothermal synthesis of hollow Mn2O3 anode and LiMn2O4 cathode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

He, Xin; Wang, Jun; Jia, Haiping; Kloepsch, Richard; Liu, Haidong; Beltrop, Kolja; Li, Jie

2015-10-01

Mn-based Mn2O3 anode and LiMn2O4 cathode materials are prepared by a solvothermal method combined with post annealing process. Environmentally friendly ionic liquid 1-Butyl-3-methylimidazolium tetrafluoroborate as both structure-directing agent and fluorine source is used to prepare hollow polyhedron MnF2 precursor. Both target materials Mn2O3 anode and LiMn2O4 cathode have the morphology of the MnF2 precursor. The Mn2O3 anode using carboxymethyl cellulose as binder could deliver slight better electrochemical performance than the one using poly (vinyldifluoride) as binder. The former has an initial charge capacity of 800 mAh g-1 at a current density of 101.8 mA g-1, and exhibits no obvious capacity decay for 150 cycles at 101.8 mA g-1. The LiMn2O4 cathode material prepared with molten salt assistant could display much better electrochemical performance than the one prepared without molten salt assistance. In particular, it has an initial discharge capacity of 117.5 mAh g-1 at a current density of 0.5C and good rate capability. In the field of lithium ion batteries, both the Mn2O3 anode and LiMn2O4 cathode materials could exhibit enhanced electrochemical performance due to the well formed morphology based on the ionic liquid-assisted solvothermal method.

A facile synthesis of 3D NiFe2O4 nanospheres anchored on a novel ionic liquid modified reduced graphene oxide for electrochemical sensing of ledipasvir: Application to human pharmacokinetic study.

PubMed

El-Wekil, Mohamed M; Mahmoud, Ashraf M; Alkahtani, Saad A; Marzouk, Adel A; Ali, Ramadan

2018-06-30

Novel and sensitive electrochemical sensor was fabricated for the assay of anti-HCV ledipasvir (LEDV) in different matrices. The designed sensor was based on 3D spinel ferromagnetic NiFe 2 O 4 nanospheres and reduced graphene oxide (RGO) supported by morpholinium acid sulphate (MHS), as an ionic liquid (RGO/NSNiFe 2 O 4 /MHS). This sensor design was assigned to synergistically tailor the unique properties of nanostructured ferrites, RGO, and ionic liquid to maximize the sensor response. Electrode modification prevented aggregation of NiFe 2 O 4, increasing electroactive surface area and allowed remarkable electro-catalytic oxidation of LEDV with an enhanced oxidation response. Differential pulse voltammetry was used for detection LEDV in complex matrices whereas; cyclic voltammetry and other techniques were employed to characterize the developed sensor properties. All experimental factors regarding sensor fabrication and chemical sensing properties were carefully studied and optimized. Under the optimum conditions, the designated sensor displayed a wide linear range (0.4-350 ng mL -1 ) with LOD of 0.133 ng mL -1 . Additionally, the proposed sensor demonstrated good selectivity, stability and reproducibility, enabling the quantitative detection of LEDV in Harvoni ® tablets, human plasma and in a pharmacokinetic study. Our findings suggest that the developed sensor is a potential prototype material for fabrication of high-performance electrochemical sensors. Copyright © 2018 Elsevier B.V. All rights reserved.

Direct electrochemistry and electrocatalysis of hemoglobin in graphene oxide and ionic liquid composite film.

PubMed

Sun, Wei; Gong, Shixing; Shi, Fan; Cao, Lili; Ling, Luyang; Zheng, Weizhe; Wang, Wencheng

2014-07-01

In this paper a novel sensing platform based on graphene oxide (GO), ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate and Nafion for the immobilization of hemoglobin (Hb) was adopted with a carbon ionic liquid electrode (CILE) as the substrate electrode, which was denoted as Nafion/Hb-GO-IL/CILE. Spectroscopic results suggested that Hb molecules were not denatured in the composite. A pair of well-defined redox peaks appeared on the cyclic voltammogram, which was attributed to the realization of direct electron transfer of Hb on the electrode. Electrochemical behaviors of Hb entrapped in the film were carefully investigated by cyclic voltammetry with the electrochemical parameters calculated. Based on the catalytic ability of the immobilized Hb, Nafion/Hb-GO-IL/CILE exhibited excellent electrocatalytic behavior towards the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.01 to 40.0mM with the detection limit as 3.12 μM (3σ), H2O2 in the concentration range from 0.08 to 635.0 μM with the detection limit as 0.0137 μM (3σ) and NaNO2 in the concentration range from 0.5 to 800.0 μM with the detection limit as 0.0104 μM (3σ). So the proposed bioelectrode could be served as a new third-generation electrochemical sensor without mediator. Copyright © 2014 Elsevier B.V. All rights reserved.

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

DOE PAGES

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; ...

2015-05-07

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

[Simultaneous determination of four compounds in Sanjing Shuanghuanglian Oral Liquid by high performance liquid chromatography-diode array detection-electrochemical detection].

PubMed

Liu, Lin; Suo, Zhirong; Zheng, Jianbin

2006-05-01

Chlorogenic acid, caffeic acid, baicalin and luteolin in Sanjing Shuanghuanglian Oral Liquid were simultaneously detected and identified using a high performance liquid chromatography coupled with diode array detection and electrochemical detection (HPLC-DAD-ECD). The separation was performed on a Zorbax SB-C18 column (150 mm x 4.6 mm i. d., 5.0 microm). The mobile phase consisted of (A) methanol and (B) methanol-water-acetic acid (50: 50: 1, v/v/v) using a linear gradient elution of 2%A-3%A at 0-3 min, 3%A-25%A at 3-15 min, 25%A-80%A at 15-20 min. The flow rate was 0.8 mL/min. The DAD detection was used at 275 nm. The ECD detection was done at 0.7 V. The column thermostat set at 30 degrees C. The limits of detection of the 4 compounds were 1 mg/L for chlorogenic acid, 0.2 mg/L for caffeic acid, 9 mg/L for baicalin, 7 mg/L for luteolin. The average recoveries were between 96.6%-99.6% with relative standard deviations (RSDs) of 2.5%-4.1%. The method is simple, rapid, reproducible and accurate. It can be used for the routine analysis of the four compounds in Shuanghuanglian Oral Liquid.

Size and Electronic Modulation of Iridium Nanoparticles on Nitrogen Functionalized Carbon toward Advanced Electrocatalysts for Alkaline Water Splitting.

PubMed

Wang, Hua; Ming, Mei; Hu, Min; Xu, Caili; Wang, Yi; Zhang, Yun; Gao, Daojiang; Bi, Jian; Fan, Guangyin; Hu, Jin-Song

2018-06-14

Developing efficient catalytic materials for electrochemical water splitting is important. Herein, uniformly dispersed and size-controllable iridium (Ir) nanoparticles (NPs) were prepared using a nitrogen-functionalized carbon (Ir/CN) as the support. We found that nitrogen function can simultaneously modulate the size of Ir NPs to substantially enhance the catalytically active sites and adjust the electronic structure of Ir, thereby promoting electrocatalytic activity for water splitting. Consequently, the as-synthesized Ir/CN shows excellent electrocatalytic performance with overpotentials of 12 and 265 mV for hydrogen and oxygen evolution reactions in basic medium, respectively. These findings may pave a way for designing and synthesizing other similar materials as efficient catalysts for electrochemical water splitting.

Acoustic Liquid Manipulation Used to Enhance Electrochemical Processes

NASA Technical Reports Server (NTRS)

Oeftering, Richard C.

2005-01-01

Working in concert with the NASA Technology Transfer and Partnership Office, the Great Lakes Industrial Technology Center, and Alchemitron Corporation of Elgin, Illinois, the NASA Glenn Research Center has applied nonlinear acoustic principles to industrial applications. High-intensity ultrasonic beam techniques employ the effects of acoustic radiation pressure and acoustic streaming to manipulate the behavior of liquids. This includes propelling liquids, moving bubbles, and ejecting liquids as droplets and fountains. Since these effects can be accomplished without mechanical pumps or moving parts, we are exploring how these techniques could be used to manipulate liquids in space applications. Some of these acoustic techniques could be used both in normal Earth gravity and in the microgravity of space.

Note: Simple hysteresis parameter inspector for camera module with liquid lens

NASA Astrophysics Data System (ADS)

Chen, Po-Jui; Liao, Tai-Shan; Hwang, Chi-Hung

2010-05-01

A method to inspect hysteresis parameter is presented in this article. The hysteresis of whole camera module with liquid lens can be measured rather than a single lens merely. Because the variation in focal length influences image quality, we propose utilizing the sharpness of images which is captured from camera module for hysteresis evaluation. Experiments reveal that the profile of sharpness hysteresis corresponds to the characteristic of contact angle of liquid lens. Therefore, it can infer that the hysteresis of camera module is induced by the contact angle of liquid lens. An inspection process takes only 20 s to complete. Thus comparing with other instruments, this inspection method is more suitable to integrate into the mass production lines for online quality assurance.

Switchable silver mirrors with long memory effects† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc01912a Click here for additional data file. Click here for additional data file.

PubMed Central

Park, Chihyun; Seo, Seogjae; Shin, Haijin; Sarwade, Bhimrao D.; Na, Jongbeom

2015-01-01

An electrochemically stable and bistable switchable mirror was achieved for the first time by introducing (1) a thiol-modified indium tin oxide (ITO) electrode for the stabilization of the metallic film and (2) ionic liquids as an anion-blocking layer, to achieve a long memory effect. The growth of the metallic film was denser and faster at the thiol-modified ITO electrode than at a bare ITO electrode. The electrochemical stability of the metallic film on the thiol-modified ITO was enhanced, maintaining the metallic state without rupture. In the voltage-off state, the metal film maintained bistability for a long period (>2 h) when ionic liquids were introduced as electrolytes for the switchable mirror. The electrical double layer in the highly viscous ionic liquid electrolyte seemed to effectively form a barrier to the bromide ions, to protect the metal thin film from them when in the voltage-off state. PMID:28936310

Comparing Triflate and Hexafluorophosphate Anions of Ionic Liquids in Polymer Electrolytes for Supercapacitor Applications.

PubMed

Liew, Chiam-Wen; Ramesh, S

2014-05-21

Two different ionic liquid-based biopolymer electrolyte systems were prepared using a solution casting technique. Corn starch and lithium hexafluorophosphate (LiPF₆) were employed as polymer and salt, respectively. Additionally, two different counteranions of ionic liquids, viz. 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF₆) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (also known as 1-butyl-3-methylimidazolium triflate) (BmImTf) were used and studied in this present work. The maximum ionic conductivities of (1.47 ± 0.02) × 10 -4 and (3.21 ± 0.01) × 10 -4 S∙cm -1 were achieved with adulteration of 50 wt% of BmImPF₆ and 80 wt% of BmImTf, respectively at ambient temperature. Activated carbon-based electrodes were prepared and used in supercapacitor fabrication. Supercapacitors were then assembled using the most conducting polymer electrolyte from each system. The electrochemical properties of the supercapacitors were then analyzed. The supercapacitor containing the triflate-based biopolymer electrolyte depicted a higher specific capacitance with a wider electrochemical stability window compared to that of the hexafluorophosphate system.

Comparing Triflate and Hexafluorophosphate Anions of Ionic Liquids in Polymer Electrolytes for Supercapacitor Applications

PubMed Central

Liew, Chiam-Wen; Ramesh, S.

2014-01-01

Two different ionic liquid-based biopolymer electrolyte systems were prepared using a solution casting technique. Corn starch and lithium hexafluorophosphate (LiPF6) were employed as polymer and salt, respectively. Additionally, two different counteranions of ionic liquids, viz. 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (also known as 1-butyl-3-methylimidazolium triflate) (BmImTf) were used and studied in this present work. The maximum ionic conductivities of (1.47 ± 0.02) × 10−4 and (3.21 ± 0.01) × 10−4 S·cm−1 were achieved with adulteration of 50 wt% of BmImPF6 and 80 wt% of BmImTf, respectively at ambient temperature. Activated carbon-based electrodes were prepared and used in supercapacitor fabrication. Supercapacitors were then assembled using the most conducting polymer electrolyte from each system. The electrochemical properties of the supercapacitors were then analyzed. The supercapacitor containing the triflate-based biopolymer electrolyte depicted a higher specific capacitance with a wider electrochemical stability window compared to that of the hexafluorophosphate system. PMID:28788662

Conductivity Scaling Relationships of Nanostructured Membranes based on Hydrated Protic Polymerized Ionic Liquids: Effect of Domain Spacing

NASA Astrophysics Data System (ADS)

Sanoja, Gabriel; Popere, Bhooshan; Beckingham, Bryan; Evans, Christopher; Lynd, Nathaniel; Segalman, Rachel

Elucidating the relationship between chemical structure, morphology, and ionic conductivity is essential for designing novel materials for electrochemical applications. In this work, the effect of lamellar domain spacing (d) on ionic conductivity (σ) is investigated for a model system of hydrated block copolymer based on a protic polymerized ionic liquid. We present a strategy that allows for the synthesis of a well-defined series of narrowly dispersed PS- b - PIL with constant volume fraction of ionic liquid moieties (fIL ~ 0.39). These materials self-assemble into ordered lamellar morphologies with variable domain spacing (23-59 nm) as demonstrated by SAXS. PS- b - PIL membranes exhibit ionic conductivities above 10-4 S/cm at room temperature, which are independent of domain spacing. The conductivity scaling relationship demonstrated in this work suggests that a mechanically robust membrane can be designed without compromising its ability to transport ions. In addition, PIL-based membranes exhibit lower water uptake (λ = 10) in comparison with many proton-conducting systems reported elsewhere. The low water content of these materials makes them promising candidates for solar-fuels electrochemical devices.

A lithium superionic conductor.

PubMed

Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, Akio

2011-07-31

Batteries are a key technology in modern society. They are used to power electric and hybrid electric vehicles and to store wind and solar energy in smart grids. Electrochemical devices with high energy and power densities can currently be powered only by batteries with organic liquid electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems very complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10(-2) S cm(-1)) only at 50-80 °C, which is one order of magnitude lower than those of organic liquid electrolytes. Here, we report a lithium superionic conductor, Li(10)GeP(2)S(12) that has a new three-dimensional framework structure. It exhibits an extremely high lithium ionic conductivity of 12 mS cm(-1) at room temperature. This represents the highest conductivity achieved in a solid electrolyte, exceeding even those of liquid organic electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochemical properties (high conductivity and wide potential window).

High capacitance of coarse-grained carbide derived carbon electrodes

DOE PAGES

Dyatkin, Boris; Gogotsi, Oleksiy; Malinovskiy, Bohdan; ...

2016-01-01

Here, we report exceptional electrochemical properties of supercapacitor electrodes composed of large, granular carbide-derived carbon (CDC) particles. We synthesized 70–250 μm sized particles with high surface area and a narrow pore size distribution, using a titanium carbide (TiC) precursor. Electrochemical cycling of these coarse-grained powders defied conventional wisdom that a small particle size is strictly required for supercapacitor electrodes and allowed high charge storage densities, rapid transport, and good rate handling ability. Moreover, the material showcased capacitance above 100 F g -1 at sweep rates as high as 250 mV s -1 in organic electrolyte. 250–1000 micron thick dense CDCmore » films with up to 80 mg cm -2 loading showed superior areal capacitances. The material significantly outperformed its activated carbon counterpart in organic electrolytes and ionic liquids. Furthermore, large internal/external surface ratio of coarse-grained carbons allowed the resulting electrodes to maintain high electrochemical stability up to 3.1 V in ionic liquid electrolyte. In addition to presenting novel insights into the electrosorption process, these coarse-grained carbons offer a pathway to low-cost, high-performance implementation of supercapacitors in automotive and grid-storage applications.« less

High capacitance of coarse-grained carbide derived carbon electrodes

NASA Astrophysics Data System (ADS)

Dyatkin, Boris; Gogotsi, Oleksiy; Malinovskiy, Bohdan; Zozulya, Yuliya; Simon, Patrice; Gogotsi, Yury

2016-02-01

We report exceptional electrochemical properties of supercapacitor electrodes composed of large, granular carbide-derived carbon (CDC) particles. Using a titanium carbide (TiC) precursor, we synthesized 70-250 μm sized particles with high surface area and a narrow pore size distribution. Electrochemical cycling of these coarse-grained powders defied conventional wisdom that a small particle size is strictly required for supercapacitor electrodes and allowed high charge storage densities, rapid transport, and good rate handling ability. The material showcased capacitance above 100 F g-1 at sweep rates as high as 250 mV s-1 in organic electrolyte. 250-1000 micron thick dense CDC films with up to 80 mg cm-2 loading showed superior areal capacitances. The material significantly outperformed its activated carbon counterpart in organic electrolytes and ionic liquids. Furthermore, large internal/external surface ratio of coarse-grained carbons allowed the resulting electrodes to maintain high electrochemical stability up to 3.1 V in ionic liquid electrolyte. In addition to presenting novel insights into the electrosorption process, these coarse-grained carbons offer a pathway to low-cost, high-performance implementation of supercapacitors in automotive and grid-storage applications.

Electrochemical preparation of nanostructured lanthanum using lanthanum chloride as a precursor in 1-butyl-3-methylimidazolium dicyanamide ionic liquid.

PubMed

Zhang, Q B; Yang, C; Hua, Y X; Li, Y; Dong, P

2015-02-14

Nanostructured lanthanum was electrochemically prepared on a platinum (Pt) substrate in the room temperature ionic liquid 1-butyl-3-methylimidazolium dicyanamide (BMI-DCA) containing anhydrous LaCl3 at 333 K. The electrochemical reduction behavior of La(iii) was investigated using cyclic voltammetry and chronoamperometry techniques. Cyclic voltammogram revealed that the reduction of La(iii) in BMI-DCA involved an irreversible process controlled by diffusion. Chronoamperometric transient analysis confirmed the diffusion controlled electrodeposition process with the diffusion coefficient of La(iii) species in the range of 10(-10) cm(2) s(-1). The strong complexing capability of DCA(-) anions facilitated the displacement of chloride ligands and induced the solubility of LaCl3. The subsequent coordination of La(iii) and DCA(-) anions forming [La(DCA)4](-) complex anions was monitored by designing amperometric titration experiments. Potentiostatically deposited La-deposits with different nanostructures were characterized by SEM, XRD and XPS analyses. The electrodeposition potential was found to play an important role in controlling the nucleation and growth kinetics of the nanocrystal during the electrodeposition process. Depending on the deposition potential, metallic lanthanum with either nanoparticles or nanoporous structures was obtained.

High performance supercapacitor from activated carbon derived from waste orange skin

NASA Astrophysics Data System (ADS)

Ahmed, Sultan; Hussain, S.; Ahmed, Ahsan; Rafat, M.

2018-05-01

Activated carbon due to its inherent properties such as large surface area and low cost is most frequently used electrode material for supercapacitor. Activated carbon has been previously derived from various biomass such as coconut shell, coffee bean etc. Herein, we report the synthesis of activated carbon from waste orange skin. The material was synthesized employing chemical activation method and the success of synthesis was confirmed by its physical and electrochemical properties. The physical properties of the as-prepared sample were studied using the techniques of XRD, SEM, Raman spectroscopy and N2 adsorption/desorption analysis while its electrochemical properties were studied in two-electrode assembly using liquid electrolyte (consisting of 1 M solution of LiTFSI dispersed in ionic liquid EMITFSI) and employing the techniques of cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge- discharge. The synthesized sample of activated carbon exhibits high specific capacitance of 115 F g-1 at 10 mV s-1. Also, the activated carbon electrode shows the retention of ˜75% in initial capacitance value for more than 2000 initial cycles, indicating the as-prepared activated carbon can be profitably used as electrode material for energy storage devices.

Methane–oxygen electrochemical coupling in an ionic liquid: a robust sensor for simultaneous quantification†

PubMed Central

Wang, Zhe; Guo, Min; Baker, Gary A.; Stetter, Joseph R.; Lin, Lu; Mason, Andrew J.

2017-01-01

Current sensor devices for the detection of methane or natural gas emission are either expensive and have high power requirements or fail to provide a rapid response. This report describes an electrochemical methane sensor utilizing a non-volatile and conductive pyrrolidinium-based ionic liquid (IL) electrolyte and an innovative internal standard method for methane and oxygen dual-gas detection with high sensitivity, selectivity, and stability. At a platinum electrode in bis(trifluoromethylsulfonyl)imide (NTf2)-based ILs, methane is electro-oxidized to produce CO2 and water when an oxygen reduction process is included. The in situ generated CO2 arising from methane oxidation was shown to provide an excellent internal standard for quantification of the electrochemical oxygen sensor signal. The simultaneous quantification of both methane and oxygen in real time strengthens the reliability of the measurements by cross-validation of two ambient gases occurring within a single sample matrix and allows for the elimination of several types of random and systematic errors in the detection. We have also validated this IL-based methane sensor employing both conventional solid macroelectrodes and flexible microfabricated electrodes using single- and double-potential step chronoamperometry. PMID:25093213

The electrode/ionic liquid interface: electric double layer and metal electrodeposition.

PubMed

Su, Yu-Zhuan; Fu, Yong-Chun; Wei, Yi-Min; Yan, Jia-Wei; Mao, Bing-Wei

2010-09-10

The last decade has witnessed remarkable advances in interfacial electrochemistry in room-temperature ionic liquids. Although the wide electrochemical window of ionic liquids is of primary concern in this new type of solvent for electrochemistry, the unusual bulk and interfacial properties brought about by the intrinsic strong interactions in the ionic liquid system also substantially influence the structure and processes at electrode/ionic liquid interfaces. Theoretical modeling and experimental characterizations have been indispensable in reaching a microscopic understanding of electrode/ionic liquid interfaces and in elucidating the physics behind new phenomena in ionic liquids. This Minireview describes the status of some aspects of interfacial electrochemistry in ionic liquids. Emphasis is placed on high-resolution and molecular-level characterization by scanning tunneling microscopy and vibrational spectroscopies of interfacial structures, and the initial stage of metal electrodeposition with application in surface nanostructuring.

Hybrid supercapacitors for reversible control of magnetism

PubMed Central

Molinari, Alan; Leufke, Philipp M.; Reitz, Christian; Dasgupta, Subho; Witte, Ralf; Kruk, Robert; Hahn, Horst

2017-01-01

Electric field tuning of magnetism is one of the most intensely pursued research topics of recent times aiming at the development of new-generation low-power spintronics and microelectronics. However, a reversible magnetoelectric effect with an on/off ratio suitable for easy and precise device operation is yet to be achieved. Here we propose a novel route to robustly tune magnetism via the charging/discharging processes of hybrid supercapacitors, which involve electrostatic (electric-double-layer capacitance) and electrochemical (pseudocapacitance) doping. We use both charging mechanisms—occurring at the La0.74Sr0.26MnO3/ionic liquid interface to control the balance between ferromagnetic and non-ferromagnetic phases of La1−xSrxMnO3 to an unprecedented extent. A magnetic modulation of up to ≈33% is reached above room temperature when applying an external potential of only about 2.0 V. Our case study intends to draw attention to new, reversible physico-chemical phenomena in the rather unexplored area of magnetoelectric supercapacitors. PMID:28489078

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C.A.; Xu, K.; Liu, C.

1996-01-16

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100 C or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors. 4 figs.

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C. Austen; Xu, Kang; Liu, Changle

1996-01-01

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors.

Liquid Lens module with wide field-of-view and variable focal length

NASA Astrophysics Data System (ADS)

Seo, Sang Won; Han, Seungoh; Seo, Jun Ho; Choi, Woo Bum; Sung, Man Young

2010-12-01

A novel wide angle and variable-focus imaging module based on a miniaturized liquid lens is presented for capsule endoscopy applications. For these applications, it is desirable to have features such as a wide field of view (FOV), variable focus, small size, and low power consumption, thereby taking full advantage of the miniaturized liquid lens. The proposed imaging module has three aspheric plastic lenses for a wide FOV, and one liquid lens that can change the focal length by as much as 24.5 cm with a bias voltage difference of 23 Vrms for variable focusing. The assembled lens module has an overall length of 8.4 mm and a FOV of 120.5°. The realized imaging module including the proposed lenses is small enough to be inserted into a capsule endoscope, and it is expected to improve the diagnostic capability of capsule endoscopes.

Nuclear Engineering Computer Modules, Thermal-Hydraulics, TH-2: Liquid Metal Fast Breeder Reactors.

ERIC Educational Resources Information Center

Reihman, Thomas C.

This learning module is concerned with the temperature field, the heat transfer rates, and the coolant pressure drop in typical liquid metal fast breeder reactor (LMFBR) fuel assemblies. As in all of the modules of this series, emphasis is placed on developing the theory and demonstrating the use with a simplified model. The heart of the module is…

Nanoscale imaging of fundamental li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters.

PubMed

Sacci, Robert L; Black, Jennifer M; Balke, Nina; Dudney, Nancy J; More, Karren L; Unocic, Raymond R

2015-03-11

The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase (SEI) formation and to track Li nucleation and growth mechanisms from a standard organic battery electrolyte (LiPF6 in EC:DMC), we used in situ electrochemical scanning transmission electron microscopy (ec-S/TEM) to perform controlled electrochemical potential sweep measurements while simultaneously imaging site-specific structures resulting from electrochemical reactions. A combined quantitative electrochemical measurement and STEM imaging approach is used to demonstrate that chemically sensitive annular dark field STEM imaging can be used to estimate the density of the evolving SEI and to identify Li-containing phases formed in the liquid cell. We report that the SEI is approximately twice as dense as the electrolyte as determined from imaging and electron scattering theory. We also observe site-specific locations where Li nucleates and grows on the surface and edge of the glassy carbon electrode. Lastly, this report demonstrates the investigative power of quantitative nanoscale imaging combined with electrochemical measurements for studying fluid-solid interfaces and their evolving chemistries.

Outstanding features of alginate-based gel electrolyte with ionic liquid for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Soeda, Kazunari; Yamagata, Masaki; Ishikawa, Masashi

2015-04-01

An alginate-based gel electrolyte with an ionic liquid (Alg/IL) is investigated for electric double-layer capacitors (EDLCs) by using physicochemical and electrochemical measurements. The Alg/EMImBF4 (EMImBF4 = 1-ethyl-3-methylimidazolium tetrafluoroborate) gel electrolyte is thermally stable up to 280 °C, where EMImBF4 decomposes. Furthermore, the EDLC with the gel electrolyte can be operated even at high temperature. The cell containing Alg/EMImBF4 is also electrochemically stable even under high voltage (∼3.5 V) operation. Thus, the alginate is a suitable host polymer for the gel electrolyte for EDLCs. According to the result of charge-discharge characteristics, the voltage drop in the charge-discharge curve for the cell with Alg/EMImBF4 gel electrolyte is considerably smaller than that with liquid-phase EMImBF4 electrolyte. To clarify the effect of Alg in contact with the activated carbon electrode, we also prepared an Alg-containing ACFC electrode (Alg + ACFC), and evaluated its EDLC characteristics in liquid EMImBF4. The results prove that the presence of Alg close to the active materials significantly reduces the internal resistance of the EDLC cell, which may be attributed to the high affinity of Alg to activated carbon.

Ultrasound Velocity Measurement in a Liquid Metal Electrode

PubMed Central

Perez, Adalberto; Kelley, Douglas H.

2015-01-01

A growing number of electrochemical technologies depend on fluid flow, and often that fluid is opaque. Measuring the flow of an opaque fluid is inherently more difficult than measuring the flow of a transparent fluid, since optical methods are not applicable. Ultrasound can be used to measure the velocity of an opaque fluid, not only at isolated points, but at hundreds or thousands of points arrayed along lines, with good temporal resolution. When applied to a liquid metal electrode, ultrasound velocimetry involves additional challenges: high temperature, chemical activity, and electrical conductivity. Here we describe the experimental apparatus and methods that overcome these challenges and allow the measurement of flow in a liquid metal electrode, as it conducts current, at operating temperature. Temperature is regulated within ±2 °C using a Proportional-Integral-Derivative (PID) controller that powers a custom-built furnace. Chemical activity is managed by choosing vessel materials carefully and enclosing the experimental setup in an argon-filled glovebox. Finally, unintended electrical paths are carefully prevented. An automated system logs control settings and experimental measurements, using hardware trigger signals to synchronize devices. This apparatus and these methods can produce measurements that are impossible with other techniques, and allow optimization and control of electrochemical technologies like liquid metal batteries. PMID:26273726

Molecularly imprinted electrochemical sensing interface based on in-situ-polymerization of amino-functionalized ionic liquid for specific recognition of bovine serum albumin.

PubMed

Wang, Yanying; Han, Miao; Liu, Guishen; Hou, Xiaodong; Huang, Yina; Wu, Kangbing; Li, Chunya

2015-12-15

A molecularly imprinted polymer film was in situ polymerized on a carboxyl functionalized multi-walled carbon nanotubes modified glassy carbon electrode surface under room temperature. This technique provides a promising imprinting approach for protein in an aqueous solution using 3-(3-aminopropyl)-1-vinylimidazolium tetrafluoroborate ionic liquid as functional monomer, N, N'-methylenebisacrylamide as crossing linker, ammonium persulfate and N,N,N',N'-tetramethylethylenediamine as initiator, and bovine serum albumin (BSA) as template. The molecularly imprinted polymerized ionic liquid film shows enhanced accessibility, high specificity and sensitivity towards BSA. Electrochemical sensing performance of the imprinted sensor was thoroughly investigated using K3Fe[CN]6/K4Fe[CN]6 as electroactive probes. Under optimal conditions, the current difference before and after specific recognition of BSA was found linearly related to its concentration in the range from 1.50×10(-9) to 1.50×10(-6) mol L(-1). The detection limit was calculated to be 3.91×10(-10) mol L(-1) (S/N=3). The practical application of the imprinted sensor was demonstrated by determining BSA in liquid milk samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of Plutonium Isotope Ratios at Very Low Levels by ICP-MS using On-Line Electrochemically Modulated Separations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liezers, Martin; Lehn, Scott A; Olsen, Khris B

2009-10-01

Electrochemically modulated separations (EMS) are shown to be a rapid and selective means of extracting and concentrating Pu from complex solutions prior to isotopic analysis by inductively coupled plasma mass spectrometry (ICP-MS). This separation is performed in a flow injection mode, on-line with the ICP-MS. A three-electrode, flow-by electrochemical cell is used to accumulate Pu at an anodized glassy carbon electrode by redox conversion of Pu(III) to Pu (IV&VI). The entire process takes place in 2% v/v (0.46M) HNO 3. No redox chemicals or acid concentration changes are required. Plutonium accumulation and release is redox dependent and controlled by themore » applied cell potential. Thus large transient volumetric concentration enhancements can be achieved. Based on more negative U(IV) potentials relative to Pu(IV), separation of Pu from uranium is efficient, thereby eliminating uranium hydride interferences. EMS-ICP-MS isotope ratio measurement performance will be presented for femtogram to attogram level plutonium concentrations.« less

Carbon Capsules of Ionic Liquid for Enhanced Performance of Electrochemical Double-Layer Capacitors.

PubMed

Luo, Qinmo; Wei, Peiran; Huang, Qianwen; Gurkan, Burcu; Pentzer, Emily B

2018-05-16

Ion accessibility, large surface area, and complete wetting of a carbonaceous electrode by the electrolyte are crucial for high-performance electrochemical double-layer capacitors. Herein, we report a facile and scalable method to prepare electrode-electrolyte hybrid materials, where an ionic liquid (IL) electrolyte is encapsulated within a shell of reduced graphene oxide (rGO) nanosheets as the active electrode material (called rGO-IL capsules). These structures were templated using a Pickering emulsion consisting of a dispersed phase of 1-methyl-3-butylimidazolium hexafluorophosphate ([bmim][PF 6 ]) and a continuous water phase; graphene oxide nanosheets were used as the surfactant, and interfacial polymerization yielded polyurea that bound the nanosheets together to form the capsule shell. This method prevents the aggregation and restacking of GO nanosheets and allows wetting of the materials by IL. The chemical composition, thermal properties, morphology, and electrochemical behavior of these new hybrid architectures are fully characterized. Specific capacitances of 80 F g -1 at 18 °C and 127 F g -1 at 60 °C were achieved at a scan rate of 10 mV s -1 for symmetric coin cells of rGO-IL capsules. These architected materials have higher capacitance at low temperature (18 °C) across many scan rates (10-500 mV s -1 ) compared with analogous cells with the porous carbon YP-50. These results demonstrate a distinct and important methodology to enhance the performance of electrochemical double-layer capacitors by incorporating electrolyte and carbon material together during synthesis.

Evaluation of Carbon Anodes for Rechargeable Lithium Cells

NASA Technical Reports Server (NTRS)

Huang, C-K.; Surampudi, S.; Attia, A.; Halpert, G.

1993-01-01

Both liquid phase intercalation technique and electrochemical intercalation technique were examined for the Li-carbon material preparation. The electrochemical techniques include a intermittent discharge method and a two step method. These two electrochemical techniques can ensure to achieve the maximum reversible Li capacity for common commercially available carbon materials. The carbon materials evaluated by the intercalacation method includes: pitch coke, petroleum cole, PAN fiber and graphite materials. Their reversible Li capacity were determined and compared. In this paper, we also demonstrate the importance of EPDM binder composition in the carbon electrode. Our results indicated that it can impact the Li intercalation and de-intercalation capacity in carbon materials. Finally, two possibilities that may help explain the capacity degradation during practical cell cycling were proposed.

Electrochemical Device Comprising Composite Bipolar Plate and Method of Using the Same

NASA Technical Reports Server (NTRS)

Mittelsteadt, Cortney K. (Inventor); Braff, William A. (Inventor)

2013-01-01

An electrochemical device and methods of using the same. In one embodiment, the electrochemical device may be used as a fuel cell and/or as an electrolyzer and includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, chemically-inert, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, as well as a fluid chamber and a non-porous an electrically-conductive plate.

Electrochemical Device Comprising Composite Bipolar Plate and Method of Using the Same

NASA Technical Reports Server (NTRS)

Mittelsteadt, Cortney K. (Inventor); Braff, William A. (Inventor)

2017-01-01

An electrochemical device and methods of using the same. In one embodiment, the electrochemical device may be used as a fuel cell and/or as an electrolyzer and includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, chemically-inert, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, as well as a fluid chamber and a non-porous an electrically-conductive plate.

Frequent Pitfalls in the Characterization of Electrodes Designed for Electrochemical Energy Conversion and Storage.

PubMed

Zeradjanin, Aleksandar R

2018-04-25

Focus on the importance of energy conversion and storage boosted research interest in various electrocatalytic materials. Characterization of solid-liquid interfaces during faradaic and non-faradaic processes is routinely conducted in many laboratories worldwide on a daily basis. This can be deemed as a very positive tendency. However, careful insight into modern literature suggests frequent misuse of electroanalytical tools. This can have very negative implications and postpone overall development of electrocatalytic materials with the desired properties. This work points out some of the frequent pitfalls in electrochemical characterization, suggests potential solutions, and above all encourages comprehensive analysis and in-depth thinking about electrochemical phenomena. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multifunctional organized mesoporous tin oxide films templated by graft copolymers for dye-sensitized solar cells.

PubMed

Park, Jung Tae; Ahn, Sung Hoon; Roh, Dong Kyu; Lee, Chang Soo; Kim, Jong Hak

2014-07-01

The synthesis of organized mesoporous SnO2 films with high porosity, larger pores, and good interconnectivity, obtained by sol-gel templating with an amphiphilic graft copolymer, poly(vinyl chloride)-graft-poly(oxyethylene methacrylate), is reported. An improved performance of dye-sensitized solar cells (DSSCs) is demonstrated by the introduction of a 400 nm thick organized mesoporous SnO2 interfacial (om-SnO2 IF) layer between nanocrystalline TiO2 (nc-TiO2 ) and a fluorine-doped tin oxide substrate. To elucidate the improved efficiency, the structural, optical, and electrochemical properties of the devices were characterized by SEM, UV/Vis spectroscopy, noncontact 3D surface profilometry, intensity-modulated photocurrent/voltage spectroscopy, incident photon-to-electron conversion efficiency, and electrochemical impedance spectroscopy measurements. The energy-conversion efficiency of the solid polymerized ionic liquid based DSSC fabricated with the om-SnO2 IF/nc-TiO2 photoanode reached 5.9% at 100 mW cm(-2) ; this is higher than those of neat nc-TiO2 (3.5%) and organized mesoporous TiO2 interfacial/nc-TiO2 layer (5.4%) photoanodes. The improved efficiency is attributed to the antireflective property, cascadal energy band gap, good interconnectivity, and high electrical conductivity of the om-SnO2 IF layer, which results in enhanced light harvesting, increased electron transport, reduced charge recombination, and decreased interfacial/internal resistance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Semi-transparent solar energy thermal storage device

DOEpatents

McClelland, John F.

1986-04-08

A visually transmitting solar energy absorbing thermal storage module includes a thermal storage liquid containment chamber defined by an interior solar absorber panel, an exterior transparent panel having a heat mirror surface substantially covering the exterior surface thereof and associated top, bottom and side walls. Evaporation of the thermal storage liquid is controlled by a low vapor pressure liquid layer that floats on and seals the top surface of the liquid. Porous filter plugs are placed in filler holes of the module. An algicide and a chelating compound are added to the liquid to control biological and chemical activity while retaining visual clarity. A plurality of modules may be supported in stacked relation by a support frame to form a thermal storage wall structure.

Semi-transparent solar energy thermal storage device

DOEpatents

McClelland, John F.

1985-06-18

A visually transmitting solar energy absorbing thermal storage module includes a thermal storage liquid containment chamber defined by an interior solar absorber panel, an exterior transparent panel having a heat mirror surface substantially covering the exterior surface thereof and associated top, bottom and side walls, Evaporation of the thermal storage liquid is controlled by a low vapor pressure liquid layer that floats on and seals the top surface of the liquid. Porous filter plugs are placed in filler holes of the module. An algicide and a chelating compound are added to the liquid to control biological and chemical activity while retaining visual clarity. A plurality of modules may be supported in stacked relation by a support frame to form a thermal storage wall structure.

Fractional capacity electrolyzer development for CO2 and H2O electrolysis

NASA Technical Reports Server (NTRS)

Wynveen, R. A.

1980-01-01

The electrolyzer module was designed to produce 0.24 kg/d (0.53 lb/d) of breathable oxygen from the electrolysis of metabolic carbon dioxide and water vapor. The fractional capacity electrolyzer module is constructed from three electrochemical tube cells and contains only three critical seals. The module design illustrated an 84 percent reduction in the total number of seals for a one person capacity oxygen generating system based on the solid electrolyte carbon dioxide and water vapor electrolysis concept. The electrolyzer module was successfully endurance tested for 71 days.

Metal-air cell with ion exchange material

DOEpatents

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2015-08-25

Embodiments of the invention are related to anion exchange membranes used in electrochemical metal-air cells in which the membranes function as the electrolyte material, or are used in conjunction with electrolytes such as ionic liquid electrolytes.

Electrochemical disinfection of repeatedly recycled blackwater in a free-standing, additive-free toilet.

PubMed

Hawkins, Brian T; Sellgren, Katelyn L; Klem, Ethan J D; Piascik, Jeffrey R; Stoner, Brian R

2017-11-01

Decentralized, energy-efficient waste water treatment technologies enabling water reuse are needed to sustainably address sanitation needs in water- and energy-scarce environments. Here, we describe the effects of repeated recycling of disinfected blackwater (as flush liquid) on the energy required to achieve full disinfection with an electrochemical process in a prototype toilet system. The recycled liquid rapidly reached a steady state with total solids reliably ranging between 0.50 and 0.65% and conductivity between 20 and 23 mS/cm through many flush cycles over 15 weeks. The increase in accumulated solids was associated with increased energy demand and wide variation in the free chlorine contact time required to achieve complete disinfection. Further studies on the system at steady state revealed that running at higher voltage modestly improves energy efficiency, and established running parameters that reliably achieve disinfection at fixed run times. These results will guide prototype testing in the field.

Determination of vitamin K1 in powdered infant formulas, using supercritical fluid extraction and liquid chromatography with electrochemical detection.

PubMed

Schneiderman, M A; Sharma, A K; Mahanama, K R; Locke, D C

1988-01-01

Vitamin K1 (phylloquinone) is extracted from commercial soy protein-based and milk-based powdered infant formulas by using supercritical fluid extraction with CO2 at 8000 psi and 60 degrees C. Quantitative extraction requires only 15 min, and does not suffer from the problems associated with conventional solvent extraction of lipophilic materials from media such as formulas. Vitamin K1 is determined in the extracts by using reverse-phase liquid chromatography (LC) with reductive mode electrochemical detection at a silver electrode polarized at -1.1 V vs SCE. LC run time is 9 min. The minimum detectable quantity is 80 pg, and response is linear over at least 5 orders of magnitude. Recovery of vitamin K1 from a milk-based powdered formula was 95.6% with RSD of 7.4%, and from a soy protein-based product, 94.4% recovery with RSD of 6.5%.

Eu3+ as a dual probe for the determination of IL anion donor power: A combined luminescence spectroscopic and electrochemical approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babai, Arash; Kopiec, Gabriel; Lackmann, Anastasia

2014-04-01

This work is aimed at giving proof that Eu(Tf2N)(3) (Tf2N = bis(trifluoromethanesulfonyl)amide) can act as both an optical and electrochemical probe for the determination of the Lewis acidity of an ionic liquid anion. For that reason the luminescence spectra and cyclic voltammograms of dilute solutions of Eu(Tf2N)(3) in various ionic liquids were investigated. The Eu2+/3+ redox potential in the investigated ILs can be related to the Lewis basicity of the IL anion. The IL cation had little influence. The lower the determined halfwave potential, the higher the IL anion basicity. The obtained ranking can be confirmed by luminescence spectroscopy wheremore » a bathochromic shift of the D-5(0) -> F-7(4) transition indicates a stronger Lewis basicity of the IL anion. (C) 2014 Published by Elsevier B.V.« less

Aluminium Electrodeposition from Ionic Liquid: Effect of Deposition Temperature and Sonication †

PubMed Central

Berretti, Enrico; Giaccherini, Andrea; Martinuzzi, Stefano M.; Innocenti, Massimo; Schubert, Thomas J.S.; Stiemke, Frank M.; Caporali, Stefano

2016-01-01

Since their discovery, ionic liquids (ILs) have attracted a wide interest for their potential use as a medium for many chemical processes, in particular electrochemistry. As electrochemical media they allow the electrodeposition of elements that are impossible to reduce in aqueous media. We have investigated the electrodeposition of aluminium from 1-butyl-3-methyl-imidazolium chloride ((Bmim)Cl)/AlCl3 (40/60 mol %) as concerns the effect of deposition parameters on the quality of the deposits. Thick (20 μm) aluminium coatings were electrodeposited on brass substrates at different temperatures and mixing conditions (mechanical stirring and sonication). These coatings were investigated by means of scanning electron microscope, roughness measurements, and X-ray diffraction to assess the morphology and the phase composition. Finally, electrochemical corrosion tests were carried out with the intent to correlate the deposition parameters to the anti-corrosion properties. PMID:28773839

Adsorption, Thermodynamic and Quantum Chemical Studies of 1-hexyl-3-methylimidazolium Based Ionic Liquids as Corrosion Inhibitors for Mild Steel in HCl

PubMed Central

Mashuga, Motsie E.; Olasunkanmi, Lukman O.; Adekunle, Abolanle S.; Yesudass, Sasikumar; Kabanda, Mwadham M.; Ebenso, Eno E.

2015-01-01

The inhibition of mild steel corrosion in 1 M HCl solution by some ionic liquids (ILs) namely, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate [HMIM][TfO], 1-hexyl-3-methylimidazolium tetrafluoroborate [HMIM][BF4], 1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM][PF6], and 1-hexyl-3-methylimidazolium iodide [HMIM][I] was investigated using electrochemical measurements, spectroscopic analyses and quantum chemical calculations. All the ILs showed appreciably high inhibition efficiency. At 303 K, the results of electrochemical measurements indicated that the studied ILs are mixed-type inhibitors. The adsorption studies showed that all the four ILs adsorb spontaneously on steel surface with [HMIM][TfO], [HMIM][BF4] and [HMIM][I] obeying Langmuir adsorption isotherm, while [HMIM][PF6] conformed better with Temkin adsorption isotherm. Spectroscopic analyses suggested the formation of Fe/ILs complexes. Some quantum chemical parameters were calculated to corroborate experimental results.

CdO nanosheet film with a (200)-preferred orientation with sensitivity to liquefied petroleum gas (LPG) at low-temperatures.

PubMed

Cui, Guangliang; Li, Zimeng; Gao, Liang; Zhang, Mingzhe

2012-12-21

CdO nanosheet film can be synthesized by electrochemical deposition in an ultra-thin liquid layer by using Cd(NO(3))(2) and HNO(3) as source materials for Cd and oxygen respectively. HNO(3) is also used to adjust the pH of the electrolyte. Studies on the detailed structure indicate that the synthesized CdO nanosheet film has a face-centered cubic structure with (200)-preferred orientation. The response of the CdO nanosheet film to liquefied petroleum gas (LPG) at low temperature has been significantly improved by the novel structure of film. It has exhibited excellent sensitivity and selectivity to LPG at low temperature. A new growth mechanism of electrochemical deposition has been proposed to elaborate the formation of nanosheet in an ultra-thin liquid layer. The self-oscillation of potential in the growth interface and intermediate hydroxide are responsible for the formation of nanosheets.

Combinatorial electrochemical cell array for high throughput screening of micro-fuel-cells and metal/air batteries.

PubMed

Jiang, Rongzhong

2007-07-01

An electrochemical cell array was designed that contains a common air electrode and 16 microanodes for high throughput screening of both fuel cells (based on polymer electrolyte membrane) and metal/air batteries (based on liquid electrolyte). Electrode materials can easily be coated on the anodes of the electrochemical cell array and screened by switching a graphite probe from one cell to the others. The electrochemical cell array was used to study direct methanol fuel cells (DMFCs), including high throughput screening of electrode catalysts and determination of optimum operating conditions. For screening of DMFCs, there is about 6% relative standard deviation (percentage of standard deviation versus mean value) for discharge current from 10 to 20 mAcm(2). The electrochemical cell array was also used to study tin/air batteries. The effect of Cu content in the anode electrode on the discharge performance of the tin/air battery was investigated. The relative standard deviations for screening of metal/air battery (based on zinc/air) are 2.4%, 3.6%, and 5.1% for discharge current at 50, 100, and 150 mAcm(2), respectively.

Efficient electrochemical degradation of multiwall carbon nanotubes.

PubMed

Reipa, Vytas; Hanna, Shannon K; Urbas, Aaron; Sander, Lane; Elliott, John; Conny, Joseph; Petersen, Elijah J

2018-07-15

As the production mass of multiwall carbon nanotubes (MWCNT) increases, the potential for human and environmental exposure to MWCNTs may also increase. We have shown that exposing an aqueous suspension of pristine MWCNTs to an intense oxidative treatment in an electrochemical reactor, equipped with an efficient hydroxyl radical generating Boron Doped Diamond (BDD) anode, leads to their almost complete mineralization. Thermal optical transmittance analysis showed a total carbon mass loss of over two orders of magnitude due to the electrochemical treatment, a result consistent with measurements of the degraded MWCNT suspensions using UV-vis absorbance. Liquid chromatography data excludes substantial accumulation of the low molecular weight reaction products. Therefore, up to 99% of the initially suspended MWCNT mass is completely mineralized into gaseous products such as CO 2 and volatile organic carbon. Scanning electron microscopy (SEM) images show sporadic opaque carbon clusters suggesting the remaining nanotubes are transformed into structure-less carbon during their electrochemical mineralization. Environmental toxicity of pristine and degraded MWCNTs was assessed using Caenorhabditis elegans nematodes and revealed a major reduction in the MWCNT toxicity after treatment in the electrochemical flow-by reactor. Published by Elsevier B.V.

In-plane pitch control of cholesteric liquid crystals by formation of artificial domains via patterned photopolymerization.

PubMed

Yoshida, Hiroyuki; Miura, Yusuke; Tokuoka, Kazuki; Suzuki, Satoshi; Fujii, Akihiko; Ozaki, Masanori

2008-11-10

A controlled helix pitch modulation in the in-plane direction of a planarly aligned cholesteric liquid crystal cell is demonstrated by using photopolymerizable cholesteric liquid crystals. By fabricating artificial domains with a closed volume via two-photon excitation laser-lithography, the degree of pitch modulation could be controlled by adjusting the surface area to volume ratio of the domain. A pitch modulation of over 60 nm was realized by designing the shape of the artificial domain.

Energy dispersive-EXAFS of Pd nucleation at a liquid/liquid interface

NASA Astrophysics Data System (ADS)

Chang, S.-Y.; Booth, S. G.; Uehara, A.; Mosselmans, J. F. W.; Cibin, G.; Pham, V.-T.; Nataf, L.; Dryfe, R. A. W.; Schroeder, S. L. M.

2016-05-01

Energy dispersive extended X-ray absorption fine structure (EDE) has been applied to Pd nanoparticle nucleation at a liquid/liquid interface under control over the interfacial potential and thereby the driving force for nucleation. Preliminary analysis focusing on Pd K edge-step height determination shows that under supersaturated conditions the concentration of Pd near the interface fluctuate over a period of several hours, likely due to the continuous formation and dissolution of sub-critical nuclei. Open circuit potential measurements conducted ex-situ in a liquid/liquid electrochemical cell support this view, showing that the fluctuations in Pd concentration are also visible as variations in potential across the liquid/liquid interface. By decreasing the interfacial potential through inclusion of a common ion (tetraethylammonium, TEA+) the Pd nanoparticle growth rate could be slowed down, resulting in a smooth nucleation process. Eventually, when the TEA+ ions reached an equilibrium potential, Pd nucleation and particle growth were inhibited.

System and method for detecting gas

DOEpatents

Chow, Oscar Ken; Moulthrop, Lawrence Clinton; Dreier, Ken Wayne; Miller, Jacob Andrew

2010-03-16

A system to detect a presence of a specific gas in a mixture of gaseous byproducts comprising moisture vapor is disclosed. The system includes an electrochemical cell, a transport to deliver the mixture of gaseous byproducts from the electrochemical cell, a gas sensor in fluid communication with the transport, the sensor responsive to a presence of the specific gas to generate a signal corresponding to a concentration of the specific gas, and a membrane to prevent transmission of liquid moisture, the membrane disposed between the transport and the gas sensor.

Optically addressed and submillisecond response phase only liquid crystal spatial light modulator

NASA Astrophysics Data System (ADS)

Zhao, Xiangjie; Duan, Jiazhu; Zhang, Dayong; Luo, Yongquan

2014-10-01

Liquid crystal based phase only spatial light modulator has attracted many research interests since last decades because of its superior advantage. Until now the liquid crystal spatial light modulator has been applied in many fields, but the response speed of nematic LC limited its further application. In this paper, an optically addressed phase only LC spatial light modulator was proposed based on polymer network liquid crystal. Morphology effect on the light scattering of PNLC was studied, which was mainly consisted of fiber and fiber bundles. The morphology nearly determined the light scattering and electro-optical property. Due to the high threshold voltage, to address the PNLC phase modulator was also concerned. Optical addressing method was proposed, in which BSO crystal was selected to replace one of the glass substrate. The response speed of PNLC was so fast that the reorientation of liquid crystal director will follow the change of effective voltage applied on LC layer, which was related with the voltage signal and especially with electron transport of photo-induced carriers due to diffusion and drift. The on state dynamic response of phase change was investigated. Based on this device, beam steering was also achieved by loading 488nm laser strip on the optical addressed phase only spatial light modulator.

Modulation transfer function of partial gating detector by liquid crystal auto-controlling light intensity

NASA Astrophysics Data System (ADS)

Yang, Xusan; Tang, Yuanhe; Liu, Kai; Liu, Hanchen; Gao, Haiyang; Li, Qing; Zhang, Ruixia; Ye, Na; Liang, Yuan; Zhao, Gaoxiang

2008-12-01

Based on the electro-optical properties of liquid crystal, we have designed a novel partial gating detector. Liquid crystal can be taken to change its own transmission according to the light intensity outside. Every single pixel of the image is real-time modulated by liquid crystal, thus the strong light is weakened and low light goes through the detector normally .The purpose of partial-gating strong light (>105lx) can be achieved by this detector. The modulation transfer function (MTF) equations of the main optical sub-systems are calculated in this paper, they are liquid crystal panels, linear fiber panel and CCD array detector. According to the relevant size, the MTF value of this system is fitted out. The result is MTF= 0.518 at Nyquist frequency.

Methods and systems for fuel production in electrochemical cells and reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marina, Olga A.; Pederson, Larry R.

Methods and systems for fuel, chemical, and/or electricity production from electrochemical cells are disclosed. A voltage is applied between an anode and a cathode of an electrochemical cell. The anode includes a metal or metal oxide electrocatalyst. Oxygen is supplied to the cathode, producing oxygen ions. The anode electrocatalyst is at least partially oxidized by the oxygen ions transported through an electrolyte from the cathode to the anode. A feed gas stream is supplied to the anode electrocatalyst, which is converted to a liquid fuel. The anode electrocatalyst is re-oxidized to higher valency oxides, or a mixture of oxide phases,more » by supplying the oxygen ions to the anode. The re-oxidation by the ions is controlled or regulated by the amount of voltage applied.« less

Cascade redox flow battery systems

DOEpatents

Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

2014-07-22

A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

Curious Case of Positive Current Collectors: Corrosion and Passivation at High Temperature.

PubMed

Sayed, Farheen N; Rodrigues, Marco-Tulio F; Kalaga, Kaushik; Gullapalli, Hemtej; Ajayan, P M

2017-12-20

In the evaluation of compatibility of different components of cell for high-energy and extreme-conditions applications, the highly focused are positive and negative electrodes and their interaction with electrolyte. However, for high-temperature application, the other components are also of significant influence and contribute toward the total health of battery. In present study, we have investigated the behavior of aluminum, the most common current collector for positive electrode materials for its electrochemical and temperature stability. For electrochemical stability, different electrolytes, organic and room temperature ionic liquids with varying Li salts (LiTFSI, LiFSI), are investigated. The combination of electrochemical and spectroscopic investigations reflects the varying mechanism of passivation at room and high temperature, as different compositions of decomposed complexes are found at the surface of metals.

An approximate theoretical treatment of ion transfer processes at asymmetric microscopic and nanoscopic liquid-liquid interfaces: Single and double potential pulse techniques

NASA Astrophysics Data System (ADS)

Molina, A.; Laborda, E.; Compton, R. G.

2014-03-01

Simple theory for the electrochemical study of reversible ion transfer processes at micro- and nano-liquid|liquid interfaces supported on a capillary is presented. Closed-form expressions are obtained for the response in normal pulse and differential double pulse voltammetries, which describe adequately the particular behaviour of these systems due to the ‘asymmetric’ ion diffusion inside and outside the capillary. The use of different potential pulse techniques for the determination of the formal potential and diffusion coefficients of the ion is examined. For this, very simple analytical expressions are presented for the half-wave potential in NPV and the peak potential in DDPV.

Electrochemistry at Edge of Single Graphene Layer in a Nanopore

PubMed Central

Banerjee, Shouvik; Shim, Jiwook; Rivera, Jose; Jin, Xiaozhong; Estrada, David; Solovyeva, Vita; You, Xiuque; Pak, James; Pop, Eric; Aluru, Narayana; Bashir, Rashid

2013-01-01

We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al2O3 dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 104 A/cm2. The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices. PMID:23249127

Transparent Electrochemical Gratings from a Patterned Bistable Silver Mirror.

PubMed

Park, Chihyun; Na, Jongbeom; Han, Minsu; Kim, Eunkyoung

2017-07-25

Silver mirror patterns were formed reversibly on a polystyrene (PS)-patterned electrode to produce gratings through the electrochemical reduction of silver ions. The electrochemical gratings exhibited high transparency (T > 95%), similar to a see-through window, by matching the refractive index of the grating pattern with the surrounding medium. The gratings switch to a diffractive state upon the formation of a mirror pattern (T < 5%) with a high diffraction efficiency up to 40%, providing reversible diffractive gratings. The diffraction state was maintained in the voltage-off state (V-off) for 40 min, which demonstrated bistable reversible electrochemical grating (BREG) behavior. By carefully combining the BREGs through period matching, dual-color switching was achieved within the full color region, which exhibited three distinct optical switching states between -2.5, 0, and +2.5 V. The wide range of light tenability using the metallic BREGs developed herein enabled IR modulation, NIR light reflection, and on-demand heat transfer.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater.

PubMed

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-03-15

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO 2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

PubMed Central

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-01-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process. PMID:28294180

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

NASA Astrophysics Data System (ADS)

Gu, Di; Gao, Simeng; Jiang, Tingting; Wang, Baohui

2017-03-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Interference from Indian diet on the internal standard in a commercial method for the measurement of urinary metanephrines by high-performance liquid chromatography with electrochemical detection.

PubMed

Madhavaram, Hima; Woollard, Gerald A

2014-05-01

Urinary metanephrines are widely used in the diagnosis of catecholamine secreting tumours. Over the past two years we have been using the commercial Recipe(®) ClinRep(®) Complete Kit for Metanephrines in Urine coupled with high-performance liquid chromatography and coulometric detection. It was noticed that the internal standards on the patient chromatograms were sporadically raised due to interference. The interference had identical chromatographic and electrochemical properties to the Recipe(®) internal standard (undisclosed identity). Inspection of the patient names showed it seemingly had a higher frequency and magnitude in patients of Indian origin. The source of the interference was tracked by dietary observation and intervention to curry leaves, a common component of Indian foods. The interference was chromatographically and electrochemically indistinguishable from the internal standard. The mass spectrum of the pentafluoropropionate derivative of the interference matched the Recipe(®) internal standard and was identified as methoxyhydroxybenzylamine by library match. The component co-elutes exactly with internal standard and artifactually decreases the metanephrine and normetanephrine results. It is surprising that it has not been described previously. Patients being assessed for catecholamine secreting tumours should be advised to withdraw from eating Indian foods at least 24 h prior to commencement of urinary collection.

Impact of isoelectric points of nanopowders in electrolytes on electrochemical characteristics of dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Mohanty, Shyama Prasad; Bhargava, Parag

2012-11-01

Nanoparticle loaded quasi solid electrolytes are important from the view point of developing electrolytes for dye sensitized solar cells (DSSCs) having long term stability. The present work shows the influence of isoelectric point of nanopowders in electrolyte on the photoelectrochemical characteristics of DSSCs. Electrolytes with nanopowders of silica, alumina and magnesia which have widely differing isoelectric points are used in the study. Adsorption of ions from the electrolyte on the nanopowder surface, characterized by zeta potential measurement, show that cations get adsorbed on silica, alumina surface while anions get adsorbed on magnesia surface. The electrochemical characteristics of nanoparticulate loaded electrolytes are examined through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). DSSCs fabricated using liquid, silica or alumina loaded electrolytes exhibit almost similar performance. But interestingly, the magnesia loaded electrolyte-based cell show lower short circuit current density (JSC) and much higher open circuit voltage (VOC), which is attributed to adsorption of anions. Such anionic adsorption prevents the dark reaction in magnesia loaded electrolyte-based cell and thus, enhances the VOC by almost 100 mV as compared to liquid electrolyte based cell. Also, higher electron life time at the titania/electrolyte interface is observed in magnesia loaded electrolyte-based cell as compared to others.

A high-sensitivity electrochemical aptasensor of carcinoembryonic antigen based on graphene quantum dots-ionic liquid-nafion nanomatrix and DNAzyme-assisted signal amplification strategy.

PubMed

Huang, Jing-Yi; Zhao, Lang; Lei, Wan; Wen, Wei; Wang, Yi-Jia; Bao, Ting; Xiong, Hua-Yu; Zhang, Xiu-Hua; Wang, Sheng-Fu

2018-01-15

In this work, we have developed an electrochemical aptasensor for high-sensitivity determination of carcinoembryonic antigen (CEA) based on lead ion (Pb 2+ )-dependent DNAzyme-assisted signal amplification and graphene quantum dot-ionic liquid-nafion (GQDs-IL-NF) composite film. We designed hairpin DNA containing CEA-specific aptamers and DNAzyme chains. In the presence of CEA, hairpin DNA recognized the target and performed a DNAzyme-assisted signal amplification reaction to yield a large number of single-stranded DNA. The GQDs-IL-NF composite film was immobilized on the glassy carbon electrode for the interaction with single-stranded DNA through noncovalent π-π stacking interaction. Therefore, the methylene blue-labeled substrate DNA (MB-substrate) was fixed on the electrode and exhibited an initial electrochemical signal. Under optimal conditions, the response current change was proportional to the concentration of CEA, demonstrating a wide linear range from 0.5fgmL -1 to 0.5ngmL -1 , with a low detection limit of 0.34fgmL -1 . Furthermore, the proposed aptasensor was successfully applied in determining CEA in serum samples, showing its superior prospects in clinical diagnosis. Copyright © 2017 Elsevier B.V. All rights reserved.

In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode–Electrolyte Interface: a SIMS Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhaoying; Zhang, Yanyan; Liu, Bingwen

The in situ molecular characterization of reaction intermediates and products at electrode-electrolyte interfaces is central to mechanistic studies of complex electrochemical processes, yet a great challenge. The coupling of electrochemistry (EC) and mass spectrometry (MS) has seen rapid development and found broad applicability in tackling challenges in analytical and bioanalytical chemistry. However, few truly in situ and real-time EC-MS studies have been reported at electrode-electrolyte interfaces. An innovative EC-MS coupling method named in situ liquid secondary ion mass spectrometry (SIMS) was recently developed by combining SIMS with a vacuum compatible microfluidic electrochemical device. Using this novel capability we report themore » first in situ elucidation of the electro-oxidation mechanism of a biologically significant organic compound, ascorbic acid (AA), at the electrode-electrolyte interface. The short-lived radical intermediate was successfully captured, which had not been detected directly before. Moreover, we demonstrated the power of this new technique in real-time monitoring of the formation and dynamic evolution of electrical double layers at the electrode-electrolyte interface. This work suggests further promising applications of in situ liquid SIMS in studying more complex chemical and biological events at the electrode-electrolyte interface.« less

Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance.

PubMed

Yamauchi, Yusuke; Tonegawa, Akihisa; Komatsu, Masaki; Wang, Hongjing; Wang, Liang; Nemoto, Yoshihiro; Suzuki, Norihiro; Kuroda, Kazuyuki

2012-03-21

Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.

Molecular Biosensors for Electrochemical Detection of Infectious Pathogens in Liquid Biopsies: Current Trends and Challenges

PubMed Central

Yáñez-Sedeño, Paloma

2017-01-01

Rapid and reliable diagnosis of infectious diseases caused by pathogens, and timely initiation of appropriate treatment are critical determinants to promote optimal clinical outcomes and general public health. Conventional in vitro diagnostics for infectious diseases are time-consuming and require centralized laboratories, experienced personnel and bulky equipment. Recent advances in electrochemical affinity biosensors have demonstrated to surpass conventional standards in regards to time, simplicity, accuracy and cost in this field. The tremendous potential offered by electrochemical affinity biosensors to detect on-site infectious pathogens at clinically relevant levels in scarcely treated body fluids is clearly stated in this review. The development and application of selected examples using different specific receptors, assay formats and electrochemical approaches focusing on the determination of specific circulating biomarkers of different molecular (genetic, regulatory and functional) levels associated with bacterial and viral pathogens are critically discussed. Existing challenges still to be addressed and future directions in this rapidly advancing and highly interesting field are also briefly pointed out. PMID:29099764

Non-Invasive Breast Cancer Diagnosis through Electrochemical Biosensing at Different Molecular Levels

PubMed Central

Campuzano, Susana

2017-01-01

The rapid and accurate determination of specific circulating biomarkers at different molecular levels with non- or minimally invasive methods constitutes a major challenge to improve the breast cancer outcomes and life quality of patients. In this field, electrochemical biosensors have demonstrated to be promising alternatives against more complex conventional strategies to perform fast, accurate and on-site determination of circulating biomarkers at low concentrations in minimally treated body fluids. In this article, after discussing briefly the relevance and current challenges associated with the determination of breast cancer circulating biomarkers, an updated overview of the electrochemical affinity biosensing strategies emerged in the last 5 years for this purpose is provided highlighting the great potentiality of these methodologies. After critically discussing the most interesting features of the electrochemical strategies reported so far for the single or multiplexed determination of such biomarkers with demonstrated applicability in liquid biopsy analysis, existing challenges still to be addressed and future directions in this field will be pointed out. PMID:28858236

Electrochemical cell

DOEpatents

Redey, Laszlo I.; Myles, Kevin M.; Vissers, Donald R.; Prakash, Jai

1996-01-01

An electrochemical cell with a positive electrode having an electrochemically active layer of at least one transition metal chloride. A negative electrode of an alkali metal and a compatible electrolyte including an alkali metal salt molten at cell operating temperature is included in the cell. The electrolyte is present at least partially as a corrugated .beta." alumina tube surrounding the negative electrode interior to the positive electrode. The ratio of the volume of liquid electrolyte to the volume of the positive electrode is in the range of from about 0.1 to about 3. A plurality of stacked electrochemical cells is disclosed each having a positive electrode, a negative electrode of an alkali metal molten at cell operating temperature, and a compatible electrolyte. The electrolyte is at least partially present as a corrugated .beta." alumina sheet separating the negative electrode and interior to the positive electrodes. The alkali metal is retained in a porous electrically conductive ceramic, and seals for sealing the junctures of the electrolyte and the adjacent electrodes at the peripheries thereof.

A comparison of electrochemically pre-treated and spark-platinized carbon fiber microelectrode. Measurement of 8-oxo-7,8-dihydro-2'-deoxyguanosine in human urine and plasma.

PubMed

Bartosova, Z; Riman, D; Halouzka, V; Vostalova, J; Simanek, V; Hrbac, J; Jirovsky, D

2016-09-07

A novel method of carbon fiber microelectrode activation using spark discharge was demonstrated and compared to conventional electrochemical pretreatment by potential cycling. The spark discharge was performed at 800 V between the microelectrode connected to positive pole of the power supply and platinum counter electrode. Spark discharge led both to trimming of the fiber tip into conical shape and to the modification of carbon fiber microelectrode with platinum, as proven by scanning electron microscopy and electron dispersive X-ray spectroscopy. After the characterization of electrochemical properties using ferricyanide voltammetry, the activated electrodes were used for electrochemical analysis of 8-oxo-7,8-dihydro-2'-deoxyguanosine, an oxidative stress marker. Subnanomolar detection limits (0.55 nmol L(-1)) in high-performance liquid chromatography were achieved for spark platinized electrodes incorporated into the flow detection cell. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular Biosensors for Electrochemical Detection of Infectious Pathogens in Liquid Biopsies: Current Trends and Challenges.

PubMed

Campuzano, Susana; Yáñez-Sedeño, Paloma; Pingarrón, José Manuel

2017-11-03

Rapid and reliable diagnosis of infectious diseases caused by pathogens, and timely initiation of appropriate treatment are critical determinants to promote optimal clinical outcomes and general public health. Conventional in vitro diagnostics for infectious diseases are time-consuming and require centralized laboratories, experienced personnel and bulky equipment. Recent advances in electrochemical affinity biosensors have demonstrated to surpass conventional standards in regards to time, simplicity, accuracy and cost in this field. The tremendous potential offered by electrochemical affinity biosensors to detect on-site infectious pathogens at clinically relevant levels in scarcely treated body fluids is clearly stated in this review. The development and application of selected examples using different specific receptors, assay formats and electrochemical approaches focusing on the determination of specific circulating biomarkers of different molecular (genetic, regulatory and functional) levels associated with bacterial and viral pathogens are critically discussed. Existing challenges still to be addressed and future directions in this rapidly advancing and highly interesting field are also briefly pointed out.

Mixtures of glyme and aprotic-protic ionic liquids as electrolytes for energy storage devices

NASA Astrophysics Data System (ADS)

Stettner, T.; Huang, P.; Goktas, M.; Adelhelm, P.; Balducci, A.

2018-05-01

Ionic liquids (ILs) have been proven to be promising electrolytes for electrochemical energy storage devices such as supercapacitors and lithium ion batteries. In the last years, due to deficiency in storage of lithium on earth, innovative systems, such as sodium-based devices, attracted considerable attention. IL-based electrolytes have been proposed also as electrolytes for these devices. Nevertheless, in the case of these systems, the advantages and limits of IL-based electrolytes need to be further investigated. In this work we report an investigation about the chemical-physical properties of mixtures containing bis(2-methoxyethyl)ether diglyme (2G), which is presently considered as one of the most interesting solvents for sodium-based devices, and the ionic liquids 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) and 1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PyrH4TFSI). The conductivities, viscosities, and densities of several mixtures of 2G and these ILs have been investigated. Furthermore, their impact on the electrochemical behaviour of activated carbon composite electrodes has been considered. The results of this investigation indicate that these mixtures are promising electrolytes for the realization of advanced sodium-based devices.

Electrochemical and structural characterization of polymer gel electrolytes based on a PEO copolymer and an imidazolium-based ionic liquid for dye-sensitized solar cells.

PubMed

Freitas, Flavio S; de Freitas, Jilian N; Ito, Bruno I; De Paoli, Marco-A; Nogueira, Ana F

2009-12-01

Polymer electrolytes based on mixtures of poly(ethylene oxide-co-propylene oxide) and 1-methyl-3-propyl-imidazolium iodide (MPII) were investigated, aiming at their application in dye-sensitized solar cells (DSSC). The interactions between the copolymer and the ionic liquid were analyzed by infrared spectroscopy and (1)H NMR. The results show interactions between the ether oxygen in the polymer and the hydrogen in the imidazolium cations. The ionic conductivities, electrochemical behaviors, and thermal properties of the electrolytes containing different concentrations of MPII were investigated. The electrolyte containing 70 wt % MPII presented the highest ionic conductivity (2.4 x 10(-3) S cm(-1)) and a diffusion coefficient of 1.9 x 10(-7) cm(2) s(-1). The influence of LiI addition to the electrolytes containing different concentrations of MPII was also investigated. The DSSC assembled with the electrolyte containing 70 wt % MPII showed an efficiency of 3.84% at 100 mW cm(-2). The stability of the devices for a period of 30 days was also evaluated using sealed cells. The devices assembled with the electrolyte containing less ionic liquid showed to be more stable.

Liquid gallium and the eutectic gallium indium (EGaIn) alloy: Dielectric functions from 1.24 to 3.1 eV by electrochemical reduction of surface oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morales, Daniel; Yu, Zhiyuan; Dickey, Michael D., E-mail: mddickey@ncsu.edu, E-mail: aspnes@ncsu.edu

Liquid metals based on gallium are promising materials for soft, stretchable, and shape reconfigurable electromagnetic devices. The behavior of these metals relates directly to the thicknesses of their surface oxide layers, which can be determined nondestructively by ellipsometry if their dielectric functions ε are known. This paper reports on the dielectric functions of liquid gallium and the eutectic gallium indium (EGaIn) alloy from 1.24 to 3.1 eV at room temperature, measured by spectroscopic ellipsometry. Overlayer-induced artifacts, a continuing problem in optical measurements of these highly reactive metals, are eliminated by applying an electrochemically reductive potential to the surface of the metalmore » immersed in an electrolyte. This technique enables measurements at ambient conditions while avoiding the complications associated with removing overlayers in a vacuum environment. The dielectric responses of both metals are closely represented by the Drude model. The EGaIn data suggest that in the absence of an oxide the surface is In-enriched, consistent with the previous vacuum-based studies. Possible reasons for discrepancies with previous measurements are discussed.« less

Oxidation and adduct formation of xenobiotics in a microfluidic electrochemical cell with boron doped diamond electrodes and an integrated passive gradient rotation mixer.

PubMed

van den Brink, Floris T G; Wigger, Tina; Ma, Liwei; Odijk, Mathieu; Olthuis, Wouter; Karst, Uwe; van den Berg, Albert

2016-10-05

Reactive xenobiotic metabolites and their adduct formation with biomolecules such as proteins are important to study as they can be detrimental to human health. Here, we present a microfluidic electrochemical cell with integrated micromixer to study phase I and phase II metabolism as well as protein adduct formation of xenobiotics in a purely instrumental approach. The newly developed microfluidic device enables both the generation of reactive metabolites through electrochemical oxidation and subsequent adduct formation with biomolecules in a chemical microreactor. This allows us to study the detoxification of reactive species with glutathione and to predict potential toxicity of xenobiotics as a result of protein modification. Efficient mixing in microfluidic systems is a slow process due to the typically laminar flow conditions in shallow channels. Therefore, a passive gradient rotation micromixer has been designed that is capable of mixing liquids efficiently in a 790 pL volume within tens of milliseconds. The mixing principle relies on turning the concentration gradient that is initially established by bringing together two streams of liquid, to take advantage of the short diffusion distances in the shallow microchannels of thin-layer flow cells. The mixer is located immediately downstream of the working electrode of an electrochemical cell with integrated boron doped diamond electrodes. In conjunction with mass spectrometry, the two microreactors integrated in a single device provide a powerful tool to study the metabolism and toxicity of xenobiotics, which was demonstrated by the investigation of the model compound 1-hydroxypyrene.

Link between the dielectric properties of mesomorphic and biological materials

NASA Astrophysics Data System (ADS)

Szwajczak, Elzbieta; Szymanski, Aleksander B.

2002-06-01

An application of liquid crystalline materials as a model materials for the use in dielectric spectroscopy of the artificial biological materials and the tissues is discussed. It is shown that an application of the standard electrochemical concepts may break in the case of liquid crystalline materials as well as biological materials. The presence of space charge regions as well as electrical non- linearities of the sample may suggest some special possibility of the time domain technique application.

Charge Density Dependent Hole Mobility and Density of States Throughout the Entire Finite Potential Window of Conductivity in Ionic Liquid Gated Poly(3-hexylthiophene)

NASA Astrophysics Data System (ADS)

Paulsen, Bryan D.; Frisbie, C. Daniel

2012-02-01

Ionic liquids, used in place of traditional gate dielectric materials, allow for the accumulation of very high 2D and 3D charge densities (>10^14 #/cm^2 and >10^21 #/cm^3 respectively) at low voltage (<5 V). Here we study the electrochemical gating of the benchmark semiconducting polymer poly(3-hexylthiophene) (P3HT) with the ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMI][FAP]). The electrochemical stability of [EMI][FAP] allowed the reproducible accumulation of 2 x 10^21 hole/cm^3, or one hole (and stabilizing anion dopant) per every two thiophene rings. A finite potential/charge density window of high electrical conductivity was observed with hole mobility reaching a maximum of 0.86 cm^2/V s at 0.12 holes per thiophene ring. Displacement current measurements, collected versus a calibrated reference electrode, allowed the mapping of the highly structured and extremely broad density of states of the P3HT/[EMI][FAP] doped composite. Variable temperature and charge density hole transport measurements revealed hole transport to be thermally activated and non-monotonic, displaying a activation energy minimum of ˜20 meV in the region of maximum conductivity and hole mobility. To show the generality of this result, the study was extended to an additional four ionic liquids and three semiconducting polymers.

Studies of Aqueous and Non-Aqueous Electrochemical Interface for Applications in Microelectronic and Energy Storage Systems

NASA Astrophysics Data System (ADS)

Zheng, Jianping

Various electrochemical techniques were utilized to study a wide range of electrochemical systems in this dissertation. Mainly they are grouped in three sections: 1) the conventional metal-aqueous systems for new applications in modern microelectronic devices, 2) unconventional ceramic-organic systems for applications in Li-ion batteries and 3) novel systems composed of ionic liquids and carbon series electrodes. The objects are to probe the electrochemical/chemical reactions and interfacial structures, which are the common features of the aforementioned systems. This dissertation mainly focuses on experimental aspects, however, some theories and new models used to elucidate the experiment data have also been developed and presented. Some new experimental techniques have been explored and their limitations and validity have also been discussed. Oxalic acid (OA)-based nonalkaline solutions with H2O 2 are found to support chemically mediated removal of Ta-oxide surface films on Ta. The associated surface reactions are critical for chemical mechanical planarization (CMP) of Ta barrier. In chapter 4, a Ta coupon electrode is used as a model system in abrasive-free solutions of OA and H2O 2, where the chemical component of CMP is selectively examined. In chapter 5, electrochemical impedance spectroscopy (EIS) is employed to study the competitive reactions of surface corrosion and passivating film formation on a Cu-rotating disc electrode (RDE) in pH-adjusted solutions of H2O2, acetic acid (HAc) and ammonium dodecyl sulfate (ADS). Micrometric LiMn2O4 particles are mechano-chemically modified by ball-milling to obtain a mixture of nano- and micro-scale particles. In chapter 6, this mixture is tested as a potential active cathode material for rapid-charge Li ion batteries, and also as a model system for studying the detailed kinetics of Li intercalation/de-intercalation in such electrodes. In chapter 7, cyclic voltammetry (CV) and EIS are compared as techniques for analyzing double layer capacitances of ionic liquids (ILs) at the surfaces of two carbon-based electrodes. These systems are relevant for energy storage supercapacitors and often are associated with unconventional electrochemical properties. In chapter 8, the electrochemical interfaces of a glassy carbon (GC) and a carbon nanotube (CNT) paper electrode have been studied in EmimBF 4 and BmimBF4 ILs using CV and EIS.

An Efficient Power Harvesting Mobile Phone-Based Electrochemical Biosensor for Point-of-Care Health Monitoring

PubMed Central

Sun, Alexander C.; Yao, Chengyang; Venkatesh, A. G.; Hall, Drew A.

2016-01-01

Cellular phone penetration has grown continually over the past two decades with the number of connected devices rapidly approaching the total world population. Leveraging the worldwide ubiquity and connectivity of these devices, we developed a mobile phone-based electrochemical biosensor platform for point-of-care (POC) diagnostics and wellness tracking. The platform consists of an inexpensive electronic module (< $20) containing a low-power potentiostat that interfaces with and efficiently harvests power from a wide variety of phones through the audio jack. Active impedance matching improves the harvesting efficiency to 79%. Excluding loses from supply rectification and regulation, the module consumes 6.9 mW peak power and can measure < 1 nA bidirectional current. The prototype was shown to operate within the available power budget set by mobile devices and produce data that matches well with that of an expensive laboratory grade instrument. We demonstrate that the platform can be used to track the concentration of secretory leukocyte protease inhibitor (SLPI), a biomarker for monitoring lung infections in cystic fibrosis patients, in its physiological range via an electrochemical sandwich assay on disposable screen-printed electrodes with a 1 nM limit of detection. PMID:27725788

Electrochemical capacitance modulation in an interacting mesoscopic capacitor induced by internal charge transfer

NASA Astrophysics Data System (ADS)

Liu, Wei; He, Jianhong; Guo, Huazhong; Gao, Jie

2018-04-01

We report experiments on the dynamic response of an interacting mesoscopic capacitor consisting of a quantum dot with two confined spin-split levels of the lowest Landau level. In high magnetic fields, states inside the dot are regulated by a mixture of Coulomb interaction and Landau-level quantization, and electrons distribute on two spatially separated regions. Quantum point contact voltage and magnetic field are employed to manipulate the number and distribution of electrons inside the quantum dot. We find that the periodicity of the electrochemical capacitance oscillations is dominated by the charging energy, and their amplitudes, due to internal charge transfer and strong internal capacitive coupling, show rich variations of modulations. Magnetocapacitance displays a sawtoothlike manner and may differ in tooth directions for different voltages, which, we demonstrate, result from a sawtoothlike electrochemical potential change induced by internal charge transfer and field-sensitive electrostatic potential. We further build a charge stability diagram, which, together with all other capacitance properties, is consistently interpreted in terms of a double-dot model. The demonstrated technique is of interest as a tool for fast and sensitive charge state readout of a double-quantum-dot qubit in the gigahertz frequency quantum electronics.

Dioxythiophene-based polymer electrodes for supercapacitor modules.

PubMed

Liu, David Y; Reynolds, John R

2010-12-01

We report on the electrochemical and capacitive behaviors of poly(2,2-dimethyl-3,4-propylene-dioxythipohene) (PProDOT-Me2) films as polymeric electrodes in Type I electrochemical supercapacitors. The supercapacitor device displays robust capacitive charging/discharging behaviors with specific capacitance of 55 F/g, based on 60 μg of PProDOT-Me2 per electrode, that retains over 85% of its storage capacity after 32 000 redox cycles at 78% depth of discharge. Moreover, an appreciable average energy density of 6 Wh/kg has been calculated for the device, along with well-behaved and rapid capacitive responses to 1.0 V between 5 to 500 mV s(-1). Tandem electrochemical supercapacitors were assembled in series, in parallel, and in combinations of the two to widen the operating voltage window and to increase the capacitive currents. Four supercapacitors coupled in series exhibited a 4.0 V charging/discharging window, whereas assembly in parallel displayed a 4-fold increase in capacitance. Combinations of both serial and parallel assembly with six supercapacitors resulted in the extension of voltage to 3 V and a 2-fold increase in capacitive currents. Utilization of bipolar electrodes facilitated the encapsulation of tandem supercapacitors as individual, flexible, and lightweight supercapacitor modules.

Electrochemical deposition of silver in room-temperature ionic liquids and its surface-enhanced Raman scattering effect.

PubMed

He, Ping; Liu, Hongtao; Li, Zhiying; Liu, Yang; Xu, Xiudong; Li, Jinghong

2004-11-09

The use of room-temperature ionic liquids (RTILs) as media for electrochemical application is very attractive. In this work, the electrochemical deposition of silver was investigated at a glassy carbon electrode in hydrophobic 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) and hydrophilic 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) RTILs and in KNO3 aqueous solution by cyclic voltammetric and potentiostatic transient techniques. The voltammograms showed the presence of reduction and oxidation peaks associated with the deposition and dissolution of silver from AgBF4 in both BMIMPF6 and BMIMBF(4), resembling the redox behavior of AgNO3 in KNO3 aqueous solution. A crossover loop was observed in all the cyclic voltammograms of these electrochemical systems, indicating a nucleation process. From the analysis of the experimental current transients, it was shown that the electrochemical deposition process of silver in these media was characteristic of 3D nucleation with diffusion-controlled hemispherical growth, and the silver nucleation closely followed the response predicted for progressive nucleation in BMIMPF6 and instantaneous nucleation in KNO3 aqueous solution, respectively. Compared with these two cases, the electrochemical deposition of silver in BMIMBF4 deviated from both the instantaneous and progressive nucleation models, which could be controlled by mixed kinetics and diffusion. On the basis of the experimental results, it was shown that parameters such as viscosity and water miscibility of RTILs would affect the electrodeposition behavior of silver. Atom force microscopy was employed to probe the surface morphology of the silver deposit, and it showed that the shining electrodeposit of silver was fairly dense and separate nanoclusters of <100 nm were in evidence, corresponding to an island growth model. The strongly enhanced Raman scattering from the monolayer film of 4-mercaptobenzoic acid demonstrated that as-prepared silver nanoparticular film was surface-enhanced Raman scattering (SERS) active. The enhancement factor was calculated to be up to 9.0 x 10(5) and 1.0 x 10(6) for the silver film obtained in BMIMPF6 and BMIMBF4 RTILs, respectively.

Submillisecond-response polymer network liquid crystal phase modulators at 1.06-μm wavelength

NASA Astrophysics Data System (ADS)

Sun, Jie; Xianyu, Haiqing; Chen, Yuan; Wu, Shin-Tson

2011-07-01

A fast-response and scattering-free polymer network liquid crystal (PNLC) light modulator is demonstrated at λ = 1.06 μm wavelength. A decay time of 117 μs for 2π phase modulation is obtained at 70 °C, which is ˜ 650 × faster than that of the host nematic LCs. The major tradeoff is the increased operating voltage. Potential applications include spatial light modulators and adaptive optics.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid-liquid microextraction for determination of 2,4,6-trinitrotoluene.

PubMed

Fernández, Elena; Vidal, Lorena; Iniesta, Jesús; Metters, Jonathan P; Banks, Craig E; Canals, Antonio

2014-03-01

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid-liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett-Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L(-1) and 9 μg L(-1), respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L(-1)), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Direct deposit of catalyst on the membrane of direct feed fuel cells

NASA Technical Reports Server (NTRS)

Chun, William (Inventor); Narayanan, Sekharipuram R. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor); Linke, Juergen (Inventor)

2001-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Catalyst utilization and catalyst/membrane interface improvements are disclosed. Specifically, the catalyst layer is applied directly onto the membrane electrolyte.

Ceramic-metal seals for advanced battery systems. [sodium sulfur and lithium sulfur batteries

NASA Technical Reports Server (NTRS)

Reed, L.

1978-01-01

The search for materials which are electrochemically compatible with the lithium sulfur and sodium sulfur systems is discussed. The use liquid or braze alloys, titanium hydrite coatings, and tungsten yttria for bonding beryllium with ceramic is examined.

Parasitic Currents Caused by Different Ionic and Electronic Conductivities in Fuel Cell Anodes.

PubMed

Schalenbach, Maximilian; Zillgitt, Marcel; Maier, Wiebke; Stolten, Detlef

2015-07-29

The electrodes in fuel cells simultaneously realize electric and ionic conductivity. In the case of acidic polymer electrolytes, the electrodes are typically made of composites of carbon-supported catalyst and Nafion polymer electrolyte binder. In this study, the interaction of the proton conduction, the electron conduction, and the electrochemical hydrogen conversion in such composite electrode materials was examined. Exposed to a hydrogen atmosphere, these composites displayed up to 10-fold smaller resistivities for the proton conduction than that of Nafion membranes. This effect was ascribed to the simultaneously occurring electrochemical hydrogen oxidation and evolution inside the composite samples, which are driven by different proton and electron resistivities. The parasitic electrochemical currents resulting were postulated to occur in the anode of fuel cells with polymer, solid oxide, or liquid alkaline electrolytes, when the ohmic drop of the ion conduction in the anode is higher with the anodic kinetic overvoltage (as illustrated in the graphical abstract). In this case, the parasitic electrochemical currents increase the anodic kinetic overpotential and the ohmic drop in the anode. Thinner fuel cell anodes with smaller ohmic drops for the ion conduction may reduce the parasitic electrochemical currents.

A polarization-independent liquid crystal phase modulation using polymer-network liquid crystals in a 90° twisted cell

NASA Astrophysics Data System (ADS)

Lin, Yi-Hsin; Chen, Ming-Syuan; Lin, Wei-Chih; Tsou, Yu-Shih

2012-07-01

A polarization-independent liquid crystal phase modulation using polymer-network liquid crystals in a 90° twisted cell (T-PNLC) is demonstrated. T-PNLC consists of three layers. Liquid crystal (LC) directors in the two layers near glass substrates are orthogonal to each other and those two layers modulate two eigen-polarizations of an incident light. As a result, two eigen-polarizations of an incident light experience the same phase shift. In the middle layer, LC directors are perpendicular to the glass substrate and contribute no phase shift. The phase shift of T-PNLC is electrically tunable and polarization-independent. T-PNLC does not require any bias voltage for operation. The phase shift is 0.28 π rad for the voltage of 30 Vrms. By measuring and analyzing the optical phase shift of T-PNLC at the oblique incidence of transverse magnetic wave, the pretilt angle of LC directors and the effective thickness of three layers are obtained and discussed. The potential applications are spatial light modulators, laser beam steering, and micro-lens arrays.

Colloidal Material Box: In-situ Observations of Colloidal Self-Assembly and Liquid Crystal Phase Transitions in Microgravity

NASA Astrophysics Data System (ADS)

Li, WeiBin; Lan, Ding; Sun, ZhiBin; Geng, BaoMing; Wang, XiaoQing; Tian, WeiQian; Zhai, GuangJie; Wang, YuRen

2016-05-01

To study the self-assembly behavior of colloidal spheres in the solid/liquid interface and elucidate the mechanism of liquid crystal phase transition under microgravity, a Colloidal Material Box (CMB) was designed which consists of three modules: (i) colloidal evaporation experimental module, made up of a sample management unit, an injection management unit and an optical observation unit; (ii) liquid crystal phase transition experimental module, including a sample management unit and an optical observation unit; (iii) electronic control module. The following two experimental plans will be performed inside the CMB aboard the SJ-10 satellite in space. (i) Self-assembly of colloidal spheres (with and without Au shell) induced by droplet evaporation, allowing observation of the dynamic process of the colloidal spheres within the droplet and the change of the droplet outer profile during evaporation; (ii) Phase behavior of Mg2Al LDHs suspensions in microgravity. The experimental results will be the first experimental observations of depositing ordered colloidal crystals and their self-assembly behavior under microgravity, and will illustrate the influence of gravity on liquid crystal phase transition.

Electropolymerization of high stable poly(3,4-ethylenedioxythiophene) in ionic liquids and its potential applications in electrochemical capacitor

NASA Astrophysics Data System (ADS)

Liu, Keke; Hu, Zhenglong; Xue, Rong; Zhang, Jianrong; Zhu, Junjie

2008-05-01

Poly(3,4-ethylenedioxythiophene) (PEDOT) has been successfully electropolymerized using a purified 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) as both the growth medium and the supporting electrolyte. The electrochemical performance of the PEDOT thin film was investigated in 1 mol L-1 H2SO4 solution. It possesses nearly ideal capacitive property, and its specific capacitance is about 130 F g-1. Compared with other conducting polymers, enhanced cycling lifetime (up to 70,000 cycles), which is close to that of active carbon materials, was observed on repetitive redox cycling.

Metal/Metal Oxide Differential Electrode pH Sensors

NASA Technical Reports Server (NTRS)

West, William; Buehler, Martin; Keymeulen, Didier

2007-01-01

Solid-state electrochemical sensors for measuring the degrees of acidity or alkalinity (in terms of pH values) of liquid solutions are being developed. These sensors are intended to supplant older electrochemical pH sensors that include glass electrode structures and reference solutions. The older sensors are fragile and subject to drift. The present developmental solid-state sensors are more rugged and are expected to be usable in harsh environments. The present sensors are based on a differential-electrode measurement principle. Each sensor includes two electrodes, made of different materials, in equilibrium with the solution of interest.

Characterization of submillisecond response optical addressing phase modulator based on low light scattering polymer network liquid crystal

NASA Astrophysics Data System (ADS)

Xiangjie, Zhao; Cangli, Liu; Jiazhu, Duan; Dayong, Zhang; Yongquan, Luo

2015-01-01

Optically addressed conventional nematic liquid crystal spatial light modulator has attracted wide research interests. But the slow response speed limited its further application. In this paper, polymer network liquid crystal (PNLC) was proposed to replace the conventional nematic liquid crystal to enhance the response time to the order of submillisecond. The maximum light scattering of the employed PNLC was suppressed to be less than 2% at 1.064 μm by optimizing polymerization conditions and selecting large viscosity liquid crystal as solvent. The occurrence of phase ripple phenomenon due to electron diffusion and drift in photoconductor was found to deteriorate the phase modulation effect of the optical addressed PNLC phase modulator. The wavelength effect and AC voltage frequency effect on the on state dynamic response of phase change was investigated by experimental methods. These effects were interpreted by electron diffusion and drift theory based on the assumption that free electron was inhomogeneously distributed in accordance with the writing beam intensity distribution along the incident direction. The experimental results indicated that the phase ripple could be suppressed by optimizing the wavelength of the writing beam and the driving AC voltage frequency when varying the writing beam intensity to generate phase change in 2π range. The modulation transfer function was also measured.

Holographic zoom system based on spatial light modulator and liquid device

NASA Astrophysics Data System (ADS)

Wang, Di; Li, Lei; Liu, Su-Juan; Wang, Qiong-Hua

2018-02-01

In this paper, two holographic zoom systems are proposed based on the programmability of spatial light modulator (SLM) and zoom characteristics of liquid lens. An active optical zoom system is proposed in which the zoom module is composed of a liquid lens and an SLM. By controlling the focal lengths of the liquid lens and the encoded digital lens on the SLM, we can change the magnification of an image without mechanical moving parts and keep the output plane stationary. Then a color holographic zoom system based on a liquid lens is proposed. The system processes the color separation of the original object for red, green, and blue components and generated three holograms respectively. A new hologram with specific reconstructed distance can be generated by combing the hologram of the digital lens with the hologram of the image. By controlling the focal lengths of the liquid lens and the encoded digital lens on the SLM, we can change the magnification of the reconstructed image.

Ionic liquids and derived materials for lithium and sodium batteries.

PubMed

Yang, Qiwei; Zhang, Zhaoqiang; Sun, Xiao-Guang; Hu, Yong-Sheng; Xing, Huabin; Dai, Sheng

2018-03-21

The ever-growing demand for advanced energy storage devices in portable electronics, electric vehicles and large scale power grids has triggered intensive research efforts over the past decade on lithium and sodium batteries. The key to improve their electrochemical performance and enhance the service safety lies in the development of advanced electrode, electrolyte, and auxiliary materials. Ionic liquids (ILs) are liquids consisting entirely of ions near room temperature, and are characterized by many unique properties such as ultralow volatility, high ionic conductivity, good thermal stability, low flammability, a wide electrochemical window, and tunable polarity and basicity/acidity. These properties create the possibilities of designing batteries with excellent safety, high energy/power density and long-term stability, and also provide better ways to synthesize known materials. IL-derived materials, such as poly(ionic liquids), ionogels and IL-tethered nanoparticles, retain most of the characteristics of ILs while being endowed with other favourable features, and thus they have received a great deal of attention as well. This review provides a comprehensive review of the various applications of ILs and derived materials in lithium and sodium batteries including Li/Na-ion, dual-ion, Li/Na-S and Li/Na-air (O 2 ) batteries, with a particular emphasis on recent advances in the literature. Their unique characteristics enable them to serve as advanced resources, medium, or ingredient for almost all the components of batteries, including electrodes, liquid electrolytes, solid electrolytes, artificial solid-electrolyte interphases, and current collectors. Some thoughts on the emerging challenges and opportunities are also presented in this review for further development.

Bragg stack-functionalized counter electrode for solid-state dye-sensitized solar cells.

PubMed

Park, Jung Tae; Prosser, Jacob H; Kim, Dong Jun; Kim, Jong Hak; Lee, Daeyeon

2013-05-01

A highly reflective counter electrode is prepared through the deposition of alternating layers of organized mesoporous TiO(2) (om-TiO(2)) and colloidal SiO(2) (col-SiO(2)) nanoparticles. We present the effects of introducing this counter electrode into dye-sensitized solar cells (DSSCs) for maximizing light harvesting properties. The om-TiO(2) layers with a high refractive index are prepared by using an atomic transfer radical polymerization and a sol-gel process, in which a polyvinyl chloride-g-poly(oxyethylene) methacrylate graft copolymer is used as a structure-directing agent. The col-SiO(2) layers with a low refractive index are prepared by spin-coating commercially available silica nanoparticles. The properties of the Bragg stack (BS)-functionalized counter electrode in DSSCs are analyzed by using a variety of techniques, including spectroscopic ellipsometry, SEM, UV/Vis spectroscopy, incident photon-to-electron conversion efficiency, electrochemical impedance spectroscopy, and intensity modulated photocurrent/voltage spectroscopy measurements, to understand the critical factors contributing to the cell performance. When incorporated into DSSCs that are used in conjunction with a polymerized ionic liquid as the solid electrolyte, the energy conversion efficiency of this solid-state DSSC (ssDSSC) approaches 6.6 %, which is one of the highest of the reported N719 dye-based ssDSSCs. Detailed optical and electrochemical analyses of the device performance show that this assembly yields enhanced light harvesting without the negative effects of charge recombination or electrolyte penetration, which thus, presents new possibilities for effective light management. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Processes Enhanced by Acoustic Liquid Manipulation

NASA Technical Reports Server (NTRS)

Oeftering, Richard C.

2004-01-01

Acoustic liquid manipulation is a family of techniques that employ the nonlinear acoustic effects of acoustic radiation pressure and acoustic streaming to manipulate the behavior of liquids. Researchers at the NASA Glenn Research Center are exploring new methods of manipulating liquids for a variety of space applications, and we have found that acoustic techniques may also be used in the normal Earth gravity environment to enhance the performance of existing fluid processes. Working in concert with the NASA Commercial Technology Office, the Great Lakes Industrial Technology Center, and Alchemitron Corporation (Elgin, IL), researchers at Glenn have applied nonlinear acoustic principles to industrial applications. Collaborating with Alchemitron Corporation, we have adapted the devices to create acoustic streaming in a conventional electroplating process.

Emerging Applications of Liquid Metals Featuring Surface Oxides

PubMed Central

2014-01-01

Gallium and several of its alloys are liquid metals at or near room temperature. Gallium has low toxicity, essentially no vapor pressure, and a low viscosity. Despite these desirable properties, applications calling for liquid metal often use toxic mercury because gallium forms a thin oxide layer on its surface. The oxide interferes with electrochemical measurements, alters the physicochemical properties of the surface, and changes the fluid dynamic behavior of the metal in a way that has, until recently, been considered a nuisance. Here, we show that this solid oxide “skin” enables many new applications for liquid metals including soft electrodes and sensors, functional microcomponents for microfluidic devices, self-healing circuits, shape-reconfigurable conductors, and stretchable antennas, wires, and interconnects. PMID:25283244

Efficient platinum-free counter electrodes for dye-sensitized solar cell applications.

PubMed

Ahmad, Shahzada; Yum, Jun-Ho; Butt, Hans-Jürgen; Nazeeruddin, Mohammad K; Grätzel, Michael

2010-09-10

Nanoporous layers of poly(3,4-propylenedioxythiophene) (PProDOT) were fabricated by electrical-field-assisted growth using hydrophobic ionic liquids as the growing medium. A series of PProDoT layers was prepared with three different ionic liquids to control the microstructure and electrochemical properties of the resulting dye-sensitized solar cells, which were highly efficient and showed a power conversion efficiency of >9% under different sunlight intensities. The current-voltage characteristics of the counter electrodes varied depending on the ionic liquids used in the synthesis of PProDOT. The most hydrophobic ionic liquids exhibited high catalytic properties, thus resulting in high power conversion efficiency and allowing the fabrication of platinum-free, stable, flexible, and cost-effective dye-sensitized solar cells.

Lithium-Air and ionic Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kellar, Michael

2015-09-01

The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to themore » typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.« less

A polarization-independent liquid crystal phase modulation using polymer-network liquid crystal with orthogonal alignment layers

NASA Astrophysics Data System (ADS)

Chen, Ming-Syuan; Lin, Wei-Chih; Tsou, Yu-Shih; Lin, Yi-Hsin

2012-10-01

A polarization-independent liquid crystal (LC) phase modulation using polymer-network liquid crystals with orthogonal alignments layers (T-PNLC) is demonstrated. T-PNLC consists of three layers. LC directors in the two layers near glass substrates are orthogonal to each other. In the middle layer, LC directors are perpendicular to the glass substrate. The advantages of such T-PNLC include polarizer-free, larger phase shift (~0.4π rad) than the residual phase type (<0.05π rad), and low operating voltage (< 30Vrms). It does not require bias voltage for avoiding scattering because the refractive index of liquid crystals matches that of polymers. The phase shift of T-PNLC is affected by the cell gap and the curing voltages. The potential applications are laser beam steering, spatial light modulators and electrically tunable micro-lens arrays.

Amorphous-silicon module intercell corrosion

NASA Astrophysics Data System (ADS)

Mon, G. R.; Ross, R. G.

1987-06-01

Three non-electrochemical, moisture-induced a-Si module degradation modes have been observed and their mechanisms studied: (1) the formation and growth of pinholes in the thin-film layers; (2) the directional interfusion of pinholes along process scribe lines to form metallization-free regions that tend to open-circuit the module; and (3) worm-like filiform corrosion in the aluminum layer. The dependency on time-of-exposure to moist environments of the amount of material erosion in the module intercell zone has been quantified by two methods—directly by EDS analysis, and indirectly by sheet resistivity measurements on fully aluminized back surface modules. In addition, changes in maximum power output, series resistance, and open circuit voltage have been documented. Consequences for fielded modules are discussed.

Electrolyte materials containing highly dissociated metal ion salts

DOEpatents

Lee, H.S.; Geng, L.; Skotheim, T.A.

1996-07-23

The present invention relates to metal ion salts which can be used in electrolytes for producing electrochemical devices, including both primary and secondary batteries, photoelectrochemical cells and electrochromic displays. The salts have a low energy of dissociation and may be dissolved in a suitable polymer to produce a polymer solid electrolyte or in a polar aprotic liquid solvent to produce a liquid electrolyte. The anion of the salts may be covalently attached to polymer backbones to produce polymer solid electrolytes with exclusive cation conductivity. 2 figs.

Copper Chloride Cathode For Liquid-Sodium Cell

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V.; Distefano, Salvador; Nagasubramanian, Ganesan; Bankston, Clyde P.

1990-01-01

Rechargeable liquid-sodium cell with copper chloride cathode offers substantial increase in energy density over cells made with other cathode materials. Unit has theoretical maximum energy density of 1135 W.h/kg. Generates electricity by electrochemical reaction of molten sodium and solid copper chloride immersed in molten electrolyte, sodium tetrachloroaluminate at temperature of equal to or greater than 200 degrees C. Wall of alumina tube separates molten electrolyte from molten sodium anode. Copper chloride cathode embedded in pores of sintered nickel cylinder or directly sintered.

Ionic liquids and their solid-state analogues as materials for energy generation and storage

NASA Astrophysics Data System (ADS)

Macfarlane, Douglas R.; Forsyth, Maria; Howlett, Patrick C.; Kar, Mega; Passerini, Stefano; Pringle, Jennifer M.; Ohno, Hiroyuki; Watanabe, Masayoshi; Yan, Feng; Zheng, Wenjun; Zhang, Shiguo; Zhang, Jie

2016-02-01

Salts that are liquid at room temperature, now commonly called ionic liquids, have been known for more than 100 years; however, their unique properties have only come to light in the past two decades. In this Review, we examine recent work in which the properties of ionic liquids have enabled important advances to be made in sustainable energy generation and storage. We discuss the use of ionic liquids as media for synthesis of electromaterials, for example, in the preparation of doped carbons, conducting polymers and intercalation electrode materials. Focusing on their intrinsic ionic conductivity, we examine recent reports of ionic liquids used as electrolytes in emerging high-energy-density and low-cost batteries, including Li-ion, Li-O2, Li-S, Na-ion and Al-ion batteries. Similar developments in electrolyte applications in dye-sensitized solar cells, thermo-electrochemical cells, double-layer capacitors and CO2 reduction are also discussed.

A novel X-ray diffractometer for studies of liquid-liquid interfaces.

PubMed

Murphy, Bridget M; Greve, Matthais; Runge, Benjamin; Koops, Christian T; Elsen, Annika; Stettner, Jochim; Seeck, Oliver H; Magnussen, Olaf M

2014-01-01

The study of liquid-liquid interfaces with X-ray scattering methods requires special instrumental considerations. A dedicated liquid surface diffractometer employing a tilting double-crystal monochromator in Bragg geometry has been designed. This diffractometer allows reflectivity and grazing-incidence scattering measurements of an immobile mechanically completely decoupled liquid sample, providing high mechanical stability. The available energy range is from 6.4 to 29.4 keV, covering many important absorption edges. The instrument provides access in momentum space out to 2.54 Å(-1) in the surface normal and out to 14.8 Å(-1) in the in-plane direction at 29.4 keV. Owing to its modular design the diffractometer is also suitable for heavy apparatus such as vacuum chambers. The instrument performance is described and examples of X-ray reflectivity studies performed under in situ electrochemical control and on biochemical model systems are given.

Corrosion Inhibition of Cast Iron in Arabian Gulf Seawater by Two Different Ionic Liquids

PubMed Central

Sherif, El-Sayed M.; Abdo, Hany S.; Zein El Abedin, Sherif

2015-01-01

In this paper we report on the corrosion inhibition of cast iron in Arabian Gulf seawater by two different ionic liquids namely, 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) and 1-butyl-1-methylpyrrolidinium chloride ([Py1,4]Cl). The inhibiting influence of the employed ionic liquids was investigated by weight loss, open circuit potential electrochemical impedance spectroscopy, and cyclic potentiodynamic polarization. The results show the corrosion inhibition impact of the employed ionic liquids (ILs). Compared with [Py1,4]Cl, [EMIm]Cl shows a higher inhibition efficiency at a short immersion time, for the examined ILs concentrations. However, [Py1,4]Cl exhibits a higher efficiency upon increasing the immersion time indicating the persistence of the inhibiting influence. The corrosion inhibition of the employed ionic liquids is attributed to the adsorption of the cations of the ionic liquids onto the surface of cast iron forming a corrosion barrier. PMID:28793413

Ionic liquid as an electrolyte additive for high performance lead-acid batteries

NASA Astrophysics Data System (ADS)

Deyab, M. A.

2018-06-01

The performance of lead-acid battery is improved in this work by inhibiting the corrosion of negative battery electrode (lead) and hydrogen gas evolution using ionic liquid (1-ethyl-3-methylimidazolium diethyl phosphate). The results display that the addition of ionic liquid to battery electrolyte (5.0 M H2SO4 solution) suppresses the hydrogen gas evolution to very low rate 0.049 ml min-1 cm-2 at 80 ppm. Electrochemical studies show that the adsorption of ionic liquid molecules on the lead electrode surface leads to the increase in the charge transfer resistance and the decrease in the double layer capacitance. I also notice a noteworthy improvement of battery capacity from 45 mAh g-1 to 83 mAh g-1 in the presence of ionic liquid compound. Scanning electron microscopy and energy dispersive X-ray analysis confirm the adsorption of ionic liquid molecules on the battery electrode surface.

Proton-conducting ionic liquid-based Proton Exchange Membrane Fuel Cell membranes: The key role of ionomer-ionic liquid interaction

NASA Astrophysics Data System (ADS)

Martinez, Mathieu; Molmeret, Yannick; Cointeaux, Laure; Iojoiu, Cristina; Leprêtre, Jean-Claude; El Kissi, Nadia; Judeinstein, Patrick; Sanchez, Jean-Yves

The paper deals with the synthesis and characterisation of proton-conducting ionic liquids (PCILs) and their polymer electrolytes obtained by blending modified Nafion membranes with different concentrations of PCILs. The PCILs are obtained by the neutralization of triethylamine with different organic acids. The first part of the paper studies the influence of acidity and acid structure on PCIL thermal and electrochemical performance, while the second part examines membrane conductivity and reveals it to depend more on PCIL structure than on its intrinsic conductivity. At 130 °C, conductivities exceeding 10 mS cm -1 were obtained in fully anhydrous conditions.

An optical microsystem based on vertical silicon-air Bragg mirror for liquid substances monitoring

NASA Astrophysics Data System (ADS)

De Stefano, Luca; Rendina, Ivo; Rea, Ilaria; Rotiroti, Lucia; De Tommasi, Edoardo; Barillaro, Giuseppe

2007-05-01

In this work, an integrated optical microsystems for the continuous detection of flammable liquids has been fabricated and characterized. The proposed system is composed of a the transducer element, which is a vertical silicon/air Bragg mirror fabricated by silicon electrochemical micromachining, sealed with a cover glass anodically bonded on its top. The device has been optically characterized in presence of liquid substances of environmental interest, such as ethanol and isopropanol. The preliminary experimental results are in good agreement with the theoretical calculations and show the possibility to use the device as an optical sensor based on the change of its reflectivity spectrum.

Spin coating of electrolytes

DOEpatents

Stetter, Joseph R.; Maclay, G. Jordan

1989-01-01

Methods for spin coating electrolytic materials onto substrates are disclosed. More particularly, methods for depositing solid coatings of ion-conducting material onto planar substrates and onto electrodes are disclosed. These spin coating methods are employed to fabricate electrochemical sensors for use in measuring, detecting and quantifying gases and liquids.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strelcov, Evgheni; Cothren, Joshua E.; Leonard, Donovan N.

Progress in rational engineering of Li-ion batteries requires better understanding of the electrochemical processes and accompanying transformations in the electrode materials on multiple length scales. In spite of recent progress in utilizing transmission electron microscopy (TEM) to analyze these materials, in situ scanning electron microscopy (SEM) was mostly overlooked as a powerful tool that allows probing these phenomena on the nano and mesoscale. In this paper, we report on in situ SEM study of lithiation in a V 2O 5-based single-nanobelt battery with ionic liquid electrolyte. Coupled with cyclic voltammetry measurements, in situ SEM revealed the peculiarities of subsurface intercalation,more » formation of solid-electrolyte interface (SEI) and electromigration of liquid. We observed that single-crystalline vanadia nanobelts do not undergo large-scale amorphization or fracture during electrochemical cycling, but rather transform topochemically with only a slight shape distortion. Lastly, the SEI layer seems to have significant influence on the lithium ion diffusion and overall capacity of the single-nanobelt battery.« less

Determination of acrylamide and acrylic acid by isocratic liquid chromatography with pulsed electrochemical detection.

PubMed

Casella, Innocenzo G; Pierri, Marianna; Contursi, Michela

2006-02-24

The electrochemical behaviour of the polycrystalline platinum electrode towards the oxidation/reduction of short-chain unsaturated aliphatic molecules such as acrylamide and acrylic acid was investigated in acidic solutions. Analytes were separated by reverse phase liquid chromatographic and quantified using a pulsed amperometric detection. A new two-step waveform, is introduced for detection of acrylamide and acrylic acid. Detection limits (LOD) of 20 nM (1. 4 microg/kg) and 45 nM (3.2 microg/kg) were determined in water solutions containing acrylamide and acrylic acid, respectively. Compared to the classical three-step waveform, the proposed two-step waveform shows favourable analytical performance in terms of LOD, linear range, precision and improved long-term reproducibility. The proposed analytical method combined with clean-up procedure accomplished by Carrez clearing reagent and subsequent extraction with a strong cation exchanger cartridges (SPE), was successfully used for the quantification of low concentrations of acrylamide in foodstuffs such as coffee and potato fries.

Electrochemical disinfection of repeatedly recycled blackwater in a free‐standing, additive‐free toilet

PubMed Central

Sellgren, Katelyn L.; Klem, Ethan J. D.; Piascik, Jeffrey R.; Stoner, Brian R.

2017-01-01

Abstract Decentralized, energy‐efficient waste water treatment technologies enabling water reuse are needed to sustainably address sanitation needs in water‐ and energy‐scarce environments. Here, we describe the effects of repeated recycling of disinfected blackwater (as flush liquid) on the energy required to achieve full disinfection with an electrochemical process in a prototype toilet system. The recycled liquid rapidly reached a steady state with total solids reliably ranging between 0.50 and 0.65% and conductivity between 20 and 23 mS/cm through many flush cycles over 15 weeks. The increase in accumulated solids was associated with increased energy demand and wide variation in the free chlorine contact time required to achieve complete disinfection. Further studies on the system at steady state revealed that running at higher voltage modestly improves energy efficiency, and established running parameters that reliably achieve disinfection at fixed run times. These results will guide prototype testing in the field. PMID:29242713

Poly(ionic liquids) functionalized polypyrrole/graphene oxide nanosheets for electrochemical sensor to detect dopamine in the presence of ascorbic acid.

PubMed

Mao, Hui; Liang, Jiachen; Zhang, Haifeng; Pei, Qi; Liu, Daliang; Wu, Shuyao; Zhang, Yu; Song, Xi-Ming

2015-08-15

Novel poly(ionic liquids) functionalized polypyrrole/graphene oxide nanosheets (PILs/PPy/GO) were prepared by the polymerization of 1-vinyl-3-ethylimidazole bromide (VEIB) on the surface of N-vinyl imidazolium modified PPy/GO nanosheets. Due to the synergistic effects of GO with well-defined lamellar structures, conductive PPy and biocompatible PILs, PILs/PPy/GO modified glassy carbon electrode (GCE) presented the excellent electrochemical catalytic activity towards dopamine (DA) with good stability, high sensitivity and wide linear range in the present of ascorbic acid (AA) with high concentration. PILs played an essential role for the simultaneous determination of DA and AA in a mixture, whose existence effectively improved the transmission mode of electrons and resulted in the different electrocatalytic performance towards the oxidation of DA and AA. It is indicated that PILs/PPy/GO nanosheets can act as a good steady and sensitive electrode material for the development of improved DA sensors. Copyright © 2015 Elsevier B.V. All rights reserved.

Phenomenological Transition of an Aluminum Surface in an Ionic Liquid and Its Beneficial Implementation in Batteries.

PubMed

Shvartsev, B; Gelman, D; Amram, D; Ein-Eli, Y

2015-12-29

Aluminum (Al) electrochemical dissolution in organic nonaqueous media and room temperature ionic liquids (RTILs) is partially hampered by the presence of a native oxide. In this work, Al activation in EMIm(HF)2.3F RTIL is reported. It was confirmed that as a result of the interaction of Al with the RTIL, a new film is formed instead of the pristine oxide layer. Aluminum surface modifications result in a transformation from a passive state to the active behavior of the metal. This was confirmed via the employment of electrochemical methods and characterization by XPS, AFM, and TEM. It was shown that the pristine oxide surface film dissolves in EMIm(HF)2.3F, allowing an Al-O-F layer to be formed instead. This newly built up layer dramatically restricts Al corrosion while enabling high rates of Al anodic dissolution. These beneficial features allow the implementation of Al as an anode in advanced portable power sources, such as aluminum-air batteries.

Simultaneous analysis of guaiacol and vanillin in a vanilla extract by using high-performance liquid chromatography with electrochemical detection.

PubMed

Takahashi, Makoto; Sakamaki, Shizuka; Fujita, Akira

2013-01-01

We developed and validated a new high-performance liquid chromatographic analysis for electrochemically detecting guaiacol and vanillin as important components in vanilla extract. Separation was achieved with Capcell Pak C-18 MG, the potential of the working electrode being set at +1000 mV. The respective calibration curves for guaiacol and vanillin were linear in the range of 1.60-460 µg/L and 5.90-1180 µg/L. The respective limits for the quantities of guaiacol and vanillin were 1.60 µg/L and 2.36 µg/L. The related standard deviations of the intra- and inter-day precision of the retention time and peak area were all less than 4%. The recovery of guaiacol and vanillin was both more than 97%, all of the validation data being within an acceptable range. This analysis method is well suited for the simultaneous and convenient analysis of guaiacol and vanillin in a vanilla extract to evaluate the quality of the vanilla extract.

High-performance liquid chromatographic separation and electrochemical or spectrophotometric determination of R(-)N-n-propylnorapomorphine and R(-)10,11-methylenedioxy-N-n-propylnoraporphine in primate plasma.

PubMed

Lampen, P; Neumeyer, J L; Baldessarini, R J

1988-04-29

The dopamine receptor agonist R(-)N-n-propylnorapomorphine (NPA) and its proposed pro-drug R(-)10,11-methylenedioxy-N-n-propylnoraporphine (MDO-NPA) were isolated simultaneously from monkey plasma using a solid-phase extraction procedure. R(-)Apomorphine (APO) and R(-)10,11-methylenedioxyaporphine (MDO-APO) were added as internal standards, and separation and quantification were by high-performance liquid chromatography with electrochemical or ultraviolet detection of the free catechol and MDO compounds, respectively. The detection limits for NPA and MDO-NPA in plasma were 0.5 and 10 ng/ml and the coefficient of variation (S.D./mean) within assays and between days of assays for both drugs was 5.6% or less. Quantification of plasma levels of NPA and MDO-NPA was possible at ranges of 2-1000 and 40-5000 ng/ml, respectively, including concentrations found after intravenous administration of these agents.

Suspended Silicon Microphotodiodes for Electrochemical and Biological Applications.

PubMed

Vargas-Estevez, Carolina; Duch, Marta; Duque, Marcos; Del Campo, Francisco Javier; Enriquez-Barreto, Lilian; Murillo, Gonzalo; Torras, Núria; Plaza, José A; Saura, Carlos A; Esteve, Jaume

2017-11-01

Local electric stimulation of tissues and cells has gained importance as therapeutic alternative in the treatment of many diseases. These alternatives aim to deliver a less invasively stimuli in liquid media, making imperative the development of versatile micro- and nanoscale solutions for wireless actuation. Here, a simple microfabrication process to produce suspended silicon microphotodiodes that can be activated by visible light to generate local photocurrents in their surrounding medium is presented. Electrical characterization using electrical probes confirms their diode behavior. To demonstrate their electrochemical performance, an indirect test is implemented in solution through photoelectrochemical reactions controlled by a white-LED lamp. Furthermore, their effects on biological systems are observed in vitro using mouse primary neurons in which the suspended microphotodiodes are activated periodically with white-LED lamp, bringing out observable morphological changes in neuronal processes. The results demonstrate a simplified and cost-effective wireless tool for photovoltaic current generation in liquid media at the microscale. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A stable room-temperature sodium-sulfur battery.

PubMed

Wei, Shuya; Xu, Shaomao; Agrawral, Akanksha; Choudhury, Snehashis; Lu, Yingying; Tu, Zhengyuan; Ma, Lin; Archer, Lynden A

2016-06-09

High-energy rechargeable batteries based on earth-abundant materials are important for mobile and stationary storage technologies. Rechargeable sodium-sulfur batteries able to operate stably at room temperature are among the most sought-after platforms because such cells take advantage of a two-electron-redox process to achieve high storage capacity from inexpensive electrode materials. Here we report a room-temperature sodium-sulfur battery that uses a microporous carbon-sulfur composite cathode, and a liquid carbonate electrolyte containing the ionic liquid 1-methyl-3-propylimidazolium-chlorate tethered to SiO2 nanoparticles. We show that these cells can cycle stably at a rate of 0.5 C (1 C=1675, mAh g(-1)) with 600 mAh g(-1) reversible capacity and nearly 100% Coulombic efficiency. By means of spectroscopic and electrochemical analysis, we find that the particles form a sodium-ion conductive film on the anode, which stabilizes deposition of sodium. We also find that sulfur remains interred in the carbon pores and undergo solid-state electrochemical reactions with sodium ions.

Longitudinal On-Column Thermal Modulation for Comprehensive Two-Dimensional Liquid Chromatography.

PubMed

Creese, Mari E; Creese, Mathew J; Foley, Joe P; Cortes, Hernan J; Hilder, Emily F; Shellie, Robert A; Breadmore, Michael C

2017-01-17

Longitudinal on-column thermal modulation for comprehensive two-dimensional liquid chromatography is introduced. Modulation optimization involved a systematic investigation of heat transfer, analyte retention, and migration velocity at a range of temperatures. Longitudinal on-column thermal modulation was realized using a set of alkylphenones and compared to a conventional valve-modulator employing sample loops. The thermal modulator showed a reduced modulation-induced pressure impact than valve modulation, resulting in reduced baseline perturbation by a factor of 6; yielding a 6-14-fold improvement in signal-to-noise. A red wine sample was analyzed to demonstrate the potential of the longitudinal on-column thermal modulator for separation of a complex sample. Discrete peaks in the second dimension using the thermal modulator were 30-55% narrower than with the valve modulator. The results shown herein demonstrate the benefits of an active focusing modulator, such as reduced detection limits and increased total peak capacity.

Frequency modulation detection atomic force microscopy in the liquid environment

NASA Astrophysics Data System (ADS)

Jarvis, S. P.; Ishida, T.; Uchihashi, T.; Nakayama, Y.; Tokumoto, H.

True atomic resolution imaging using frequency modulation detection is already well established in ultra-high vacuum. In this paper we demonstrate that it also has great potential in the liquid environment. Using a combination of magnetic activation and high-aspect-ratio carbon nanotube probes, we show that imaging can be readily combined with point spectroscopy, revealing both the tip-sample interaction and the structure of the intermediate liquid.

Moisture-temperature degradation in module encapsulants: The general problem of moisture in photovoltaic encapsulants

NASA Technical Reports Server (NTRS)

Mon, G. R.

1985-01-01

A general research approach was outlined toward understanding water-module interactions and the influence of temperature involving the need to: quantify module performance loss versus level of accumulated degradation, establish the dependence of the degradation reaction rate on module moisture and temperature levels, and determine module moisture and temperature levels in field environments. These elements were illustrated with examples drawn from studies of the now relatively well understood module electrochemical degradation process. Research data presented include temperature and humidity-dependent equilibrium leakage current values for multiparameter module material and design configurations. The contributions of surface, volume, and interfacial conductivities was demonstrated. Research directions were suggested to more fully understand the contributions to overall module conductivity of surface, volume, and interfacial conductivities over ranges of temperature and relative humidity characteristic of field environments.

Rapid Measurement of Room Temperature Ionic Liquid Electrochemical Gas Sensor using Transient Double Potential Amperometry

PubMed Central

Wan, Hao; Yin, Heyu; Mason, Andrew J.

2016-01-01

Intense study on gas sensors has been conducted to implement fast gas sensing with high sensitivity, reliability and long lifetime. This paper presents a rapid amperometric method for gas sensing based on a room temperature ionic liquid electrochemical gas sensor. To implement a miniaturized sensor with a fast response time, a three electrode system with gold interdigitated electrodes was fabricated by photolithography on a porous polytetrafluoroethylene substrate that greatly enhances gas diffusion. Furthermore, based on the reversible reaction of oxygen, a new transient double potential amperometry (DPA) was explored for electrochemical analysis to decrease the measurement time and reverse reaction by-products that could cause current drift. Parameters in transient DPA including oxidation potential, oxidation period, reduction period and sample point were investigated to study their influence on the performance of the sensor. Oxygen measurement could be accomplished in 4 s, and the sensor presented a sensitivity of 0.2863 μA/[%O2] and a linearity of 0.9943 when tested in air samples with different oxygen concentrations. Repeatability and long-term stability were also investigated, and the sensor was shown to exhibit good reliability. In comparison to conventional constant potential amperometry, transient DPA was shown to reduce relative standard deviation by 63.2%. With transient DPA, the sensitivity, linearity, repeatability, measurement time and current drift characteristics demonstrated by the presented gas sensor are promising for acute exposure applications. PMID:28603384

Electrochemical Reduction of Oxygen in Aprotic Ionic Liquids Containing Metal Cations: A Case Study on the Na-O2 system.

PubMed

Azaceta, Eneko; Lutz, Lukas; Grimaud, Alexis; Vicent-Luna, Jose Manuel; Hamad, Said; Yate, Luis; Cabañero, German; Grande, Hans-Jurgen; Anta, Juan A; Tarascon, Jean-Marie; Tena-Zaera, Ramon

2017-04-10

Metal-air batteries are intensively studied because of their high theoretical energy-storage capability. However, the fundamental science of electrodes, electrolytes, and reaction products still needs to be better understood. In this work, the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) was chosen to study the influence of a wide range of metal cations (M n+ ) on the electrochemical behavior of oxygen. The relevance of the theory of Lewis hard and soft acids and bases to predict satisfactorily the reduction potential of oxygen in electrolytes containing metal cations is demonstrated. Systems with soft and intermediate M n+ acidity are shown to facilitate oxygen reduction and metal oxide formation, whereas oxygen reduction is hampered by hard acid cations such as sodium and lithium. Furthermore, DFT calculations on the energy of formation of the resulting metal oxides rationalize the effect of M n+ on oxygen reduction. A case study on the Na-O 2 system is described in detail. Among other things, the Na + concentration of the electrolyte is shown to control the electrochemical pathway (solution precipitation vs. surface deposition) by which the discharge product grows. All in all, fundamental insights for the design of advanced electrolytes for metal-air batteries, and Na-air batteries in particular, are provided. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid Measurement of Room Temperature Ionic Liquid Electrochemical Gas Sensor using Transient Double Potential Amperometry.

PubMed

Wan, Hao; Yin, Heyu; Mason, Andrew J

2017-04-01

Intense study on gas sensors has been conducted to implement fast gas sensing with high sensitivity, reliability and long lifetime. This paper presents a rapid amperometric method for gas sensing based on a room temperature ionic liquid electrochemical gas sensor. To implement a miniaturized sensor with a fast response time, a three electrode system with gold interdigitated electrodes was fabricated by photolithography on a porous polytetrafluoroethylene substrate that greatly enhances gas diffusion. Furthermore, based on the reversible reaction of oxygen, a new transient double potential amperometry (DPA) was explored for electrochemical analysis to decrease the measurement time and reverse reaction by-products that could cause current drift. Parameters in transient DPA including oxidation potential, oxidation period, reduction period and sample point were investigated to study their influence on the performance of the sensor. Oxygen measurement could be accomplished in 4 s, and the sensor presented a sensitivity of 0.2863 μA/[%O 2 ] and a linearity of 0.9943 when tested in air samples with different oxygen concentrations. Repeatability and long-term stability were also investigated, and the sensor was shown to exhibit good reliability. In comparison to conventional constant potential amperometry, transient DPA was shown to reduce relative standard deviation by 63.2%. With transient DPA, the sensitivity, linearity, repeatability, measurement time and current drift characteristics demonstrated by the presented gas sensor are promising for acute exposure applications.

Force modulation and electrochemical gating of conductance in a cytochrome

NASA Astrophysics Data System (ADS)

Davis, Jason J.; Peters, Ben; Xi, Wang

2008-09-01

Scanning probe methods have been used to measure the effect of electrochemical potential and applied force on the tunnelling conductance of the redox metalloprotein yeast iso-1-cytochrome c (YCC) at a molecular level. The interaction of a proximal probe with any sample under test will, at this scale, be inherently perturbative. This is demonstrated with conductive probe atomic force microscopy (CP-AFM) current-voltage spectroscopy in which YCC, chemically adsorbed onto pristine Au(111) via its surface cysteine residue, is observed to become increasingly compressed as applied load is increased, with concomitant decrease in junction resistance. Electrical contact at minimal perturbation, where probe-molecule coupling is comparable to that in scanning tunnelling microscopy, brings with it the observation of negative differential resistance, assigned to redox-assisted probe-substrate tunnelling. The role of the redox centre in conductance is also resolved in electrochemical scanning tunnelling microscopy assays where molecular conductance is electrochemically gateable through more than an order of magnitude.

Low voltage polymer network liquid crystal for infrared spatial light modulators.

PubMed

Peng, Fenglin; Xu, Daming; Chen, Haiwei; Wu, Shin-Tson

2015-02-09

We report a low-voltage and fast-response polymer network liquid crystal (PNLC) infrared phase modulator. To optimize device performance, we propose a physical model to understand the curing temperature effect on average domain size. Good agreement between model and experiment is obtained. By optimizing the UV curing temperature and employing a large dielectric anisotropy LC host, we have lowered the 2π phase change voltage to 22.8V at 1.55μm wavelength while keeping response time at about 1 ms. Widespread application of such a PNLC integrated into a high resolution liquid-crystal-on-silicon (LCoS) for infrared spatial light modulator is foreseeable.

Design and implementation of an array of micro-electrochemical detectors for two-dimensional liquid chromatography--proof of principle.

PubMed

Abia, Jude A; Putnam, Joel; Mriziq, Khaled; Guiochon, Georges A

2010-03-05

Simultaneous two-dimensional liquid chromatography (2D-LC) is an implementation of two-dimensional liquid chromatography which has the potential to provide very fast, yet highly efficient separations. It is based on the use of time x space and space x space separation systems. The basic principle of this instrument has been validated long ago by the success of two-dimensional thin layer chromatography. The construction of a pressurized wide and flat column (100 mm x 100 mm x 1 mm) operated under an inlet pressure of up to 50 bar was described previously. However, to become a modern analytical method, simultaneous 2D-LC requires the development of detectors suitable for the monitoring of the composition of the eluent of this pressurized planar, wide column. An array of five equidistant micro-electrochemical sensors was built for this purpose and tested. Each sensor is a three-electrode system, with the working electrode being a 25 microm polished platinum micro-electrode. The auxiliary electrode is a thin platinum wire and the reference electrode an Ag/AgCl (3M sat. KCl) electrode. In this first implementation, proof of principle is demonstrated, but the final instrument will require a much larger array. 2010 Elsevier B.V. All rights reserved.

Poly(zwitterionic liquids) functionalized polypyrrole/graphene oxide nanosheets for electrochemically detecting dopamine at low concentration.

PubMed

Mao, Hui; Liang, Jiachen; Ji, Chunguang; Zhang, Haifeng; Pei, Qi; Zhang, Yuyang; Zhang, Yu; Hisaeda, Yoshio; Song, Xi-Ming

2016-08-01

Poly(3-(1-vinylimidazolium-3-yl)propane-1-sulfonate) (PVIPS), a novel kind of poly(zwitterionic liquids) (PZILs) containing both imidazolium cation and sulfonate anion, was successfully modified on the surface of polypyrrole/graphene oxide nanosheets (PPy/GO) by covalent bonding. The obtained novel PZILs functionalized PPy/GO nanosheets (PVIPS/PPy/GO) modified glassy carbon electrode (GCE) presented the excellent electrochemical catalytic activity towards dopamine (DA) with high stability, sensitivity, selectivity and wide linear range (40-1220nM), especially having a lower detection limit (17.3nM). The excellent analytical performance is attributed to the strongly negative charges on the surface of modified GCE in aqueous solution, which is different from conventional poly(ionic liquids) modified GCE. DA cations could be quickly enriched on the electrode surface by electrostatic interaction in solution due to the existence of SO3(-) groups with negative charge at the end of pendant groups in zwitterionic PVIPS, resulting in a change of the electrons transmission mode in the oxidation of DA, that is, from a typical diffusion-controlled process at conventional poly(1-vinyl-3-ethylimidazole bromide) (PVEIB)/PPy/GO modified GCE to a typical surface-controlled process. Copyright © 2016 Elsevier B.V. All rights reserved.

A novel polythiophene - ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis.

PubMed

Pelit, Füsun Okçu; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E E; Türkmen, Hayati; Ertaş, F N

2015-02-15

This report comprises the novel usage of polythiophene - ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett-Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box-Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002-0.667ng mL(-1). Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues. Copyright © 2014 Elsevier B.V. All rights reserved.

Optimized performance of quasi-solid-state DSSC with PEO-bismaleimide polymer blend electrolytes filled with a novel procedure.

PubMed

Lee, Dong Ha; Sun, Kyung Chul; Qadir, Muhammad Bilal; Jeong, Sung Hoon

2014-12-01

Dye-sensitized solar cell (DSSC) is an attractive renewable energy technology currently under intense investigation. Electrolyte plays an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. In this study, DSSC is developed by using quasi-solid electrolyte and a novel procedure is adopted for filling this electrolyte. The quasi-solid-state electrolyte was prepared by mixing Poly ethylene oxide (PEO) and bismaleimide together and constitution was taken as PEO (15 wt%) at various bismaleimide concentrations (1, 3, 5 wt%). The novel procedure of filling electrolyte consists of three major steps (first step: filling liquid electrolyte, second step: vaporization of liquid electrolyte, third step: refilling quasi-solid-state electrolyte). The electrochemical and photovoltaic performances of DSSCs with these electrolytes were also investigated. The electrochemical impedance spectroscopy (EIS) indicated that TiO2/Dye/electrolyte impedance is reduced and electron lifetime is increased, and consequently efficiency of cell has been improved after using this novel procedure. The photovoltaic power conversion efficiency of 6.39% has been achieved under AM 1.5 simulated sunlight (100 W/cm2) through this novel procedure and by using specified blend of polymers.

Synthesis of Mesoporous Carbons from Rice Husk for Supercapacitors with High Energy Density in Ionic Liquid Electrolytes.

PubMed

He, Xiaojun; Zhang, Hebao; Xie, Kang; Xia, Youyi; Zhao, Zhigang; Wang, Xiaoting

2016-03-01

High-performance mesoporous carbons (MCs) for supercapacitors were made from rice husk by one-step microwave-assisted ZnCl2 activation. The microstructures of MCs as-made were characterized by field emission scanning electron microscopy and transmission electron microscopy. The pore structure parameters of MCs were obtained by N2 adsorption technique. The electrochemical properties of MC electrodes were studied by constant current charge-discharge, cyclic voltammetry and electrochemical impedance spectroscopy in different electrolytes. The results showed that the specific surface area of MC4 made at the ZnCl2/rice husk mass of 4:1 reached 1737 m2 g(-1). The specific capacitance and energy density of the electrodes fabricated from the mixture of MC4 and microporous carbon increased with the mass percentage of MC4, reaching 157 F g(-1) and 84 Wh kg(-1) at 0.05 A g(-1), and showed good cycle stability in 1-butyl-3-methylimidazolium hexafluorophosphate electrolyte. Compared to the often-used aqueous and organic electrolytes, MC4 capacitor exhibited extremely high energy density in ionic liquid electrolyte, remaining at 28 Wh kg(-1) at 1684 W kg(-1). This work paves a new way to produce cost-effective MCs from biomass for supercapacitors with extremely high energy density in ionic liquid electrolytes.

The Atmospheric Scanning Electron Microscope with open sample space observes dynamic phenomena in liquid or gas.

PubMed

Suga, Mitsuo; Nishiyama, Hidetoshi; Konyuba, Yuji; Iwamatsu, Shinnosuke; Watanabe, Yoshiyuki; Yoshiura, Chie; Ueda, Takumi; Sato, Chikara

2011-12-01

Although conventional electron microscopy (EM) requires samples to be in vacuum, most chemical and physical reactions occur in liquid or gas. The Atmospheric Scanning Electron Microscope (ASEM) can observe dynamic phenomena in liquid or gas under atmospheric pressure in real time. An electron-permeable window made of pressure-resistant 100 nm-thick silicon nitride (SiN) film, set into the bottom of the open ASEM sample dish, allows an electron beam to be projected from underneath the sample. A detector positioned below captures backscattered electrons. Using the ASEM, we observed the radiation-induced self-organization process of particles, as well as phenomena accompanying volume change, including evaporation-induced crystallization. Using the electrochemical ASEM dish, we observed tree-like electrochemical depositions on the cathode. In silver nitrate solution, we observed silver depositions near the cathode forming incidental internal voids. The heated ASEM dish allowed observation of patterns of contrast in melting and solidifying solder. Finally, to demonstrate its applicability for monitoring and control of industrial processes, silver paste and solder paste were examined at high throughput. High resolution, imaging speed, flexibility, adaptability, and ease of use facilitate the observation of previously difficult-to-image phenomena, and make the ASEM applicable to various fields. Copyright © 2011 Elsevier B.V. All rights reserved.

Designing 3D Multihierarchical Heteronanostructures for High-Performance On-Chip Hybrid Supercapacitors: Poly(3,4-(ethylenedioxy)thiophene)-Coated Diamond/Silicon Nanowire Electrodes in an Aprotic Ionic Liquid.

PubMed

Aradilla, David; Gao, Fang; Lewes-Malandrakis, Georgia; Müller-Sebert, Wolfgang; Gentile, Pascal; Boniface, Maxime; Aldakov, Dmitry; Iliev, Boyan; Schubert, Thomas J S; Nebel, Christoph E; Bidan, Gérard

2016-07-20

A versatile and robust hierarchically multifunctionalized nanostructured material made of poly(3,4-(ethylenedioxy)thiophene) (PEDOT)-coated diamond@silicon nanowires has been demonstrated to be an excellent capacitive electrode for supercapacitor devices. Thus, the electrochemical deposition of nanometric PEDOT films on diamond-coated silicon nanowire (SiNW) electrodes using N-methyl-N-propylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide ionic liquid displayed a specific capacitance value of 140 F g(-1) at a scan rate of 1 mV s(-1). The as-grown functionalized electrodes were evaluated in a symmetric planar microsupercapacitor using butyltrimethylammonium bis((trifluoromethyl)sulfonyl)imide aprotic ionic liquid as the electrolyte. The device exhibited extraordinary energy and power density values of 26 mJ cm(-2) and 1.3 mW cm(-2) within a large voltage cell of 2.5 V, respectively. In addition, the system was able to retain 80% of its initial capacitance after 15 000 galvanostatic charge-discharge cycles at a high current density of 1 mA cm(-2) while maintaining a Coulombic efficiency around 100%. Therefore, this multifunctionalized hybrid device represents one of the best electrochemical performances concerning coated SiNW electrodes for a high-energy advanced on-chip supercapacitor.

Removal of herbicidal ionic liquids by electrochemical advanced oxidation processes combined with biological treatment.

PubMed

Pęziak-Kowalska, Daria; Fourcade, Florence; Niemczak, Michał; Amrane, Abdeltif; Chrzanowski, Łukasz; Lota, Grzegorz

2017-05-01

Recently a new group of ionic liquids (ILs) with herbicidal properties has been proposed for use in agriculture. Owing to the design of specific physicochemical properties, this group, referred to as herbicidal ionic liquids (HILs), allows for reducing herbicide field doses. Several ILs comprising phenoxy herbicides as anions and quaternary ammonium cations have been synthesized and tested under greenhouse and field conditions. However, since they are to be introduced into the environment, appropriate treatment technologies should be developed in order to ensure their proper removal and avoid possible contamination. In this study, didecyldimethylammonium (4-chloro-2-methylphenoxy) acetate was selected as a model HIL to evaluate the efficiency of a hybrid treatment method. Electrochemical oxidation or electro-Fenton was considered as a pretreatment step, whereas biodegradation was selected as the secondary treatment method. Both processes were carried out in current mode, at 10 mA with carbon felt as working electrode. The efficiency of degradation, oxidation and mineralization was evaluated after 6 h. Both processes decreased the total organic carbon and chemical oxygen demand (COD) values and increased the biochemical oxygen demand (BOD 5 ) on the COD ratio to a value close to 0.4, showing that the electrolyzed solutions can be considered as 'readily biodegradable.'

Electrochemistry of hemoglobin entrapped in a Nafion/nano-ZnO film on carbon ionic liquid electrode.

PubMed

Sun, Wei; Zhai, ZiQin; Wang, DanDan; Liu, ShuFeng; Jiao, Kui

2009-02-01

A stable composite film composed of the ionomer Nafion, the ZnO nanoparticle and the protein hemoglobin was cast on the surface of an ionic liquid modified carbon paste electrode (CILE) to establish a modified electrode denoted as Nafion/nano-ZnO/Hb/CILE. UV-vis and FT-IR spectrum showed that hemoglobin in the film retained its native conformation. The electrochemical behaviors of hemoglobin entrapped in the film were carefully investigated with cyclic voltammetry. A pair of well-defined and quasi-reversible redox voltammetric peaks for Hb Fe(III)/Fe(II) was obtained with the standard potential (E(0)') located at -0.344 V (vs. SCE) in phosphate buffer solution (PBS, pH 7.0), which was attributed to the direct electron transfer of Hb with electrode in the microenvironments of ZnO nanoparticle and ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The electrochemical parameters of Hb in the composite film were further carefully calculated with the results of the electron-transfer rate constant (k(s)) as 0.139 s(-1), the charge transfer coefficient (alpha) as 0.413 and the number of electron transferred (n) as 0.95. The Hb modified electrode showed good electrocatalytic ability toward the reduction of trichloroacetic acid (TCA).

Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy

DOE PAGES

Leenheer, Andrew J.; Jungjohann, Katherine L.; Zavadil, Kevin R.; ...

2016-05-31

Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. In this study, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge–discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed formore » the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Lastly, our results show that electrochemically induced solid–solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.« less

Nanosecond liquid crystalline optical modulator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borshch, Volodymyr; Shiyanovskii, Sergij V.; Lavrentovich, Oleg D.

2016-07-26

An optical modulator includes a liquid crystal cell containing liquid crystal material having liquid crystal molecules oriented along a quiescent director direction in the unbiased state, and a voltage source configured to apply an electric field to the liquid crystal material wherein the direction of the applied electric field does not cause the quiescent director direction to change. An optical source is arranged to transmit light through or reflect light off the liquid crystal cell with the light passing through the liquid crystal material at an angle effective to undergo phase retardation in response to the voltage source applying themore » electric field. The liquid crystal material may have negative dielectric anisotropy, and the voltage source configured to apply an electric field to the liquid crystal material whose electric field vector is transverse to the quiescent director direction. Alternatively, the liquid crystal material may have positive dielectric anisotropy and the voltage source configured to apply an electric field to the liquid crystal material whose electric field vector is parallel with the quiescent director direction.« less

Distributed electrochemical sensors: recent advances and barriers to market adoption.

PubMed

Hoekstra, Rafael; Blondeau, Pascal; Andrade, Francisco J

2018-07-01

Despite predictions of their widespread application in healthcare and environmental monitoring, electrochemical sensors are yet to be distributed at scale, instead remaining largely confined to R&D labs. This contrasts sharply with the situation for physical sensors, which are now ubiquitous and seamlessly embedded in the mature ecosystem provided by electronics and connectivity protocols. Although chemical sensors could be integrated into the same ecosystem, there are fundamental issues with these sensors in the three key areas of analytical performance, usability, and affordability. Nevertheless, advances are being made in each of these fields, leading to hope that the deployment of automated and user-friendly low-cost electrochemical sensors is on the horizon. Here, we present a brief survey of key challenges and advances in the development of distributed electrochemical sensors for liquid samples, geared towards applications in healthcare and wellbeing, environmental monitoring, and homeland security. As will be seen, in many cases the analytical performance of the sensor is acceptable; it is usability that is the major barrier to commercial viability at this moment. Were this to be overcome, the issue of affordability could be addressed. Graphical Abstract ᅟ.

Physical Properties of Pyridinium Fluorohydrogenate, [pyridine · H+][H2F3]-

NASA Astrophysics Data System (ADS)

Hulse, Ryan; Singh, Rajiv

2008-12-01

Ionic liquids (ILs), also referred to as molten salts, have found application as electrolytes for batteries and super-capacitors, in electroplating baths, as designer solvents, and as reaction media. A few of the desired properties of a super-capacitor electrolyte are nonflammability, thermal stability, and electrochemical stability. ILs containing aromatic cations have been shown to have low viscosity which results in a high electrochemical conductivity. There is a delicate balance between increasing the thermal stability, or decreasing the melting point, and increasing the electrochemical conductivity of the IL. This study focuses on pyridinium fluorohydrogenate, [pyridine · H+][H2F3]-. Pyridinium fluorohydrogenate has been synthesized by the reaction of pyridine and anhydrous hydrofluoric acid. This IL has a relatively high electrical conductivity (~98 mS · cm-1 at 23 °C), a wide electrochemical window, and a boiling point of 186 °C. A stable gel can also be formed by combining [pyridine · H+][H2F3]- and a super absorbent polymer such as polyacrylic acid. The gel adds mechanical stability to the matrix while not greatly affecting the conductivity of the IL.

In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, J Y; Zhong, L; Wang, C M

2010-12-09

We report the creation of a nanoscale electrochemical device inside a transmission electron microscope—consisting of a single tin dioxide (SnO{sub 2}) nanowire anode, an ionic liquid electrolyte, and a bulk lithium cobalt dioxide (LiCoO{sub 2}) cathode—and the in situ observation of the lithiation of the SnO{sub 2} nanowire during electrochemical charging. Upon charging, a reaction front propagated progressively along the nanowire, causing the nanowire to swell, elongate, and spiral. The reaction front is a “Medusa zone” containing a high density of mobile dislocations, which are continuously nucleated and absorbed at the moving front. This dislocation cloud indicates large in-plane misfitmore » stresses and is a structural precursor to electrochemically driven solid-state amorphization. Because lithiation-induced volume expansion, plasticity, and pulverization of electrode materials are the major mechanical effects that plague the performance and lifetime of high-capacity anodes in lithium-ion batteries, our observations provide important mechanistic insight for the design of advanced batteries.« less

Electrochemical cell

DOEpatents

Redey, L.I.; Myles, K.M.; Vissers, D.R.; Prakash, J.

1996-07-02

An electrochemical cell is described with a positive electrode having an electrochemically active layer of at least one transition metal chloride. A negative electrode of an alkali metal and a compatible electrolyte including an alkali metal salt molten at cell operating temperature is included in the cell. The electrolyte is present at least partially as a corrugated {beta}{double_prime} alumina tube surrounding the negative electrode interior to the positive electrode. The ratio of the volume of liquid electrolyte to the volume of the positive electrode is in the range of from about 0.1 to about 3. A plurality of stacked electrochemical cells is disclosed each having a positive electrode, a negative electrode of an alkali metal molten at cell operating temperature, and a compatible electrolyte. The electrolyte is at least partially present as a corrugated {beta}{double_prime} alumina sheet separating the negative electrode and interior to the positive electrodes. The alkali metal is retained in a porous electrically conductive ceramic, and seals for sealing the junctures of the electrolyte and the adjacent electrodes at the peripheries thereof. 8 figs.

Electrochemical synthesis of 1D core-shell Si/TiO2 nanotubes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Kowalski, Damian; Mallet, Jeremy; Thomas, Shibin; Nemaga, Abirdu Woreka; Michel, Jean; Guery, Claude; Molinari, Michael; Morcrette, Mathieu

2017-09-01

Silicon negative electrode for lithium ion battery was designed in the form of self-organized 1D core-shell nanotubes to overcome shortcomings linked to silicon volume expansion upon lithiation/delithiation typically occurring with Si nanoparticles. The negative electrode was formed on TiO2 nanotubes in two step electrochemical synthesis by means of anodizing of titanium and electrodeposition of silicon using ionic liquid electrolytes. Remarkably, it was found that the silicon grows perpendicularly to the z-axis of nanotube and therefore its thickness can be precisely controlled by the charge passed in the electrochemical protocol. Deposited silicon creates a continuous Si network on TiO2 nanotubes without grain boundaries and particle-particle interfaces, defining its electrochemical characteristics under battery testing. In the core-shell system the titania nanotube play a role of volume expansion stabilizer framework holding the nanostructured silicon upon lithiation/delithiation. The nature of Si shell and presence of titania core determine stable performance as negative electrode tested in half cell of CR2032 coin cell battery.

A Zinc Oxide Nanoflower-Based Electrochemical Sensor for Trace Detection of Sunset Yellow

PubMed Central

Ya, Yu; Jiang, Cuiwen; Li, Tao; Liao, Jie; Fan, Yegeng; Wei, Yuning; Yan, Feiyan; Xie, Liping

2017-01-01

Zinc oxide nanoflower (ZnONF) was synthesized by a simple process and was used to construct a highly sensitive electrochemical sensor for the detection of sunset yellow (SY). Due to the large surface area and high accumulation efficiency of ZnONF, the ZnONF-modified carbon paste electrode (ZnONF/CPE) showed a strong enhancement effect on the electrochemical oxidation of SY. The electrochemical behaviors of SY were investigated using voltammetry with the ZnONF-based sensor. The optimized parameters included the amount of ZnONF, the accumulation time, and the pH value. Under optimal conditions, the oxidation peak current was linearly proportional to SY concentration in the range of 0.50–10 μg/L and 10–70 μg/L, while the detection limit was 0.10 μg/L (signal-to-noise ratio = 3). The proposed method was used to determine the amount of SY in soft drinks with recoveries of 97.5%–103%, and the results were in good agreement with the results obtained by high-performance liquid chromatography. PMID:28282900

On the behavior of reduced graphene oxide based electrodes coated with dispersed platinum by alternate current methods in the electrochemical degradation of reactive dyes.

PubMed

Del Río, A I; García, C; Molina, J; Fernández, J; Bonastre, J; Cases, F

2017-09-01

The electrochemical behavior of different carbon-based electrodes with and without nanoparticles of platinum electrochemically dispersed on their surface has been studied. Among others, reduced graphene oxide based electrodes was used to determine the best conditions for the decolorization/degradation of the reactive dye C.I. Reactive Orange 4 in sulfuric medium. Firstly, the electrochemical behavior was evaluated by cyclic voltammetry. Secondly, different electrolyses were performed using two cell configurations: cell with anodic and cathodic compartments separated (divided configuration) and without any separation (undivided configuration). The best results were obtained when reduced graphene oxide based anodes were used. The degree of decolorization was monitored by spectroscopic methods and high performance liquid chromatography. It was found that all of them followed pseudo-first order kinetics. When reduced graphene oxide-based electrodes coated with dispersed platinum by alternate current methods electrodes were used, the lowest energy consumption and the higher decolorization kinetics rate were obtained. Scanning Electronic Microscopy was used to observe the morphological surface differences. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gelation Mechanisms and Characterization of Electrochemically Generated Protein Films at Metal Interfaces

NASA Astrophysics Data System (ADS)

Martin, Elizabeth J.

Although the electrochemical behavior of metals used in orthopedic implants has been studied extensively, the material interactions with proteins during corrosion processes remains poorly understood. Some studies suggest that metal-protein interactions accelerate corrosion, while others suggest that proteins protect the material from degradation. Corrosion of implant materials is a major concern due to the metal ion release that can sometimes cause adverse local tissue reactions and ultimately, failure of the implant. The initial purpose of this research was therefore to study the corrosion behavior of CoCrMo, an alloy commonly used in hip replacements, with a quartz crystal microbalance (QCM) in physiologically relevant media. The QCM enables in situ characterization of surface changes accompanying corrosion and is sensitive to viscoelastic effects at its surface. Results of QCM studies in proteinaceous media showed film deposition on the alloy surface under electrochemical conditions that otherwise produced mass loss if proteins were not present in the electrolyte. Additional studies on pure Co, Cr, and Mo demonstrated that the protein films also form on Mo surfaces after a release of molybdate ions, suggesting that these ions are essential for film formation. The electrochemically generated protein films are reminiscent of carbonaceous films that form on implant surfaces in vivo, therefore a second goal of the research was to delineate mechanisms that cause the films to form. In the second stage of this research, electrochemical QCM tests were conducted on models of the CoCrMo system consisting of Cr electrodes in proteinaceous or polymeric media containing dissolved molybdate ions. Studies indicated that films can be generated through electrochemical processes so long as both amine functional groups and molybdate ions are present in the electrolyte solution. These results suggest that the films form due to an ionic cross-linking reaction between the positively charged amine groups in the proteins and the negatively charged molybdate ions. Results also indicated that film generation is controlled by the potential at the electrode surface. Numerical analysis on the model systems suggest that a drop in the local pH at the corroding electrode surface may influence film generation, but a critical concentration of molybdate-amine cross-links must be exceeded for gels to form. A final goal of this research was to develop a technique to characterize the viscoelastic properties of polymer films in liquid media using the QCM as a high-frequency rheometer. The work showed that by measuring frequency and dissipation shifts at multiple harmonics of the QCM resonant frequency, the viscoelastic phase angle, density-modulus product, and areal mass of a film submersed in liquid can be quantified in situ. The method was successfully applied to characterize the electrochemically generated protein films. Results implied that the films are composed of a weakly cross-linked network with properties similar to concentrated albumin solutions containing 40 wt% protein. The analysis technique can be extended to characterize any polymer film in a liquid environment, with applications including adsorption, self-assembly, or cell-substrate interactions.

Apparatus and methods for direct conversion of gaseous hydrocarbons to liquids

DOEpatents

Kong, Peter C.; Lessing, Paul A.

2006-04-25

A chemical reactor for direct conversion of hydrocarbons includes a dielectric barrier discharge plasma cell and a solid oxide electrochemical cell in fluid communication therewith. The discharge plasma cell comprises a pair of electrodes separated by a dielectric material and passageway therebetween. The electrochemical cell comprises a mixed-conducting solid oxide electrolyte membrane tube positioned between a porous cathode and a porous anode, and a gas inlet tube for feeding oxygen containing gas to the porous cathode. An inlet is provided for feeding hydrocarbons to the passageway of the discharge plasma cell, and an outlet is provided for discharging reaction products from the reactor. A packed bed catalyst may optionally be used in the reactor to increase efficiency of conversion. The reactor can be modified to allow use of a light source for directing ultraviolet light into the discharge plasma cell and the electrochemical cell.

Effect of Pd Interlayer on Electrochemical Properties of ENIG Surface Finish in 3.5 wt.% NaCl Solution

NASA Astrophysics Data System (ADS)

Nam, N. D.; Bui, Q. V.; Nhan, H. T.; Phuong, D. V.; Bian, M. Z.

2014-09-01

The corrosion resistance of a multilayered (NiP-Pd-Au) coating with various thicknesses of palladium (Pd) interlayer deposited on copper by an electroless method was investigated using electrochemical techniques including potentiodynamic polarization and electrochemical impedance spectroscopy. In addition, the surface finish was examined by x-ray diffraction analysis and scanning electron microscopy, and the contact angle of the liquid-solid interface was recorded. The corrosion resistance of the copper substrate was considerably improved by Pd interlayer addition. Increase of the thickness of the Pd interlayer enhanced the performance of the Cu-NiP-Pd-Au coating due to low porosity, high protective efficiency, high charge-transfer resistance, and contact angle. These are attributed to the diffusion of layers in the Cu-NiP-Pd-Au coating acting as a physical barrier layer, leading to the protection provided by the coating.

Enzyme-based electrochemical biosensors for determination of organophosphorus and carbamate pesticides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Everett, W.R.; Rechnitz, G.A.

1999-01-01

A mini review of enzyme-based electrochemical biosensors for inhibition analysis of organophosphorus and carbamate pesticides is presented. Discussion includes the most recent literature to present advances in detection limits, selectivity and real sample analysis. Recent reviews on the monitoring of pesticides and their residues suggest that the classical analytical techniques of gas and liquid chromatography are the most widely used methods of detection. These techniques, although very accurate in their determinations, can be quite time consuming and expensive and usually require extensive sample clean up and pro-concentration. For these and many other reasons, the classical techniques are very difficult tomore » adapt for field use. Numerous researchers, in the past decade, have developed and made improvements on biosensors for use in pesticide analysis. This mini review will focus on recent advances made in enzyme-based electrochemical biosensors for the determinations of organophosphorus and carbamate pesticides.« less

The sequential use of washing and an electrochemical reduction process for the remediation of lead-contaminated soils.

PubMed

Demir, Aydeniz; Köleli, Nurcan

2013-01-01

A two-step method for the remediation of three different types of lead (Pb)-contaminated soil was evaluated. The first step included soil washing with ethylenediaminetetraacetic acid (EDTA) to remove Pb from soils. The washing experiments were performed with 0.05 M Na2EDTA at 1:10 soil to liquid ratio. Following the washing, Pb removal efficiency from soils ranged within 50-70%. After the soil washing process, Pb2+ ions in the washing solution were reduced electrochemically in a fixed-bed reactor. Lead removal efficiency with the electrochemical reduction at -2.0 V potential ranged within 57-76%. The overall results indicate that this two-step method is an environmentally-friendly and effective technology to remediate Pb-contaminated soils, as well as Pb-contaminated wastewater treatment due to the transformation of toxic Pb2+ ions into a non-hazardous metallic form (Pb(0)).

Impurity Effects on Charging Mechanism and Energy Storage of Nanoporous Supercapacitors

DOE PAGES

Lian, Cheng; Liu, Kun; Liu, Honglai; ...

2017-06-08

Room-temperature ionic liquids (RTILs) have been widely used as electrolytes to enhance the capacitive performance of electrochemical capacitors also known as supercapacitors. Whereas impurities are ubiquitous in RTILs (e.g., water, alkali salts, and organic solvents), little is known about their influences on the electrochemical behavior of electrochemical devices. In this work, we investigate different impurities in RTILs within the micropores of carbon electrodes via the classical density functional theory (CDFT). We find that under certain conditions impurities can significantly change the charging behavior of electric double layers and the shape of differential capacitance curves even at very low concentrations. Moremore » interestingly, an impurity with a strong affinity to the nanopore can increase the energy density beyond a critical charging potential. As a result, our theoretical predictions provide further understanding of how impurity in RTILs affects the performance of supercapacitors.« less

Electrochemical Device Comprising an Electrically-Conductive, Selectively-Permeable Membrane

NASA Technical Reports Server (NTRS)

Laicer, Castro S. T. (Inventor); Mittelsteadt, Cortney K. (Inventor); Harrison, Katherine E. (Inventor); McPheeters, Bryn M. (Inventor)

2017-01-01

An electrochemical device, such as a fuel cell or an electrolyzer. In one embodiment, the electrochemical device includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, the membrane including a solid polymer electrolyte and a non-particulate, electrically-conductive material, such as carbon nanotubes, carbon nanofibers, and/or metal nanowires. In addition, each bipolar plate also includes an electrically-conductive fluid chamber in contact with the electrically-conductive, selectively-permeable membrane and further includes a non-porous and electrically-conductive plate in contact with the fluid chamber.

Investigation on direct electrochemical and electrocatalytic behavior of hemoglobin on palladium-graphene modified electrode.

PubMed

Chen, Wei; Niu, Xueliang; Li, Xiaoyan; Li, Xiaobao; Li, Guangjiu; He, Bolin; Li, Qiutong; Sun, Wei

2017-11-01

Palladium-graphene (Pd-GR) nanocomposite was acted as modifier for construction of the modified electrode with direct electrochemistry of hemoglobin (Hb) realized. By using Nafion as the immobilization film, Hb was fixed tightly on Pd-GR nanocomposite modified carbon ionic liquid electrode. Electrochemical behaviors of Hb modified electrode were checked by cyclic voltammetry and a pair of redox peaks originated from direct electron transfer of Hb was appeared. The Hb modified electrode had excellent electrocatalytic activity to the reduction of trichloroacetic acid and sodium nitrite in the concentration range from 0.6 to 13.0mmol·L -1 and from 0.04 to 0.5 mmol·L -1 . Therefore Pd-GR nanocomposite was proven to be a good candidate for the fabrication of third-generation electrochemical biosensor. Copyright © 2017 Elsevier B.V. All rights reserved.

Method for direct conversion of gaseous hydrocarbons to liquids

DOEpatents

Kong, Peter C.; Lessing, Paul A.

2006-03-07

A chemical reactor for direct conversion of hydrocarbons includes a dielectric barrier discharge plasma cell and a solid oxide electrochemical cell in fluid communication therewith. The discharge plasma cell comprises a pair of electrodes separated by a dielectric material and passageway therebetween. The electrochemical cell comprises a mixed-conducting solid oxide electrolyte membrane tube positioned between a porous cathode and a porous anode, and a gas inlet tube for feeding oxygen containing gas to the porous cathode. An inlet is provided for feeding hydrocarbons to the passageway of the discharge plasma cell, and an outlet is provided for discharging reaction products from the reactor. A packed bed catalyst may optionally be used in the reactor to increase efficiency of conversion. The reactor can be modified to allow use of a light source for directing ultraviolet light into the discharge plasma cell and the electrochemical cell.

Nanoparticles in ionic liquids: interactions and organization.

PubMed

He, Zhiqi; Alexandridis, Paschalis

2015-07-28

Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.

Electrochemical Control of Peptide Self-Organization on Atomically Flat Solid Surfaces: A Case Study with Graphite.

PubMed

Seki, Takakazu; So, Christopher R; Page, Tamon R; Starkebaum, David; Hayamizu, Yuhei; Sarikaya, Mehmet

2018-02-06

The nanoscale self-organization of biomolecules, such as proteins and peptides, on solid surfaces under controlled conditions is an important issue in establishing functional bio/solid soft interfaces for bioassays, biosensors, and biofuel cells. Electrostatic interaction between proteins and surfaces is one of the most essential parameters in the adsorption and self-assembly of proteins on solid surfaces. Although the adsorption of proteins has been studied with respect to the electrochemical surface potential, the self-assembly of proteins or peptides forming well-organized nanostructures templated by lattice structure of the solid surfaces has not been studied in the relation to the surface potential. In this work, we utilize graphite-binding peptides (GrBPs) selected by the phage display method to investigate the relationship between the electrochemical potential of the highly ordered pyrolytic graphite (HOPG) and peptide self-organization forming long-range-ordered structures. Under modulated electrical bias, graphite-binding peptides form various ordered structures, such as well-ordered nanowires, dendritic structures, wavy wires, amorphous (disordered) structures, and islands. A systematic investigation of the correlation between peptide sequence and self-organizational characteristics reveals that the presence of the bias-sensitive amino acid modules in the peptide sequence has a significant effect on not only surface coverage but also on the morphological features of self-assembled structures. Our results show a new method to control peptide self-assembly by means of applied electrochemical bias as well as peptide design-rules for the construction of functional soft bio/solid interfaces that could be integrated in a wide range of practical implementations.

Spectroelectrochemical Sensors: New Polymer Films for Improved Sensitivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morris, Laura K.; Seliskar, Carl J.; Bryan, Samuel A.

2014-10-31

The selectivity of an optical sensor can be improved by combining optical detection with electrochemical oxidation or reduction of the target analyte to change its spectral properties. The changing signal can distinguish the analyte from interferences with similar spectral properties that would otherwise interfere. The analyte is detected by measuring the intensity of the electrochemically modulated signal. In one form this spectroelectrochemical sensor consists of an optically transparent electrode (OTE) coated with a film that preconcentrates the target analyte. The OTE functions as an optical waveguide for attenuated total reflectance (ATR) spectroscopy, which detects the analyte by absorption. Sensitivity reliesmore » in part on a large change in molar absorptivity between the two oxidation states used for electrochemical modulation of the optical signal. A critical part of the sensor is the ion selective film. It should preconcentrate the analyte and exclude some interferences. At the same time the film must not interfere with the electrochemistry or the optical detection. Therefore, since the debut of the sensor’s concept one major focus of our group has been developing appropriate films for different analytes. Here we report the development of a series of quaternized poly(vinylpyridine)-co-styrene (QPVP-co-S) anion exchange films for use in spectroelectrochemical sensors to enable sensitive detection of target anionic analytes in complex samples. The films were either 10% or 20% styrene and were prepared with varying degrees of quaternized pyridine groups, up to 70%. Films were characterized with respect to thickness with spectroscopic ellipsometry, degree of quaternization with FTIR, and electrochemically and spectroelectrochemically using the anions ferrocyanide and pertechnetate.« less

Simultaneous Interfacial Reactivity and Topography Mapping with Scanning Ion Conductance Microscopy.

PubMed

Momotenko, Dmitry; McKelvey, Kim; Kang, Minkyung; Meloni, Gabriel N; Unwin, Patrick R

2016-03-01

Scanning ion conductance microscopy (SICM) is a powerful technique for imaging the topography of a wide range of materials and interfaces. In this report, we develop the use and scope of SICM, showing how it can be used for mapping spatial distributions of ionic fluxes due to (electro)chemical reactions occurring at interfaces. The basic idea is that there is a change of ion conductance inside a nanopipet probe when it approaches an active site, where the ionic composition is different to that in bulk solution, and this can be sensed via the current flow in the nanopipet with an applied bias. Careful tuning of the tip potential allows the current response to be sensitive to either topography or activity, if desired. Furthermore, the use of a distance modulation SICM scheme allows reasonably faithful probe positioning using the resulting ac response, irrespective of whether there is a reaction at the interface that changes the local ionic composition. Both strategies (distance modulation or tuned bias) allow simultaneous topography-activity mapping with a single channel probe. The application of SICM reaction imaging is demonstrated on several examples, including voltammetric mapping of electrocatalytic reactions on electrodes and high-speed electrochemical imaging at rates approaching 4 s per image frame. These two distinct approaches provide movies of electrochemical current as a function of potential with hundreds of frames (images) of surface reactivity, to reveal a wealth of spatially resolved information on potential- (and time) dependent electrochemical phenomena. The experimental studies are supported by detailed finite element method modeling that places the technique on a quantitative footing.

Field Effect Modulation of Heterogeneous Charge Transfer Kinetics at Back-Gated Two-Dimensional MoS2 Electrodes.

PubMed

Wang, Yan; Kim, Chang-Hyun; Yoo, Youngdong; Johns, James E; Frisbie, C Daniel

2017-12-13

The ability to improve and to modulate the heterogeneous charge transfer kinetics of two-dimensional (2D) semiconductors, such as MoS 2 , is a major challenge for electrochemical and photoelectrochemical applications of these materials. Here we report a continuous and reversible physical method for modulating the heterogeneous charge transfer kinetics at a monolayer MoS 2 working electrode supported on a SiO 2 /p-Si substrate. The heavily doped p-Si substrate serves as a back gate electrode; application of a gate voltage (V BG ) to p-Si tunes the electron occupation in the MoS 2 conduction band and shifts the conduction band edge position relative to redox species dissolved in electrolyte in contact with the front side of the MoS 2 . The gate modulation of both charge density and energy band alignment impacts charge transfer kinetics as measured by cyclic voltammetry (CV). Specifically, cyclic voltammograms combined with numerical simulations suggest that the standard heterogeneous charge transfer rate constant (k 0 ) for MoS 2 in contact with the ferrocene/ferrocenium (Fc 0/+ ) redox couple can be modulated by over 2 orders of magnitude from 4 × 10 -6 to 1 × 10 -3 cm/s, by varying V BG . In general, the field effect offers the potential to tune the electrochemical properties of 2D semiconductors, opening up new possibilities for fundamental studies of the relationship between charge transfer kinetics and independently controlled electronic band alignment and band occupation.

ECLSS Universal Waste Management System (UWMS) Metal Materials Compatibility Study- Electrochemical and Crevice Corrosion Evaluation

NASA Technical Reports Server (NTRS)

Lee, R. E.

2017-01-01

Electrochemical and crevice corrosion laboratory test results are presented for three noble metal candidates with possible application on the Universal Waste Management System (UWMS) in support of the Environmental Control and Life Support System (ECLSS) aboard the International Space Station (ISS). The three metal candidates, which included Inconel 625, Hastelloy C276 and Titanium 6Al-4V, were evaluated in two solutions representative of the acidic pretreatment formulations utilized during processing of waste liquids within the ECLSS. Final test results and data analysis indicated that the passive layer on all three metals provides excellent corrosion protection in both solutions under standard test conditions.

Design and Operation of an Electrochemical Methanol Concentration Sensor for Direct Methanol Fuel Cell Systems

NASA Technical Reports Server (NTRS)

Narayanan, S. R.; Valdez, T. I.; Chun, W.

2000-01-01

The development of a 150-Watt packaged power source based on liquid feed direct methanol fuel cells is being pursued currently at the Jet propulsion Laboratory for defense applications. In our studies we find that the concentration of methanol in the fuel circulation loop affects the electrical performance and efficiency the direct methanol fuel cell systems significantly. The practical operation of direct methanol fuel cell systems, therefore, requires accurate monitoring and control of methanol concentration. The present paper reports on the principle and demonstration of an in-house developed electrochemical sensor suitable for direct methanol fuel cell systems.

In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

PubMed

Li, Bin; Yu, Bo; Zhou, Feng

2013-02-12

Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fuel Cells Using the Protic Ionic Liquid and Rotator Phase Solid Electrolyte Principles

DTIC Science & Technology

2008-02-13

Talk “High temperature Polymer Electrolyte Membrane Fuel Cells (HT- PEMFCs ) for Portable Power in Large-Scale Energy Storage Devices”, Paper Number 195...Membrane Fuel Cells (HT- PEMFCs ) for Portable Power in Large-Scale Energy Storage Devices”, Paper Number 195, 212th Meeting of the Electrochemical

Composition and stability of phytochemicals in five varieties of black soybeans (glycine max)

USDA-ARS?s Scientific Manuscript database

Phytochemical compositions of five varieties of black soybeans (Glycine max) and their stabilities at room temperature, 4 deg.C and -80 deg.C over 14 months were determined by HPLC systems with electrochemical (HPLC-ECD) and UV detectors. Polyphenol profiling was carried out by liquid chromatography...

High conductivity electrolyte solutions and rechargeable cells incorporating such solutions

DOEpatents

Angell, C.A.; Zhang, S.S.; Xu, K.

1998-10-20

This invention relates generally to electrolyte solvents for use in liquid or rubbery polymer electrolyte solutions as are used, for example, in electrochemical devices. More specifically, this invention relates to sulfonyl/phospho-compound electrolyte solvents and sulfonyl/phospho-compound electrolyte solutions incorporating such solvents. 9 figs.

A Twice Electrochemical-Etching Method to Fabricate Superhydrophobic-Superhydrophilic Patterns for Biomimetic Fog Harvest.

PubMed

Yang, Xiaolong; Song, Jinlong; Liu, Junkai; Liu, Xin; Jin, Zhuji

2017-08-18

Superhydrophobic-superhydrophilic patterned surfaces have attracted more and more attention due to their great potential applications in the fog harvest process. In this work, we developed a simple and universal electrochemical-etching method to fabricate the superhydrophobic-superhydrophilic patterned surface on metal superhydrophobic substrates. The anti-electrochemical corrosion property of superhydrophobic substrates and the dependence of electrochemical etching potential on the wettability of the fabricated dimples were investigated on Al samples. Results showed that high etching potential was beneficial for efficiently producing a uniform superhydrophilic dimple. Fabrication of long-term superhydrophilic dimples on the Al superhydrophobic substrate was achieved by combining the masked electrochemical etching and boiling-water immersion methods. A long-term wedge-shaped superhydrophilic dimple array was fabricated on a superhydrophobic surface. The fog harvest test showed that the surface with a wedge-shaped pattern array had high water collection efficiency. Condensing water on the pattern was easy to converge and depart due to the internal Laplace pressure gradient of the liquid and the contact angle hysteresis contrast on the surface. The Furmidge equation was applied to explain the droplet departing mechanism and to control the departing volume. The fabrication technique and research of the fog harvest process may guide the design of new water collection devices.

Electrochemical degradation of the antihypertensive losartan in aqueous medium by electro-oxidation with boron-doped diamond electrode.

PubMed

Salazar, Claudio; Contreras, Nicole; Mansilla, Héctor D; Yáñez, Jorge; Salazar, Ricardo

2016-12-05

In this work the electrochemical oxidation of losartan, an emerging pharmaceutical pollutant, was studied. Electrochemical oxidation was carried out in batch mode, in an open and undivided cell of 100cm(3) using a boron-doped diamond (BDD)/stainless steel system. With Cl(-) medium 56% of mineralization was registered, while with the trials containing SO4(2-) as supporting electrolyte a higher mineralization yield of 67% was reached, even obtaining a total removal of losartan potassium at 80mAcm(-2) and 180min of reaction time at pH 7.0. Higher losartan potassium concentrations enhanced the mineralization degree and the efficiency of the electrochemical oxidation process. During the mineralization up to 4 aromatic intermediates were identified by ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Moreover, short-linear carboxylic acids, like oxalic, succinic and oxamic were detected and quantified by ion-exclusion HPLC. Finally, the ability of the electrochemical oxidation process to mineralize dissolved commercial tablets containing losartan was achieved, obtaining TOC removal up to 71% under optimized conditions (10mAcm(-2), 0.05M Na2SO4, pH 7.0 and 25°C and 360min of electrolysis). Copyright © 2016 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy.more » SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

Smart lighting using a liquid crystal modulator

NASA Astrophysics Data System (ADS)

Baril, Alexandre; Thibault, Simon; Galstian, Tigran

2017-08-01

Now that LEDs have massively invaded the illumination market, a clear trend has emerged for more efficient and targeted lighting. The project described here is at the leading edge of the trend and aims at developing an evaluation board to test smart lighting applications. This is made possible thanks to a new liquid crystal light modulator recently developed for broadening LED light beams. The modulator is controlled by electrical signals and is characterized by a linear working zone. This feature allows the implementation of a closed loop control with a sensor feedback. This project shows that the use of computer vision is a promising opportunity for cheap closed loop control. The developed evaluation board integrates the liquid crystal modulator, a webcam, a LED light source and all the required electronics to implement a closed loop control with a computer vision algorithm.

Calibration of a spatial light modulator containing dual frequency liquid crystal

NASA Astrophysics Data System (ADS)

Gu, Dong-Feng; Winker, Bruce; Wen, Bing; Taber, Don; Brackley, Andrew; Wirth, Allan; Albanese, Marc; Landers, Frank

2005-08-01

Characterization and calibration process for a liquid crystal (LC) spatial light modulator (SLM) containing dual frequency liquid crystal is described. Special care was taken when dealing with LC cell gap non-uniformity and defect pixels. The calibration results were fed into a closed loop control algorithm to demonstrate correction of wavefront distortions. The performance characteristics of the device were reported. Substantial improvements were made in speed (bandwidth), resolution, power consumption and system weight/volume.

A Simple and Inexpensive Solar Energy Experiment.

ERIC Educational Resources Information Center

Evans, J. H.; Pedersen, L. G.

1979-01-01

An experiment is presented which utilizes the current solid state technology to demonstrate electrochemical generation of hydrogen gas, direct generation of electricity for pumping water, and energy conversion efficiency. The experimental module costs about $100 and can be used repeatedly. (BB)

Optical correlator using very-large-scale integrated circuit/ferroelectric-liquid-crystal electrically addressed spatial light modulators

NASA Technical Reports Server (NTRS)

Turner, Richard M.; Jared, David A.; Sharp, Gary D.; Johnson, Kristina M.

1993-01-01

The use of 2-kHz 64 x 64 very-large-scale integrated circuit/ferroelectric-liquid-crystal electrically addressed spatial light modulators as the input and filter planes of a VanderLugt-type optical correlator is discussed. Liquid-crystal layer thickness variations that are present in the devices are analyzed, and the effects on correlator performance are investigated through computer simulations. Experimental results from the very-large-scale-integrated / ferroelectric-liquid-crystal optical-correlator system are presented and are consistent with the level of performance predicted by the simulations.

Surface modification of active material structures in battery electrodes

DOEpatents

Erickson, Michael; Tikhonov, Konstantin

2016-02-02

Provided herein are methods of processing electrode active material structures for use in electrochemical cells or, more specifically, methods of forming surface layers on these structures. The structures are combined with a liquid to form a mixture. The mixture includes a surface reagent that chemically reacts and forms a surface layer covalently bound to the structures. The surface reagent may be a part of the initial liquid or added to the mixture after the liquid is combined with the structures. In some embodiments, the mixture may be processed to form a powder containing the structures with the surface layer thereon. Alternatively, the mixture may be deposited onto a current collecting substrate and dried to form an electrode layer. Furthermore, the liquid may be an electrolyte containing the surface reagent and a salt. The liquid soaks the previously arranged electrodes in order to contact the structures with the surface reagent.

Stimuli Responsive Ionogels for Sensing Applications—An Overview

PubMed Central

Kavanagh, Andrew; Byrne, Robert; Diamond, Dermot; Fraser, Kevin J.

2012-01-01

This overview aims to summarize the existing potential of “Ionogels” as a platform to develop stimuli responsive materials. Ionogels are a class of materials that contain an Ionic Liquid (IL) confined within a polymer matrix. Recently defined as “a solid interconnected network spreading throughout a liquid phase”, the ionogel therefore combines the properties of both its solid and liquid components. ILs are low melting salts that exist as liquids composed entirely of cations and anions at or around 100 °C. Important physical properties of these liquids such as viscosity, density, melting point and conductivity can be altered to suit a purpose by choice of the cation/anion. Here we provide an overview to highlight the literature thus far, detailing the encapsulation of IL and responsive materials within these polymeric structures. Exciting applications in the areas of optical and electrochemical sensing, solid state electrolytes and actuating materials shall be discussed. PMID:24957961

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores

PubMed Central

Futamura, Ryusuke; Iiyama, Taku; Takasaki, Yuma; Gogotsi, Yury; Biggs, Mark J.; Salanne, Mathieu; Ségalini, Julie; Simon, Patrice; Kaneko, Katsumi

2017-01-01

Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of the widely used ionic liquid (EMI-TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can only accommodate a single layer of ions. Instead, equally-charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. This finding opens the door for the design of better materials for electrochemical applications. PMID:28920938

Graphene Microcapsule Arrays for Combinatorial Electron Microscopy and Spectroscopy in Liquids

DOE PAGES

Yulaev, Alexander; Guo, Hongxuan; Strelcov, Evgheni; ...

2017-04-27

Atomic-scale thickness, molecular impermeability, low atomic number, and mechanical strength make graphene an ideal electron-transparent membrane for material characterization in liquids and gases with scanning electron microscopy and spectroscopy. Here in this paper, we present a novel sample platform made of an array of thousands of identical isolated graphene-capped microchannels with high aspect ratio. A combination of a global wide field of view with high resolution local imaging of the array allows for high throughput in situ studies as well as for combinatorial screening of solutions, liquid interfaces, and immersed samples. We demonstrate the capabilities of this platform by studyingmore » a pure water sample in comparison with alkali halide solutions, a model electrochemical plating process, and beam-induced crystal growth in liquid electrolyte. Spectroscopic characterization of liquid interfaces and immersed objects with Auger and X-ray fluorescence analysis through the graphene membrane are also demonstrated.« less