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

Biologically Derived Nanoparticle Arrays via a Site-Specific Reconstitution of Ferritin and their Electrochemistry

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Elliott, James R.; Chu, Sang-Hyon; Park, Yeonjoon; Watt, Gerald D.

2004-01-01

Nanoparticle arrays biologically derived from an electrochemically-controlled site-specific biomineralization were fabricated on a gold substrate through the immobilization process of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, the fabrication of self-assembled arrays with the immobilized ferritin, and the electrochemical characterization of various core materials. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of electrochemical site-specific biomineralization with a protein cage loads ferritins with different core materials such as Pt, Co, Mn, and Ni. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. The nano-sized metalcored ferritins on a gold substrate displayed a good electrochemical activity for the electron transport and storage, which is suitable for bioelectronics applications such as biofuel cell, bionanobattery, biosensors, etc. Keywords: Ferritin, immobilization, site-specific reconstitution, biomineralization, and bioelectronics

Electrochemical cell and separator plate thereof

DOEpatents

Baker, Bernard S.; Dharia, Dilip J.

1979-10-02

A fuel cell includes a separator plate having first and second flow channels extending there through contiguously with an electrode and respectively in flow communication with the cell electrolyte and in flow isolation with respect to such electrolyte. In fuel cell system arrangement, the diverse type channels are supplied in common with process gas for thermal control purposes. The separator plate is readily formed by corrugation of integral sheet material. 10 figs.

Integration of serpentine channels for microchip electrophoresis with a palladium decoupler and electrochemical detection

PubMed Central

Bowen, Amanda L; Martin, R. Scott

2010-01-01

While it has been shown that microchip electrophoresis with electrochemical detection can be used to separate and detect electroactive species, there is a need to increase the separation performance of these devices so that complex mixtures can be routinely analyzed. Previous work in microchip electrophoresis has demonstrated that increasing the separation channel length leads to an increase in resolution between closely eluting analytes. This paper details the use of lengthened serpentine microchannels for microchip electrophoresis and electrochemical detection where a palladium decoupler is used to ground the separation voltage so that the working electrodes remain in the fluidic network. In this work, palladium electrodepositions were used to increase the decoupler surface area and more efficiently dissipate hydrogen produced at the decoupler. Dopamine and norepinephrine, which only differ in structure by a hydroxyl group, were used as model analytes. It was found that increasing the separation channel length led to improvements in both resolution and the number of theoretical plates for these analytes. The use of a bi-layer valving device, where PDMS-based valves are utilized for the injection process, along with serpentine microchannels and amperometric detection resulted in a multi-analyte separation and an average of 28,700 theoretical plates. It was also shown that the increased channel length is beneficial when separating and detecting analytes from a high ionic strength matrix. This was demonstrated by monitoring the stimulated release of neuro-transmitters from a confluent layer of PC 12 cells. PMID:19739137

Electrochemical formation of field emitters

DOEpatents

Bernhardt, Anthony F.

1999-01-01

Electrochemical formation of field emitters, particularly useful in the fabrication of flat panel displays. The fabrication involves field emitting points in a gated field emitter structure. Metal field emitters are formed by electroplating and the shape of the formed emitter is controlled by the potential imposed on the gate as well as on a separate counter electrode. This allows sharp emitters to be formed in a more inexpensive and manufacturable process than vacuum deposition processes used at present. The fabrication process involves etching of the gate metal and the dielectric layer down to the resistor layer, and then electroplating the etched area and forming an electroplated emitter point in the etched area.

Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; Chu, Sang-Hong; King, Glen C.; Watt, Gerald D.

2007-01-01

Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic 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.

Prioritized List of Research Needs to support MRWFD Case Study Flowsheet Advancement

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

Law, Jack Douglas; Soelberg, Nicholas Ray

In FY-13, a case study evaluation was performed of full recycle technologies for both the processing of light-water reactor (LWR) used nuclear fuels as well as fast reactor (FR) fuel in the full recycle option. This effort focused on the identification of the case study processes and the initial preparation of material balance flowsheets for the identified technologies. In identifying the case study flowsheets, it was decided that two cases would be developed: one which identifies the flowsheet as currently developed and another near-term target flowsheet which identifies the flowsheet as envisioned within two years, pending the results of ongoingmore » research. The case study focus is on homogeneous aqueous recycle of the U/TRU resulting from the processing of LWR fuel as feed for metal fuel fabrication. The metal fuel is utilized in a sodium-cooled fast reactor, and the used fast reactor fuel is processed using electrochemical separations. The recovered U/TRU from electrochemical separations is recycled to fuel fabrication and the fast reactor. Waste streams from the aqueous and electrochemical processing are treated and prepared for disposition. Off-gas from the separations and waste processing are also treated. As part of the FY-13 effort, preliminary process unknowns and research needs to advance the near-term target flowsheets were identified. In FY-14, these research needs were updated, expanded and prioritized. This report again updates the prioritized list of research needs based upon results to date in FY-15. The research needs are listed for each of the main portions of the flowsheet: 1) Aqueous headend, 2) Headend tritium pretreatment off-gas, 3) Aqueous U/Pu/Np recovery, 4) Aqueous TRU product solidification, 5) Aqueous actinide/lanthanide separation, 6) Aqueous off-gas treatment, 7) Aqueous HLW management, 8) Treatment of aqueous process wastes, 9) E-chem actinide separations, 10) E-chem off-gas, 11) E-chem HLW management. The identified research needs were prioritized within each of these areas. No effort was made to perform an overall prioritization. This information will be used by the MRWFD Campaign leadership in research planning for FY-16. Additionally, this information will be incorporated into the next version of the Case Study Report scheduled to be issued September 2015.« less

Microfluidic devices with thick-film electrochemical detection

DOEpatents

Wang, Joseph; Tian, Baomin; Sahlin, Eskil

2005-04-12

An apparatus for conducting a microfluidic process and analysis, including at least one elongated microfluidic channel, fluidic transport means for transport of fluids through the microfluidic channel, and at least one thick-film electrode in fluidic connection with the outlet end of the microfluidic channel. The present invention includes an integrated on-chip combination reaction, separation and thick-film electrochemical detection microsystem, for use in detection of a wide range of analytes, and methods for the use thereof.

Separator material for electrochemical cells

DOEpatents

Cieslak, Wendy R.; Storz, Leonard J.

1991-01-01

An electrochemical cell characterized as utilizing an aramid fiber as a separator material. The aramid fibers are especially suited for lithium/thionyl chloride battery systems. The battery separator made of aramid fibers possesses superior mechanical strength, chemical resistance, and is flame retardant.

Separator material for electrochemical cells

DOEpatents

Cieslak, W.R.; Storz, L.J.

1991-03-26

An electrochemical cell is characterized as utilizing an aramid fiber as a separator material. The aramid fibers are especially suited for lithium/thionyl chloride battery systems. The battery separator made of aramid fibers possesses superior mechanical strength, chemical resistance, and is flame retardant.

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

Carlson, Steven Allen; Anakor, Ifenna Kingsley; Farrell, Greg Robert

Provided are separators for use in an electrochemical cell comprising (a) an inorganic oxide and (b) an organic polymer, wherein the inorganic oxide comprises organic substituents. Also provided are electrochemical cells comprising such separators.

Electrochemical formation of field emitters

DOEpatents

Bernhardt, A.F.

1999-03-16

Electrochemical formation of field emitters, particularly useful in the fabrication of flat panel displays is disclosed. The fabrication involves field emitting points in a gated field emitter structure. Metal field emitters are formed by electroplating and the shape of the formed emitter is controlled by the potential imposed on the gate as well as on a separate counter electrode. This allows sharp emitters to be formed in a more inexpensive and manufacturable process than vacuum deposition processes used at present. The fabrication process involves etching of the gate metal and the dielectric layer down to the resistor layer, and then electroplating the etched area and forming an electroplated emitter point in the etched area. 12 figs.

Electrochemical separation is an attractive strategy for development of radionuclide generators for medical applications.

PubMed

Chakravarty, Rubel; Dash, Ashutosh; Pillai, M R A

2012-07-01

Electrochemical separation techniques are not widely used in radionuclide generator technology and only a few studies have been reported [1-4]. Nevertheless, this strategy is useful when other parent-daughter separation techniques are not effective or not possible. Such situations are frequent when low specific activity (LSA) parent radionuclides are used for instance with adsorption chromatographic separations, which can result in lower concentration of the daughter radionuclide in the eluent. In addition, radiation instability of the column matrix in many cases can affect the performance of the generator when long lived parent radionuclides are used. Intricate knowledge of the chemistry involved in the electrochemical separation is crucial to develop a reproducible technology that ensures that the pure daughter radionuclide can be obtained in a reasonable time of operation. Crucial parameters to be critically optimized include the applied potential, choice of electrolyte, selection of electrodes, temperature of electrolyte bath and the time of electrolysis in order to ensure that the daughter radionuclide can be reproducibly recovered in high yields and high purity. The successful electrochemical generator technologies which have been developed and are discussed in this paper include the (90)Sr/(90)Y, (188)W/(188)Re and (99)Mo/(99m)Tc generators. Electrochemical separation not only acts as a separation technique but also is an effective concentration methodology which yields high radioactive concentrations of the daughter products. The lower consumption of reagents and minimal generation of radioactive wastes using such electrochemical techniques are compatible with 'green chemistry' principles.

Steel refining with an electrochemical cell

DOEpatents

Blander, M.; Cook, G.M.

1988-05-17

Apparatus is described for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom. 2 figs.

Steel refining with an electrochemical cell

DOEpatents

Blander, M.; Cook, G.M.

1985-05-21

Disclosed is an apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Steel refining with an electrochemical cell

DOEpatents

Blander, Milton; Cook, Glenn M.

1988-01-01

Apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Refractory lining for electrochemical cell

DOEpatents

Blander, Milton; Cook, Glenn M.

1987-01-01

Apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contcat with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Separators used in microbial electrochemical technologies: Current status and future prospects.

PubMed

Daud, Siti Mariam; Kim, Byung Hong; Ghasemi, Mostafa; Daud, Wan Ramli Wan

2015-11-01

Microbial electrochemical technologies (METs) are emerging green processes producing useful products from renewable sources without causing environmental pollution and treating wastes. The separator, an important part of METs that greatly affects the latter's performance, is commonly made of Nafion proton exchange membrane (PEM). However, many problems have been identified associated with the Nafion PEM such as high cost of membrane, significant oxygen and substrate crossovers, and transport of cations other than protons protons and biofouling. A variety of materials have been offered as alternative separators such as ion-exchange membranes, salt bridges, glass fibers, composite membranes and porous materials. It has been claimed that low cost porous materials perform better than PEM. These include J-cloth, nylon filter, glass fiber mat, non-woven cloth, earthen pot and ceramics that enable non-ion selective charge transfer. This paper provides an up-to-date review on porous separators and plots directions for future studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

Microchannel-electrode alignment and separation parameters comparison in microchip capillary electrophoresis by scanning electrochemical microscopy.

PubMed

Wang, Kang; Xia, Xing-Hua

2006-03-31

The end of separation channel in a microchip was electrochemically mapped using the feedback imaging mode of scanning electrochemical microscopy (SECM). This method provides a convenient way for microchannel-electrode alignment in microchip capillary electrophoresis. Influence of electrode-to-channel positions on separation parameters in this capillary electrophoresis-electrochemical detection (CE-ED) was then investigated. For the trapezoid shaped microchannel, detection in the central area resulted in the best apparent separation efficiency and peak shape. In the electrode-to-channel distance ranging from 65 to 15mum, the limiting peak currents of dopamine increased with the decrease of the detection distance due to the limited diffusion and convection of the sample band. Results showed that radial position and axial distance of the detection electrode to microchannel was important for the improvement of separation parameters in CE amperometric detection.

Separators - Technology review: Ceramic based separators for secondary batteries

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

Nestler, Tina; Schmid, Robert; Münchgesang, Wolfram

Besides a continuous increase of the worldwide use of electricity, the electric energy storage technology market is a growing sector. At the latest since the German energy transition ('Energiewende') was announced, technological solutions for the storage of renewable energy have been intensively studied. Storage technologies in various forms are commercially available. A widespread technology is the electrochemical cell. Here the cost per kWh, e. g. determined by energy density, production process and cycle life, is of main interest. Commonly, an electrochemical cell consists of an anode and a cathode that are separated by an ion permeable or ion conductive membranemore » - the separator - as one of the main components. Many applications use polymeric separators whose pores are filled with liquid electrolyte, providing high power densities. However, problems arise from different failure mechanisms during cell operation, which can affect the integrity and functionality of these separators. In the case of excessive heating or mechanical damage, the polymeric separators become an incalculable security risk. Furthermore, the growth of metallic dendrites between the electrodes leads to unwanted short circuits. In order to minimize these risks, temperature stable and non-flammable ceramic particles can be added, forming so-called composite separators. Full ceramic separators, in turn, are currently commercially used only for high-temperature operation systems, due to their comparably low ion conductivity at room temperature. However, as security and lifetime demands increase, these materials turn into focus also for future room temperature applications. Hence, growing research effort is being spent on the improvement of the ion conductivity of these ceramic solid electrolyte materials, acting as separator and electrolyte at the same time. Starting with a short overview of available separator technologies and the separator market, this review focuses on ceramic-based separators. Two prominent examples, the lithium-ion and sodium-sulfur battery, are described to show the current stage of development. New routes are presented as promising technologies for safe and long-life electrochemical storage cells.« less

Separators - Technology review: Ceramic based separators for secondary batteries

NASA Astrophysics Data System (ADS)

Nestler, Tina; Schmid, Robert; Münchgesang, Wolfram; Bazhenov, Vasilii; Schilm, Jochen; Leisegang, Tilmann; Meyer, Dirk C.

2014-06-01

Besides a continuous increase of the worldwide use of electricity, the electric energy storage technology market is a growing sector. At the latest since the German energy transition ("Energiewende") was announced, technological solutions for the storage of renewable energy have been intensively studied. Storage technologies in various forms are commercially available. A widespread technology is the electrochemical cell. Here the cost per kWh, e. g. determined by energy density, production process and cycle life, is of main interest. Commonly, an electrochemical cell consists of an anode and a cathode that are separated by an ion permeable or ion conductive membrane - the separator - as one of the main components. Many applications use polymeric separators whose pores are filled with liquid electrolyte, providing high power densities. However, problems arise from different failure mechanisms during cell operation, which can affect the integrity and functionality of these separators. In the case of excessive heating or mechanical damage, the polymeric separators become an incalculable security risk. Furthermore, the growth of metallic dendrites between the electrodes leads to unwanted short circuits. In order to minimize these risks, temperature stable and non-flammable ceramic particles can be added, forming so-called composite separators. Full ceramic separators, in turn, are currently commercially used only for high-temperature operation systems, due to their comparably low ion conductivity at room temperature. However, as security and lifetime demands increase, these materials turn into focus also for future room temperature applications. Hence, growing research effort is being spent on the improvement of the ion conductivity of these ceramic solid electrolyte materials, acting as separator and electrolyte at the same time. Starting with a short overview of available separator technologies and the separator market, this review focuses on ceramic-based separators. Two prominent examples, the lithium-ion and sodium-sulfur battery, are described to show the current stage of development. New routes are presented as promising technologies for safe and long-life electrochemical storage cells.

Use of ion conductors in the pyrochemical reduction of oxides

DOEpatents

Miller, William E.; Tomczuk, Zygmunt

1994-01-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO.sub.2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a .beta.-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca.degree. used for reducing UO.sub.2 and PuO.sub.2 to U and Pu.

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.

Energy conversion and storage program

NASA Astrophysics Data System (ADS)

Cairns, E. J.

1992-03-01

The Energy Conversion and Storage Program applies chemistry and materials science principles to solve problems in: (1) production of new synthetic fuels; (2) development of high-performance rechargeable batteries and fuel cells; (3) development of advanced thermochemical processes for energy conversion; (4) characterization of complex chemical processes; and (5) application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis. Electrochemistry research aims to develop advanced power systems for electric vehicle and stationary energy storage applications. Topics include identification of new electrochemical couples for advanced rechargeable batteries, improvements in battery and fuel-cell materials, and the establishment of engineering principles applicable to electrochemical energy storage and conversion. Chemical Applications research includes topics such as separations, catalysis, fuels, and chemical analyses. Included in this program area are projects to develop improved, energy-efficient methods for processing waste streams from synfuel plants and coal gasifiers. Other research projects seek to identify and characterize the constituents of liquid fuel-system streams and to devise energy-efficient means for their separation. Materials Applications research includes the evaluation of the properties of advanced materials, as well as the development of novel preparation techniques. For example, the use of advanced techniques, such as sputtering and laser ablation, are being used to produce high-temperature superconducting films.

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.

Electrochemically assisted photocatalysis: Highly efficient treatment using thermal titanium oxides doped and non-doped electrodes for water disinfection.

PubMed

Dos Santos, Andreia Betina Kreuser; Claro, Elis Marina Turini; Montagnolli, Renato Nallin; Cruz, Jaqueline Matos; Lopes, Paulo Renato Matos; Bidoia, Ederio Dino

2017-12-15

Electrochemically assisted photocatalysis (by electronic drainage) is a highly promising method for disinfection of water. In this research, the efficiency of photolytic oxidation using UV-A radiation and electrochemically assisted photocatalysis (with electric potential of 1.5 V) was studied by using electrodes prepared by thermal treatment and doped with silver, for inactivation of Escherichia coli and Staphylococcus aureus. The Chick-Watson microorganism inactivation model was applied and the electrical energy consumption of the process was calculated. It was observed no significant inactivation of microorganisms when UV-A light or electric potential were applied separately. However, the electrochemically assisted photocatalytic process, with Ag-doped electrode completely inactivated the microbial population after 10 (E. coli) and 60 min (S. aureus). The best performing non-doped electrodes achieved 52.74% (E. coli) and 44.09% (S. aureus) inactivation rates after 60 min. Thus, electrochemically assisted photocatalytic activity was not only effective for the inactivation of microorganisms, but also notably low on electrical energy consumption during the treatment due to small current and low electric potential applied. Copyright © 2017 Elsevier Ltd. All rights reserved.

In-channel electrochemical detection in the middle of microchannel under high electric field.

PubMed

Kang, Chung Mu; Joo, Segyeong; Bae, Je Hyun; Kim, Yang-Rae; Kim, Yongseong; Chung, Taek Dong

2012-01-17

We propose a new method for performing in-channel electrochemical detection under a high electric field using a polyelectrolytic gel salt bridge (PGSB) integrated in the middle of the electrophoretic separation channel. The finely tuned placement of a gold working electrode and the PGSB on an equipotential surface in the microchannel provided highly sensitive electrochemical detection without any deterioration in the separation efficiency or interference of the applied electric field. To assess the working principle, the open circuit potentials between gold working electrodes and the reference electrode at varying distances were measured in the microchannel under electrophoretic fields using an electrically isolated potentiostat. In addition, "in-channel" cyclic voltammetry confirmed the feasibility of electrochemical detection under various strengths of electric fields (∼400 V/cm). Effective separation on a microchip equipped with a PGSB under high electric fields was demonstrated for the electrochemical detection of biological compounds such as dopamine and catechol. The proposed "in-channel" electrochemical detection under a high electric field enables wider electrochemical detection applications in microchip electrophoresis.

Ion-/proton-conducting apparatus and method

DOEpatents

Yates, Matthew [Penfield, NY; Liu, Dongxia [Rochester, NY

2011-05-17

A c-axis-oriented HAP thin film synthesized by seeded growth on a palladium hydrogen membrane substrate. An exemplary synthetic process includes electrochemical seeding on the substrate, and secondary and tertiary hydrothermal treatments under conditions that favor growth along c-axes and a-axes in sequence. By adjusting corresponding synthetic conditions, an HAP this film can be grown to a controllable thickness with a dense coverage on the underlying substrate. The thin films have relatively high proton conductivity under hydrogen atmosphere and high temperature conditions. The c-axis oriented films may be integrated into fuel cells for application in the intermediate temperature range of 200-600.degree. C. The electrochemical-hydrothermal deposition technique may be applied to create other oriented crystal materials having optimized properties, useful for separations and catalysis as well as electronic and electrochemical applications, electrochemical membrane reactors, and in chemical sensors.

Innovative approach for the valorization of useful metals from waste electric and electronic equipment (WEEE)

NASA Astrophysics Data System (ADS)

Soare, V.; Burada, M.; Dumitrescu, D. V.; Constantin, I.; Soare, V.; Popescu, A.-M. J.; Carcea, I.

2016-08-01

Waste electric and electronic equipment are an important secondary source of rare and precious metals and their processing through ecological technologies constitutes a major concern in the European Union and significantly contributes to the reduction of environmental pollution and to the preservation of valuable resources of nonferrous metals. The paper presents an innovative approach for the complex valorization of useful metals contained in WEEE. The method consists in the melting of WEEE in a furnace in a microwave field at temperatures of 1000 ÷1200°C, for the complete separation of the metallic fraction from the organic components. The gases resulting from the melting process were also treated/neutralized in a microwave environment and the obtained metallic bulk (multi-component alloy) was processed through combined hydrometallurgical and electrochemical methods. The major elements in the metallic bulk (Cu, Sn, Zn, Pb) were separated/recovered by anodic dissolution, respectively by leaching in nitric acid followed by cementation using various agents, or by electrodeposition. Depending on the electrochemical parameters, cathodic deposits consisting of Cu, with a purity higher than 99.9%, or of Cu-Sn and Cu-Sn-Zn alloys were obtained. Silver was valorized by leaching/precipitation with NaCl and the gold concentrated in the anodic slime will be recovered by thiourea extraction. The experiments performed demonstrate the possibility of ecological and efficient processing of WEEE in a microwave field and the recovery of nonferrous and precious metals through combined hydrometallurgical and electrochemical methods.

Nano-TiO2 decorated carbon coating on the separator to physically and chemically suppress the shuttle effect for lithium-sulfur battery

NASA Astrophysics Data System (ADS)

Shao, Hongyuan; Wang, Weikun; Zhang, Hao; Wang, Anbang; Chen, Xiaonong; Huang, Yaqin

2018-02-01

Despite recent progress in designing modified separators for lithium-sulfur (Li-S) batteries, detail in optimizing the synergistic effect between chemical and physical immobilization for lithium polysulfides (LiPS) in modified separator hasn't been investigated totally. Here, a nano-TiO2 decorated carbon layer (T-DCL) has been successfully applied to modify separator for the Li-S battery. The results indicate that appropriate weight percentage of nano-TiO2 uniformly distributed in conductive carbon layer is effective to chemically and physically immobilize for LiPS, and promote the electron transfer during discharge/charge process. The performance of the modified Li-S battery with T-DCL separator are significantly enhanced, with a specific capacity of 883 mAh g-1 retained after 180 cycles at 0.1 C and 762 mAh g-1 retained after 200 cycles at 0.5C, which are much higher than that of separators only coated with TiO2 layer or conductive carbon layer. Besides, the separator coated with T-DCL also shows low electrochemical impedance and good lithium anode protection. These results indicate that separator with T-DCL is promising to balance the physical and chemical LiPS trapping effect, and optimize the electrochemical performance for Li-S battery.

Magnetic separation of antibiotics by electrochemical magnetic seeding

NASA Astrophysics Data System (ADS)

Ihara, I.; Toyoda, K.; Beneragama, N.; Umetsu, K.

2009-03-01

Magnetic separation of several classes of antibiotics was investigated using electrochemical magnetic seeding. Electrocoagulation with a sacrificial anode followed by addition of magnetite particles was applied for the magnetic seeding of antibiotics. With electrochemical magnetic seeding using an iron anode, tetracycline antibiotics (oxytetracycline, chlortetracycline, doxycycline and tetracycline) and cephalosporin antibiotic (cefdinir) were rapidly removed from synthetic wastewater by magnetic separation using a neodymium magnet. Iron and aluminium anodes were suitable for magnetic seeding of the antibiotics. The results indicated that the ability of antibiotics to form strong complex with iron and aluminium allowed the higher removal by magnetic separation. This method would be appropriate for rapid treatment of antibiotics in wastewater.

Investigations of Physical Processes in Microgravity Relevant to Space Electrochemical Power Systems

NASA Technical Reports Server (NTRS)

Lvovich, Vadim F.; Green, Robert; Jakupca, Ian

2015-01-01

NASA has performed physical science microgravity flight experiments in the areas of combustion science, fluid physics, material science and fundamental physics research on the International Space Station (ISS) since 2001. The orbital conditions on the ISS provide an environment where gravity driven phenomena, such as buoyant convection, are nearly negligible. Gravity strongly affects fluid behavior by creating forces that drive motion, shape phase boundaries and compress gases. The need for a better understanding of fluid physics has created a vigorous, multidisciplinary research community whose ongoing vitality is marked by the continuous emergence of new fields in both basic and applied science. In particular, the low-gravity environment offers a unique opportunity for the study of fluid physics and transport phenomena that are very relevant to management of fluid - gas separations in fuel cell and electrolysis systems. Experiments conducted in space have yielded rich results. These results provided valuable insights into fundamental fluid and gas phase behavior that apply to space environments and could not be observed in Earth-based labs. As an example, recent capillary flow results have discovered both an unexpected sensitivity to symmetric geometries associated with fluid container shape, and identified key regime maps for design of corner or wedge-shaped passive gas-liquid phase separators. In this presentation we will also briefly review some of physical science related to flight experiments, such as boiling, that have applicability to electrochemical systems, along with ground-based (drop tower, low gravity aircraft) microgravity electrochemical research. These same buoyancy and interfacial phenomena effects will apply to electrochemical power and energy storage systems that perform two-phase separation, such as water-oxygen separation in life support electrolysis, and primary space power generation devices such as passive primary fuel cell.

Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple

DOE PAGES

Ellis, Ross J.; Bera, Mrinal K.; Reinhart, Benjamin; ...

2016-11-07

Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, thismore » presents a new route for controlling anion transfer in electrochemically-driven separation applications.« less

Parameter optimization of electrochemical machining process using black hole algorithm

NASA Astrophysics Data System (ADS)

Singh, Dinesh; Shukla, Rajkamal

2017-12-01

Advanced machining processes are significant as higher accuracy in machined component is required in the manufacturing industries. Parameter optimization of machining processes gives optimum control to achieve the desired goals. In this paper, electrochemical machining (ECM) process is considered to evaluate the performance of the considered process using black hole algorithm (BHA). BHA considers the fundamental idea of a black hole theory and it has less operating parameters to tune. The two performance parameters, material removal rate (MRR) and overcut (OC) are considered separately to get optimum machining parameter settings using BHA. The variations of process parameters with respect to the performance parameters are reported for better and effective understanding of the considered process using single objective at a time. The results obtained using BHA are found better while compared with results of other metaheuristic algorithms, such as, genetic algorithm (GA), artificial bee colony (ABC) and bio-geography based optimization (BBO) attempted by previous researchers.

Evaluating the trade-off between mechanical and electrochemical performance of separators for lithium-ion batteries: Methodology and application

NASA Astrophysics Data System (ADS)

Plaimer, Martin; Breitfuß, Christoph; Sinz, Wolfgang; Heindl, Simon F.; Ellersdorfer, Christian; Steffan, Hermann; Wilkening, Martin; Hennige, Volker; Tatschl, Reinhard; Geier, Alexander; Schramm, Christian; Freunberger, Stefan A.

2016-02-01

Lithium-ion batteries are in widespread use in electric vehicles and hybrid vehicles. Besides features like energy density, cost, lifetime, and recyclability the safety of a battery system is of prime importance. The separator material impacts all these properties and requires therefore an informed selection. The interplay between the mechanical and electrochemical properties as key selection criteria is investigated. Mechanical properties were investigated using tensile and puncture penetration tests at abuse relevant conditions. To investigate the electrochemical performance in terms of effective conductivity a method based on impedance spectroscopy was introduced. This methodology is applied to evaluate ten commercial separators which allows for a trade-off analysis of mechanical versus electrochemical performance. Based on the results, and in combination with other factors, this offers an effective approach to select suitable separators for automotive applications.

Production of nuclear grade zirconium: A review

NASA Astrophysics Data System (ADS)

Xu, L.; Xiao, Y.; van Sandwijk, A.; Xu, Q.; Yang, Y.

2015-11-01

Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium as a fuel cladding material. This paper provides an overview of the processes for nuclear grade zirconium production with emphasis on the methods of Zr-Hf separation. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The known pyrometallurgical Zr-Hf separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt-metal equilibrium. In the present paper, the available Zr-Hf separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

Copper recovery and gold enrichment from waste printed circuit boards by mediated electrochemical oxidation.

PubMed

Fogarasi, Szabolcs; Imre-Lucaci, Florica; Imre-Lucaci, Arpád; Ilea, Petru

2014-05-30

The present study aims to develop an eco-friendly chemical-electrochemical process for the simultaneous recovery of copper and separation of a gold rich residue from waste printed circuit boards (WPCBs). The process was carried out by employing two different types of reactors coupled in series: a leaching reactor with a perforated rotating drum, for the dissolution of base metals and a divided electrochemical reactor for the regeneration of the leaching solution with the parallel electrowinning of copper. The process performances were evaluated on the basis of the dissolution efficiency, current efficiency and specific energy consumptions. Finally a process scale up was realized taking into consideration the optimal values of the operating parameters. The laboratory scale leaching plant allowed the recovery of a high purity copper deposit (99.04wt.%) at a current efficiency of 63.84% and specific energy consumption of 1.75kWh/kg cooper. The gold concentration in the remained solid residue was 25 times higher than the gold concentration in the initial WPCB samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Separator-spacer for electrochemical systems

DOEpatents

Grimes, Patrick G.; Einstein, Harry; Newby, Kenneth R.; Bellows, Richard J.

1983-08-02

An electrochemical cell construction features a novel co-extruded plastic electrode in an interleaved construction with a novel integral separator-spacer. Also featured is a leak and impact resistant construction for preventing the spill of corrosive materials in the event of rupture.

Comparison of phthalic acid removal from aqueous solution by electrochemical methods: Optimization, kinetic and sludge study.

PubMed

Sandhwar, Vishal Kumar; Prasad, Basheshwar

2017-12-01

In this work, comparative study between electrochemical processes such as electrocoagulation (EC), peroxi-coagulation (PC) and peroxi-electrocoagulation (PEC) was performed for the removal of phthalic acid (PA) and chemical oxygen demand (COD) from aqueous medium. Initially, acid treatment was studied at various pH (1-3) and temperature (10-55 °C). Subsequently, the supernatant was re-treated by electrochemical processes such as EC, PC and PEC separately. Independent parameters viz. pH, current density (CD), electrolyte concentration (m), electrode gap (g), H 2 O 2 concentration and electrolysis time (t) were optimized by Central Composite Design (CCD) for these electrochemical processes. All three processes were compared based on removal, energy consumption, kinetic analysis, operating cost and sludge characteristics. In this study, PEC process was found more efficient among EC, PC and PEC processes in order to get maximum removal, minimum energy consumption and minimum operating cost. Maximum removal of PA- 68.21%, 74.36%, 82.25% & COD- 64.79%, 68.15%, 75.21% with energy consumption - 120.95, 97.51, 65.68 (kWh/kg COD removed) were attained through EC, PC and PEC processes respectively at their corresponding optimum conditions. Results indicated that PA and COD removals are in order of PEC > PC > EC under optimum conditions. First order kinetic model was found able to describe the degradation kinetics and provided best correlation for the removal rate within the acceptable error range. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ion-conducting ceramic apparatus, method, fabrication, and applications

DOEpatents

Yates, Matthew [Penfield, NY; Liu, Dongxia [Rochester, NY

2012-03-06

A c-axis-oriented HAP thin film synthesized by seeded growth on a palladium hydrogen membrane substrate. An exemplary synthetic process includes electrochemical seeding on the substrate, and secondary and tertiary hydrothermal treatments under conditions that favor growth along c-axes and a-axes in sequence. By adjusting corresponding synthetic conditions, an HAP this film can be grown to a controllable thickness with a dense coverage on the underlying substrate. The thin films have relatively high proton conductivity under hydrogen atmosphere and high temperature conditions. The c-axis oriented films may be integrated into fuel cells for application in the intermediate temperature range of 200-600.degree. C. The electrochemical-hydrothermal deposition technique may be applied to create other oriented crystal materials having optimized properties, useful for separations and catalysis as well as electronic and electrochemical applications, electrochemical membrane reactors, and in chemical sensors.

Use of ion conductors in the pyrochemical reduction of oxides

DOEpatents

Miller, W.E.; Tomczuk, Z.

1994-02-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO[sub 2] oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a [beta]-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca[sup o] used for reducing UO[sub 2] and PuO[sub 2] to U and Pu. 2 figures.

Scalable and efficient separation of hydrogen isotopes using graphene-based electrochemical pumping

NASA Astrophysics Data System (ADS)

Lozada-Hidalgo, M.; Zhang, S.; Hu, S.; Esfandiar, A.; Grigorieva, I. V.; Geim, A. K.

2017-05-01

Thousands of tons of isotopic mixtures are processed annually for heavy-water production and tritium decontamination. The existing technologies remain extremely energy intensive and require large capital investments. New approaches are needed to reduce the industry's footprint. Recently, micrometre-size crystals of graphene are shown to act as efficient sieves for hydrogen isotopes pumped through graphene electrochemically. Here we report a fully-scalable approach, using graphene obtained by chemical vapour deposition, which allows a proton-deuteron separation factor of around 8, despite cracks and imperfections. The energy consumption is projected to be orders of magnitude smaller with respect to existing technologies. A membrane based on 30 m2 of graphene, a readily accessible amount, could provide a heavy-water output comparable to that of modern plants. Even higher efficiency is expected for tritium separation. With no fundamental obstacles for scaling up, the technology's simplicity, efficiency and green credentials call for consideration by the nuclear and related industries.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance.

PubMed

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-02-12

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance

PubMed Central

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-01-01

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization. PMID:29439514

Supported liquid membrane electrochemical separators

DOEpatents

Pemsler, J. Paul; Dempsey, Michael D.

1986-01-01

Supported liquid membrane separators improve the flexibility, efficiency and service life of electrochemical cells for a variety of applications. In the field of electrochemical storage, an alkaline secondary battery with improved service life is described in which a supported liquid membrane is interposed between the positive and negative electrodes. The supported liquid membranes of this invention can be used in energy production and storage systems, electrosynthesis systems, and in systems for the electrowinning and electrorefining of metals.

Separation of Zirconium and Hafnium: A Review

NASA Astrophysics Data System (ADS)

Xu, L.; Xiao, Y.; van Sandwijk, A.; Xu, Q.; Yang, Y.

Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium. This paper provides an overview of the processes for separating hafnium from zirconium. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The current dominant zirconium production route involves pyrometallurgical ore cracking, multi-step hydrometallurgical liquid-liquid extraction for hafnium removal and the reduction of zirconium tetrachloride to the pure metal by the Kroll process. The lengthy hydrometallurgical Zr-Hf separation operations leads to high production cost, intensive labour and heavy environmental burden. Using a compact pyrometallurgical separation method can simplify the whole production flowsheet with a higher process efficiency. The known separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt extraction. The commercially operating extractive distillation process is a significant advance in Zr-Hf separation technology but it suffers from high process maintenance cost. The recently developed new process based on molten salt-metal equilibrium for Zr-Hf separation shows a great potential for industrial application, which is compact for nuclear grade zirconium production starting from crude ore. In the present paper, the available separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

Aluminum oxyhydroxide based separator/electrolyte and battery system, and a method making the same

DOEpatents

Gerald, II, Rex E.; Klingler, Robert J [Glenview, IL; Rathke, Jerome W [Homer Glen, IL

2011-03-08

The instant invention relates a solid-state electrochemical cell and a novel separator/electrolyte incorporated therein. A preferred embodiment of the invented electrochemical cell generally comprises a unique metal oxyhydroxide based (i.e. AlOOH) separator/electrolyte membrane sandwiched between a first electrode and a second electrode. A preferred novel separator/electrolyte comprises a nanoparticulate metal oxyhydroxide, preferably AlOOH and a salt which are mixed and then pressed together to form a monolithic metal oxyhydroxide-salt membrane.

Aluminum oxyhydroxide based separator/electrolyte and battery system, and a method of making the same

DOEpatents

Gerald, II; Rex, E [Brookfield, IL; Klingler, Robert J [Glenview, IL; Rathke, Jerome W [Homer Glen, IL

2011-02-15

The instant invention relates a solid-state electrochemical cell and a novel separator/electrolyte incorporated therein. The invented electrochemical cell generally comprising: a unique metal oxyhydroxide based (i.e. AlOOH) separator/electrolyte membrane sandwiched between a first electrode and a second electrode. The novel separator/electrolyte comprises a nanoparticulate metal oxyhydroxide, preferably AlOOH and a salt which are mixed and then pressed together to form a monolithic metal oxyhydroxide-salt membrane.

Polarization Resistance Measurement in Tap Water: The Influence of Rust Electrochemical Activity

NASA Astrophysics Data System (ADS)

Vasyliev, Georgii

2017-08-01

Corrosion rate of mild steel in tap water during 4300 h was estimated by LPR and weight-loss methods coupled with OCP measurements. The LPR results were found to be overestimated compared to the weight-loss data within initial 2000 h of exposure. The electrochemical activity of the rust separated from the metal surface was studied by cycling voltammetry using a home-built powder graphite electrode. High redox currents corresponding to the initial 2000 h of exposure were detected. Rust composition was characterized with IR and XRD, and the highest amounts of electrochemically active β- and γ-FeOOH were again detected for the initial 2000 h. Current consumption in rust transformation processes during LPR measurement in the galvanostatic mode accounts for overestimation of the corrosion rate. The time dependence of rust electrochemical activity correlates with OCP variation with time. During initial 2000 h, OCP values are shifted by 50 mV to cathodic side. For the period of a higher rust electrochemical activity, the use of a reduced B is suggested to increase accuracy of LPR technique in tap water.

Electrochemical Cell with Improved Water or Gas Management

NASA Technical Reports Server (NTRS)

LaGrange, Jay W. (Inventor); Smith, William F. (Inventor); McElroy, James F. (Inventor)

2015-01-01

An electrochemical cell having a water/gas porous separator prepared from a polymeric material and one or more conductive cell components that pass through, or are located in close proximity to, the water/gas porous separator, is provided. The inventive cell provides a high level of in-cell electrical conductivity.

Modeling integrated photovoltaic–electrochemical devices using steady-state equivalent circuits

PubMed Central

Winkler, Mark T.; Cox, Casandra R.; Nocera, Daniel G.; Buonassisi, Tonio

2013-01-01

We describe a framework for efficiently coupling the power output of a series-connected string of single-band-gap solar cells to an electrochemical process that produces storable fuels. We identify the fundamental efficiency limitations that arise from using solar cells with a single band gap, an arrangement that describes the use of currently economic solar cell technologies such as Si or CdTe. Steady-state equivalent circuit analysis permits modeling of practical systems. For the water-splitting reaction, modeling defines parameters that enable a solar-to-fuels efficiency exceeding 18% using laboratory GaAs cells and 16% using all earth-abundant components, including commercial Si solar cells and Co- or Ni-based oxygen evolving catalysts. Circuit analysis also provides a predictive tool: given the performance of the separate photovoltaic and electrochemical systems, the behavior of the coupled photovoltaic–electrochemical system can be anticipated. This predictive utility is demonstrated in the case of water oxidation at the surface of a Si solar cell, using a Co–borate catalyst.

Tunneling Mode of Scanning Electrochemical Microscopy: Probing Electrochemical Processes at Single Nanoparticles.

PubMed

Sun, Tong; Wang, Dengchao; Mirkin, Michael V

2018-06-18

Electrochemical experiments at individual nanoparticles (NPs) can provide new insights into their structure-activity relationships. By using small nanoelectrodes as tips in a scanning electrochemical microscope (SECM), we recently imaged individual surface-bound 10-50 nm metal NPs. Herein, we introduce a new mode of SECM operation based on tunneling between the tip and a nanoparticle immobilized on the insulating surface. The obtained current vs. distance curves show the transition from the conventional feedback response to electron tunneling between the tip and the NP at separation distances of less than about 3 nm. In addition to high-resolution imaging of the NP topography, the tunneling mode enables measurement of the heterogeneous kinetics at a single NP without making an ohmic contact with it. The developed method should be useful for studying the effects of nanoparticle size and geometry on electrocatalytic activity in real-world applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Origin of Capacity Fading in Nano-Sized Co3O4 Electrodes: Electrochemical Impedance Spectroscopy Study

NASA Astrophysics Data System (ADS)

Kang, Jin-Gu; Ko, Young-Dae; Park, Jae-Gwan; Kim, Dong-Wan

2008-10-01

Transition metal oxides have been suggested as innovative, high-energy electrode materials for lithium-ion batteries because their electrochemical conversion reactions can transfer two to six electrons. However, nano-sized transition metal oxides, especially Co3O4, exhibit drastic capacity decay during discharge/charge cycling, which hinders their practical use in lithium-ion batteries. Herein, we prepared nano-sized Co3O4 with high crystallinity using a simple citrate-gel method and used electrochemical impedance spectroscopy method to examine the origin for the drastic capacity fading observed in the nano-sized Co3O4 anode system. During cycling, AC impedance responses were collected at the first discharged state and at every subsequent tenth discharged state until the 100th cycle. By examining the separable relaxation time of each electrochemical reaction and the goodness-of-fit results, a direct relation between the charge transfer process and cycling performance was clearly observed.

Safety shutdown separators

DOEpatents

Carlson, Steven Allen; Anakor, Ifenna Kingsley; Farrell, Greg Robert

2015-06-30

The present invention pertains to electrochemical cells which comprise (a) an anode; (b) a cathode; (c) a solid porous separator, such as a polyolefin, xerogel, or inorganic oxide separator; and (d) a nonaqueous electrolyte, wherein the separator comprises a porous membrane having a microporous coating comprising polymer particles which have not coalesced to form a continuous film. This microporous coating on the separator acts as a safety shutdown layer that rapidly increases the internal resistivity and shuts the cell down upon heating to an elevated temperature, such as 110.degree. C. Also provided are methods for increasing the safety of an electrochemical cell by utilizing such separators with a safety shutdown layer.

Electrochemical processing of lead-containing waste ballistics

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

Huber, C.O.; Olsen, G.P.

1995-12-31

Literature review indicates that propellant ingredients in NOSIH-AA2 have been investigated electrochemical separation. Papers on related electroanalytical chemistry offer help in indicating which electrolytic separation systems to investigate. These included copper and nickel electrodes in alkaline solution. Voltammetry studies in 0.1 M NaOH showed that lead metal can be readily collected at a copper cathode and that lead dioxide can be deposited at a nickel anode. Cathodic and anodic deposition reactions begin at less than minus or plus 0.5 V. resp. Other species present in the propellant are also reactive at the anode. Deposits with good mechanical properties resulted, evenmore » with 40 mA/cm{sup 2} current density. Lead concentrations in alkaline solutions can readily be monitored using anodic amperometry with the nickel electrode. Separations from actual propellant solutions in 3 M NaOH were demonstrated using nickel as anode and cathode. Gravimetric monitoring of both anode and cathode showed accumulations suggesting the exhaustive lead collection. Associated voltammetry data showed decreasing amounts of other electroactive species at the anode as well as lead.« less

Functionalized-graphene modified graphite electrode for the selective determination of dopamine in presence of uric acid and ascorbic acid.

PubMed

Mallesha, Malledevaru; Manjunatha, Revanasiddappa; Nethravathi, C; Suresh, Gurukar Shivappa; Rajamathi, Michael; Melo, Jose Savio; Venkatesha, Thimmappa Venkatarangaiah

2011-06-01

Graphene is chemically synthesized by solvothermal reduction of colloidal dispersions of graphite oxide. Graphite electrode is modified with functionalized-graphene for electrochemical applications. Electrochemical characterization of functionalized-graphene modified graphite electrode (FGGE) is carried out by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The behavior of FGGE towards ascorbic acid (AA), dopamine (DA) and uric acid (UA) has been investigated by CV, differential pulse voltammetry (DPV) and chronoamperommetry (CA). The FGGE showed excellent catalytic activity towards electrochemical oxidation of AA, DA and UA compared to that of the bare graphite electrode. The electrochemical oxidation signals of AA, DA and UA are well separated into three distinct peaks with peak potential separation of 193mv, 172mv and 264mV between AA-DA, DA-UA and AA-UA respectively in CV studies and the corresponding peak potential separations in DPV mode are 204mv, 141mv and 345mv. The FGGE is successfully used for the simultaneous detection of AA, DA and UA in their ternary mixture and DA in serum and pharmaceutical samples. The excellent electrocatalytic behavior of FGGE may lead to new applications in electrochemical analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

Pyroprocessing of Light Water Reactor Spent Fuels Based on an Electrochemical Reduction Technology

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

Ohta, Hirokazu; Inoue, Tadashi; Sakamura, Yoshiharu

A concept of pyroprocessing light water reactor (LWR) spent fuels based on an electrochemical reduction technology is proposed, and the material balance of the processing of mixed oxide (MOX) or high-burnup uranium oxide (UO{sub 2}) spent fuel is evaluated. Furthermore, a burnup analysis for metal fuel fast breeder reactors (FBRs) is conducted on low-decontamination materials recovered by pyroprocessing. In the case of processing MOX spent fuel (40 GWd/t), UO{sub 2} is separately collected for {approx}60 wt% of the spent fuel in advance of the electrochemical reduction step, and the product recovered through the rare earth (RE) removal step, which hasmore » the composition uranium:plutonium:minor actinides:fission products (FPs) = 76.4:18.4:1.7:3.5, can be applied as an ingredient of FBR metal fuel without a further decontamination process. On the other hand, the electroreduced alloy of high-burnup UO{sub 2} spent fuel (48 GWd/t) requires further decontamination of residual FPs by an additional process such as electrorefining even if RE FPs are removed from the alloy because the recovered plutonium (Pu) is accompanied by almost the same amount of FPs in addition to RE. However, the amount of treated materials in the electrorefining step is reduced to {approx}10 wt% of the total spent fuel owing to the prior UO{sub 2} recovery step. These results reveal that the application of electrochemical reduction technology to LWR spent oxide fuel is a promising concept for providing FBR metal fuel by a rationalized process.« less

Electrochemical ion separation in molten salts

DOEpatents

Spoerke, Erik David; Ihlefeld, Jon; Waldrip, Karen; Wheeler, Jill S.; Brown-Shaklee, Harlan James; Small, Leo J.; Wheeler, David R.

2017-12-19

A purification method that uses ion-selective ceramics to electrochemically filter waste products from a molten salt. The electrochemical method uses ion-conducting ceramics that are selective for the molten salt cations desired in the final purified melt, and selective against any contaminant ions. The method can be integrated into a slightly modified version of the electrochemical framework currently used in pyroprocessing of nuclear wastes.

Separation of metal ions from aqueous solutions

DOEpatents

Almon, Amy C.

1994-01-01

A process and apparatus for quantitatively and selectively separating metal ions from mixtures thereof in aqueous solution. The apparatus includes, in combination, a horizontal electrochemical flow cell containing flow bulk electrolyte solution and an aqueous, metal ion-containing solution, the cell containing a metal mesh working electrode, a counter electrode positioned downstream from the working electrode, an independent variable power supply/potentiostat positioned outside of the flow cell and connected to the electrodes, and optionally a detector such as a chromatographic detector, positioned outside the flow cell. This apparatus and its operation has significant application where trace amounts of metal ions are to be separated.

Electrochemical cell with powdered electrically insulative material as a separator

DOEpatents

Mathers, James P.; Olszanski, Theodore W.; Boquist, Carl W.

1978-01-01

A secondary electrochemical cell includes electrodes separated by a layer of electrically insulative powder. The powder includes refractory materials selected from the oxides and nitrides of metals and metaloids. The powdered refractory material, blended with electrolyte particles, can be compacted in layers with electrode materials to form an integral electrode structure or separately assembled into the cell. The assembled cell is heated to operating temperature leaving porous layers of electrically insulative, refractory particles, containing molten electrolyte between the electrodes.

Electrochemical Conversion of Biologically Produced Muconic Acid: Key Considerations for Scale-Up and Corresponding Technoeconomic Analysis

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

Matthiesen, John E.; Suástegui, Miguel; Wu, Yutong

We present muconic acid, an unsaturated diacid that can be produced from cellulosic sugars and lignin monomers by fermentation, emerges as a promising intermediate for the sustainable manufacture of commodity polyamides and polyesters including Nylon-6,6 and polyethylene terephthalate (PET). Current conversion schemes consist in the biological production of cis,cis-muconic acid using metabolically engineered yeasts and bacteria, and the subsequent diversification to adipic acid, terephthalic acid, and their derivatives using chemical catalysts. In some instances, conventional precious metal catalysts can be advantageously replaced by base metal electrocatalysts. Here, we show the economic relevance of utilizing a hybrid biological–electrochemical conversion scheme tomore » convert glucose to trans-3-hexenedioic acid (t3HDA), a monomer used for the synthesis of bioadvantaged Nylon-6,6. Potential roadblocks to biological and electrochemical integration in a single reactor, including electrocatalyst deactivation due to biogenic impurities and low faradaic efficiency inherent to side reactions in complex media, have been studied and addressed. In this study, t3HDA was produced with 94% yield and 100% faradaic efficiency. With consideration of the high t3HDA yield and faradaic efficiency, a technoeconomic analysis was developed on the basis of the current yield and titer achieved for muconic acid, the figures of merit defined for industrial electrochemical processes, and the separation of the desired product from the medium. On the basis of this analysis, t3HDA could be produced for approximately $2.00 kg –1. The low cost for t3HDA is a primary factor of the electrochemical route being able to cascade biological catalysis and electrocatalysis in one pot without separation of the muconic acid intermediate from the fermentation broth.« less

Electrochemical Conversion of Biologically Produced Muconic Acid: Key Considerations for Scale-Up and Corresponding Technoeconomic Analysis

DOE PAGES

Matthiesen, John E.; Suástegui, Miguel; Wu, Yutong; ...

2016-10-05

We present muconic acid, an unsaturated diacid that can be produced from cellulosic sugars and lignin monomers by fermentation, emerges as a promising intermediate for the sustainable manufacture of commodity polyamides and polyesters including Nylon-6,6 and polyethylene terephthalate (PET). Current conversion schemes consist in the biological production of cis,cis-muconic acid using metabolically engineered yeasts and bacteria, and the subsequent diversification to adipic acid, terephthalic acid, and their derivatives using chemical catalysts. In some instances, conventional precious metal catalysts can be advantageously replaced by base metal electrocatalysts. Here, we show the economic relevance of utilizing a hybrid biological–electrochemical conversion scheme tomore » convert glucose to trans-3-hexenedioic acid (t3HDA), a monomer used for the synthesis of bioadvantaged Nylon-6,6. Potential roadblocks to biological and electrochemical integration in a single reactor, including electrocatalyst deactivation due to biogenic impurities and low faradaic efficiency inherent to side reactions in complex media, have been studied and addressed. In this study, t3HDA was produced with 94% yield and 100% faradaic efficiency. With consideration of the high t3HDA yield and faradaic efficiency, a technoeconomic analysis was developed on the basis of the current yield and titer achieved for muconic acid, the figures of merit defined for industrial electrochemical processes, and the separation of the desired product from the medium. On the basis of this analysis, t3HDA could be produced for approximately $2.00 kg –1. The low cost for t3HDA is a primary factor of the electrochemical route being able to cascade biological catalysis and electrocatalysis in one pot without separation of the muconic acid intermediate from the fermentation broth.« less

ssDNA degradation along capillary electrophoresis process using a Tris buffer.

PubMed

Ric, Audrey; Ong-Meang, Varravaddheay; Poinsot, Verena; Martins-Froment, Nathalie; Chauvet, Fabien; Boutonnet, Audrey; Ginot, Frédéric; Ecochard, Vincent; Paquereau, Laurent; Couderc, François

2017-06-01

Tris-Acetate buffer is currently used in the selection and the characterization of ssDNA by capillary electrophoresis (CE). By applying high voltage, the migration of ionic species into the capillary generates a current that induces water electrolysis. This phenomenon is followed by the modification of the pH and the production of Tris derivatives. By injecting ten times by capillary electrophoresis ssDNA (50 nM), the whole oligonucleotide was degraded. In this paper, we will show that the Tris buffer in the running vials is modified along the electrophoretic process by electrochemical reactions. We also observed that the composition of the metal ions changes in the running buffer vials. This phenomenon, never described in CE, is important for fluorescent ssDNA analysis using Tris buffer. The oligonucleotides are degraded by electrochemically synthesized species (present in the running Tris vials) until it disappears, even if the separation buffer in the capillary is clean. To address these issues, we propose to use a sodium phosphate buffer that we demonstrate to be electrochemically inactive. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

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

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

Nondestructive inspection assessment of eddy current and electrochemical analysis to separate inconel and stainless steel alloys

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

Moore, D.G.; Sorensen, N.R.

1998-02-01

This report presents a nondestructive inspection assessment of eddy current and electrochemical analysis to separate inconel alloys from stainless steel alloys as well as an evaluation of cleaning techniques to remove a thermal oxide layer on aircraft exhaust components. The results of this assessment are presented in terms of how effective each technique classifies a known exhaust material. Results indicate that either inspection technique can separate inconel and stainless steel alloys. Based on the experiments conducted, the electrochemical spot test is the optimum for use by airframe and powerplant mechanics. A spot test procedure is proposed for incorporation into themore » Federal Aviation Administration Advisory Circular 65-9A Airframe & Powerplant Mechanic - General Handbook. 3 refs., 70 figs., 7 tabs.« less

Process for manufacturing a lithium alloy electrochemical cell

DOEpatents

Bennett, William R.

1992-10-13

A process for manufacturing a lithium alloy, metal sulfide cell tape casts slurried alloy powders in an organic solvent containing a dissolved thermoplastic organic binder onto casting surfaces. The organic solvent is then evaporated to produce a flexible tape removable adhering to the casting surface. The tape is densified to increase its green strength and then peeled from the casting surface. The tape is laminated with a separator containing a lithium salt electrolyte and a metal sulfide electrode to form a green cell. The binder is evaporated from the green cell at a temperature lower than the melting temperature of the lithium salt electrolyte. Lithium alloy, metal sulfide and separator powders may be tape cast.

Treatment of paint manufacturing wastewater by coagulation/electrochemical methods: Proposals for disposal and/or reuse of treated water.

PubMed

da Silva, Larissa F; Barbosa, Andreia D; de Paula, Heber M; Romualdo, Lincoln L; Andrade, Leonardo S

2016-09-15

This paper describes and discusses an investigation into the treatment of paint manufacturing wastewater (water-based acrylic texture) by coagulation (aluminum sulfate) coupled to electrochemical methods (BDD electrode). Two proposals are put forward, based on the results. The first proposal considers the feasibility of reusing wastewater treated by the methods separately and in combination, while the second examines the possibility of its disposal into water bodies. To this end, parameters such as toxicity, turbidity, color, organic load, dissolved aluminum, alkalinity, hardness and odor are evaluated. In addition, the proposal for water reuse is strengthened by the quality of the water-based paints produced using the wastewater treated by the two methods (combined and separate), which was evaluated based on the typical parameters for the quality control of these products. Under optimized conditions, the use of the chemical coagulation (12 mL/L of Al2(SO4)3 dosage) treatment, alone, proved the feasibility of reusing the treated wastewater in the paint manufacturing process. However, the use of the electrochemical method (i = 10 mA/cm(2) and t = 90 min) was required to render the treated wastewater suitable for discharge into water bodies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ball Lightning–Aerosol Electrochemical Power Source or A Cloud of Batteries

PubMed Central

2007-01-01

Despite numerous attempts, an adequate theoretical and experimental simulation of ball lightning still remains incomplete. According to the model proposed here, the processes of electrochemical oxidation within separate aerosol particles are the basis for this phenomenon, and ball lightning is a cloud of composite nano or submicron particles, where each particle is a spontaneously formed nanobattery which is short-circuited by the surface discharge because it is of such a small size. As free discharge-shorted current loops, aerosol nanobatteries are exposed to a powerful mutual magnetic dipole–dipole attraction. The gaseous products and thermal energy produced by each nanobattery as a result of the intra-particle self-sustaining electrochemical reactions, cause a mutual repulsion of these particles over short distances and prevent their aggregation, while a collectivization of the current loops of separate particles, due to the electric arc overlapping between adjacent particles, weakens their mutual magnetic attraction over short distances. Discharge currents in the range of several amperes to several thousand amperes as well as the pre-explosive mega ampere currents, generated in the reduction–oxidation reactions and distributed between all the aerosol particles, explain both the magnetic attraction between the elements of the ball lightning substance and the impressive electromagnetic effects of ball lightning.

Integrated hybrid polystyrene-polydimethylsiloxane device for monitoring cellular release with microchip electrophoresis and electrochemical detection

PubMed Central

Johnson, Alicia S.; Mehl, Benjamin T.; Martin, R. Scott

2015-01-01

In this work, a polystyrene (PS)-polydimethylsiloxane (PDMS) hybrid device was developed to enable the integration of cell culture with analysis by microchip electrophoresis and electrochemical detection. It is shown that this approach combines the fundamental advantages of PDMS devices (the ability to integrate pumps and valves) and PS devices (the ability to permanently embed fluidic tubing and electrodes). The embedded fused-silica capillary enables high temporal resolution measurements from off-chip cell culture dishes and the embedded electrodes provide close to real-time analysis of small molecule neurotransmitters. A novel surface treatment for improved (reversible) adhesion between PS and PDMS is described using a chlorotrimethylsilane stamping method. It is demonstrated that a Pd decoupler is efficient at handling the high current (and cathodic hydrogen production) resulting from use of high ionic strength buffers needed for cellular analysis; thus allowing an electrophoretic separation and in-channel detection. The separation of norepinephrine (NE) and dopamine (DA) in highly conductive biological buffers was optimized using a mixed surfactant system. This PS-PDMS hybrid device integrates multiple processes including continuous sampling from a cell culture dish, on-chip pump and valving technologies, microchip electrophoresis, and electrochemical detection to monitor neurotransmitter release from PC 12 cells. PMID:25663849

SPE (tm) regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications

NASA Technical Reports Server (NTRS)

Mcelroy, J. F.

1990-01-01

Viewgraphs on SPE regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications are presented. Topics covered include: hydrogen-oxygen regenerative fuel cell energy storage system; electrochemical cell reactions; SPE cell voltage stability; passive water removal SPE fuel cell; fuel cell performance; SPE water electrolyzers; hydrophobic oxygen phase separator; hydrophilic/electrochemical hydrogen phase separator; and unitized regenerative fuel cell.

Validation of Electrochemically Modulated Separations Performed On-Line with MC-ICP-MS for Uranium and Plutonium Isotopic Analyses

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

Liezers, Martin; Olsen, Khris B.; Mitroshkov, Alexandre V.

2010-08-11

The most time consuming process in uranium or plutonium isotopic analyses is performing the requisite chromatographic separation of the actinides. Filament preparation for thermal ionization (TIMS) adds further delays, but is generally accepted due to the unmatched performance in trace isotopic analyses. Advances in Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) are beginning to rival the performance of TIMS. Methods, such as Electrochemically Modulated Separations (EMS) can efficiently pre-concentrate U or Pu quite selectively from small solution volumes in a matrix of 0.5 M nitric acid. When performed in-line with ICP-MS, the rapid analyte release from the electrode is fast,more » and large transient analyte signal enhancements of >100 fold can be achieved as compared to more conventional continuous nebulization of the original starting solution. This makes the approach ideal for very low level isotope ratio measurements. In this paper, some aspects of EMS performance are described. These include low level Pu isotope ratio behavior versus concentration by MC-ICP-MS and uranium rejection characteristics that are also important for reliable low level Pu isotope ratio determinations.« less

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.

Electrochemical cell having an alkali-metal-nitrate electrode

DOEpatents

Roche, M.F.; Preto, S.K.

1982-06-04

A power-producing secondary electrochemical cell includes a molten alkali metal as the negative-electrode material and a molten-nitrate salt as the positive-electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali-metal-ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium ..beta..'' alumina.

A Highly Thermostable Ceramic-Grafted Microporous Polyethylene Separator for Safer Lithium-Ion Batteries.

PubMed

Zhu, Xiaoming; Jiang, Xiaoyu; Ai, Xinping; Yang, Hanxi; Cao, Yuliang

2015-11-04

The safety concern is a critical obstacle to large-scale energy storage applications of lithium-ion batteries. A thermostable separator is one of the most effective means to construct the safe lithium-ion batteries. Herein, we demonstrate a novel ceramic (SiO2)-grafted PE separator prepared by electron beam irradiation. The separator shows similar thickness and pore structure to the bare separator, while displaying strong dimensional thermostability, as the shrinkage ratio is only 20% even at an elevated temperature of 180 °C. Besides, the separator is highly electrochemically inert, showing no adverse effect on the energy and power output of the batteries. Considering the excellent electrochemical and thermal stability, the SiO2-grafted PE separator developed in this work is greatly beneficial for constructing safer lithium-ion batteries.

Electrochemical delignification of wood pulp using polyoxometalate mediators

Treesearch

R.S. Reiner; E.L. Springer; R.H. Atalla

2003-01-01

It has been found that polyoxometalates (POMs) can act as mediators in the electrochemical oxidation of lignin in pulps. An electrochemical cell, with a Nafion® membrane separating the anode and cathode compartments, was used in the delignification experiments. A softwood kraft pulp was placed in the anode compartment with a buffered 0.01M solution of the...

Method of preparing porous, rigid ceramic separators for an electrochemical cell

DOEpatents

Bandyopadhyay, Gautam; Dusek, Joseph T.

1981-01-01

Porous, rigid separators for electrochemical cells are prepared by first calcining particles of ceramic material at temperatures above about 1200.degree. C. for a sufficient period of time to reduce the sinterability of the particles. A ceramic powder that has not been calcined is blended with the original powder to control the porosity of the completed separator. The ceramic blend is then pressed into a sheet of the desired shape and sintered at a temperature somewhat lower than the calcination temperature. Separator sheets of about 1 to 2.5 mm thickness and 30 to 70% porosity can be prepared by this technique. Ceramics such as yttria, magnesium oxide and magnesium-aluminum oxide have advantageously been used to form separators by this method.

3D nanostructured inkjet printed graphene via UV-pulsed laser irradiation enables paper-based electronics and electrochemical devices.

PubMed

Das, Suprem R; Nian, Qiong; Cargill, Allison A; Hondred, John A; Ding, Shaowei; Saei, Mojib; Cheng, Gary J; Claussen, Jonathan C

2016-09-21

Emerging research on printed and flexible graphene-based electronics is beginning to show tremendous promise for a wide variety of fields including wearable sensors and thin film transistors. However, post-print annealing/reduction processes that are necessary to increase the electrical conductivity of the printed graphene degrade sensitive substrates (e.g., paper) and are whole substrate processes that are unable to selectively anneal/reduce only the printed graphene-leaving sensitive device components exposed to damaging heat or chemicals. Herein a pulsed laser process is introduced that can selectively irradiate inkjet printed reduced graphene oxide (RGO) and subsequently improve the electrical conductivity (Rsheet∼0.7 kΩ□(-1)) of printed graphene above previously published reports. Furthermore, the laser process is capable of developing 3D petal-like graphene nanostructures from 2D planar printed graphene. These visible morphological changes display favorable electrochemical sensing characteristics-ferricyanide cyclic voltammetry with a redox peak separation (ΔEp) ≈ 0.7 V as well as hydrogen peroxide (H2O2) amperometry with a sensitivity of 3.32 μA mM(-1) and a response time of <5 s. Thus this work paves the way for not only paper-based electronics with graphene circuits, it enables the creation of low-cost and disposable graphene-based electrochemical electrodes for myriad applications including sensors, biosensors, fuel cells, and theranostic devices.

Electrochemical Cell for Obtaining Oxygen from Carbon Dioxide Atmospheres

NASA Technical Reports Server (NTRS)

Hooker, Matthew; Rast, H. Edward; Rogers, Darren K.; Borja, Luis; Clark, Kevin; Fleming, Kimberly; Mcgurren, Michael; Oldaker, Tom; Sweet, Nanette

1989-01-01

To support human life on the Martian surface, an electrochemical device will be required to obtain oxygen from the carbon dioxide rich atmosphere. The electrolyte employed in such a device must be constructed from extremely thin, dense membranes to efficiently acquire the oxygen necessary to support life. A forming process used industrially in the production of multilayer capacitors and electronic substrates was adapted to form the thin membranes required. The process, known as the tape casting, involves the suspension consisting of solvents and binders. The suspension is passed under a blade, resulting in the production of ceramic membranes between 0.1 and 0.5 mm thick. Once fired, the stabilized zirconia membranes were assembled into the cell design by employing a zirconium phosphate solution as the sealing agent. The resulting ceramic-to-ceramic seals were found to be structurally sound and gas-tight. Furthermore, by using a zirconia-based solution to assemble the cell, the problem of a thermal expansion mismatch was alleviated. By adopting an industrial forming process to produce thin membranes, an electrochemical cell for obtaining oxygen from carbon dioxide was produced. The proposed cell design is unique in that it does not require a complicated manifold system for separating the various gases present in this process, nor does it require a series of complex electrical connections. Thus, the device can reliably obtain the vital oxygen supply from the toxic carbon dioxide atmosphere.

Method of enhancing the wettability of boron nitride for use as an electrochemical cell separator

DOEpatents

McCoy, L.R.

1981-01-23

A felt or other fabric of boron nitride suitable for use as an interelectrode separator within an electrochemical cell is wetted with a solution containing a thermally decomposable organic salt of an alkaline earth metal. An aqueous solution of magnesium acetate is the preferred solution for this purpose. After wetting the boron nitride, the solution is dried by heating at a sufficiently low temperature to prevent rapid boiling and the creation of voids within the separator. The dried material is then calcined at an elevated temperature in excess of 400/sup 0/C to provide a coating of an oxide of magnesium on the surface of the boron nitride fibers. A fabric or felt of boron nitride treated in this manner is easily wetted by molten electrolytic salts, such as the alkali metal halides or alkaline earth metal halides, that are used in high temperature, secondary electrochemical cells.

Method of enhancing the wettability of boron nitride for use as an electrochemical cell separator

DOEpatents

McCoy, Lowell R.

1982-01-01

A felt or other fabric of boron nitride suitable for use as an interelecte separator within an electrochemical cell is wetted with a solution containing a thermally decomposable organic salt of an alkaline earth metal. An aqueous solution of magnesium acetate is the preferred solution for this purpose. After wetting the boron nitride, the solution is dried by heating at a sufficiently low temperature to prevent rapid boiling and the creation of voids within the separator. The dried material is then calcined at an elevated temperature in excess of 400.degree. C. to provide a coating of an oxide of magnesium on the surface of the boron nitride fibers. A fabric or felt of boron nitride treated in this manner is easily wetted by molten electrolytic salts, such as the alkali metal halides or alkaline earth metal halides, that are used in high temperature, secondary electrochemical cells.

Insights into electrochemical reactions from ambient pressure photoelectron spectroscopy.

PubMed

Stoerzinger, Kelsey A; Hong, Wesley T; Crumlin, Ethan J; Bluhm, Hendrik; Shao-Horn, Yang

2015-11-17

The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent in situ studies on model electrochemical components as well as operando studies performed by our groups at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory to illustrate that AP-XPS is both a chemically and an electrically specific tool since photoelectrons carry information on both the local chemistry and electrical potentials. The applications of AP-XPS to oxygen electrocatalysis shown in this Account span well-defined studies of (1) the oxide/oxygen gas interface, (2) the oxide/water vapor interface, and (3) operando measurements of half and full electrochemical cells. Using specially designed model devices, we can expose and isolate the electrode or interface of interest to the incident X-ray beam and AP-XPS analyzer to relate the electrical potentials to the composition/chemical state of the key components and interfaces. We conclude with an outlook on new developments of AP-XPS end stations, which may provide significant improvement in the observation of dynamics over a wide range of time scales, higher spatial resolution, and improved characterization of boundary or interface layers (solid/solid and liquid/solid).

Hybrid supercapacitor-battery materials for fast electrochemical charge storage

PubMed Central

Vlad, A.; Singh, N.; Rolland, J.; Melinte, S.; Ajayan, P. M.; Gohy, J.-F.

2014-01-01

High energy and high power electrochemical energy storage devices rely on different fundamental working principles - bulk vs. surface ion diffusion and electron conduction. Meeting both characteristics within a single or a pair of materials has been under intense investigations yet, severely hindered by intrinsic materials limitations. Here, we provide a solution to this issue and present an approach to design high energy and high power battery electrodes by hybridizing a nitroxide-polymer redox supercapacitor (PTMA) with a Li-ion battery material (LiFePO4). The PTMA constituent dominates the hybrid battery charge process and postpones the LiFePO4 voltage rise by virtue of its ultra-fast electrochemical response and higher working potential. We detail on a unique sequential charging mechanism in the hybrid electrode: PTMA undergoes oxidation to form high-potential redox species, which subsequently relax and charge the LiFePO4 by an internal charge transfer process. A rate capability equivalent to full battery recharge in less than 5 minutes is demonstrated. As a result of hybrid's components synergy, enhanced power and energy density as well as superior cycling stability are obtained, otherwise difficult to achieve from separate constituents. PMID:24603843

Separator for alkaline electric batteries and method of making

NASA Technical Reports Server (NTRS)

Pfluger, H. L. (Inventor); Hoyt, H. E.

1970-01-01

Battery separator membranes of high electrolytic conductivity comprising a cellulose ether and a compatible metallic salt of water soluble aliphatic acids and their hydroxy derivatives are described. It was found that methyl cellulose can be modified by another class of materials, nonpolymeric in nature, to form battery separator membranes of low electrolytic resistance but which have the flexibility of membranes made of unmodified methyl cellulose, and which in many cases enhance flexibility over membranes made with unmodified methyl cellulose. Separator membranes for electrochemical cells comprising a cellulose ether and a modified selected from the group consisting of metallic salts of water soluble alphatic acids and their hydroxy derivatives and to electrochemical cells utilizing said membranes are described.

Treatment of electrochemical cell components with lithium tetrachloroaluminate (LiAlCl.sub.4) to promote electrolyte wetting

DOEpatents

Eberhart, James G.; Battles, James E.

1980-01-01

Electrochemical cell components such as interelectrode separators, retaining screens and current collectors are contacted with lithium tetrachloroaluminate prior to contact with molten electrolytic salt to improve electrolyte wetting. The LiAlCl.sub.4 can be applied in powdered, molten or solution form but, since this material has a lower melting point than the electrolytic salt used in high-temperature cells, the powdered LiAlCl.sub.4 forms a molten flux prior to contact by the molten electrolyte when both materials are initially provided in solid form. Components of materials such as boron nitride and other materials which are difficult to wet with molten salts are advantageously treated by this process.

Polyethylene/Potassium Titanate Separators For Ni/H2 Cells

NASA Technical Reports Server (NTRS)

Scott, William E.

1995-01-01

Experimental separators fabricated on paper-making machine. Two-layer, paperlike composite of polyethylene fibers and potassium titanate pigment shows promise for replacing asbestos as separator material in nickel/hydrogen electrochemical cells.

Electrochemical construction

DOEpatents

Einstein, Harry; Grimes, Patrick G.

1983-08-23

An electrochemical cell construction features a novel co-extruded plastic electrode in an interleaved construction with a novel integral separator-spacer. Also featured is a leak and impact resistant construction for preventing the spill of corrosive materials in the event of rupture.

Monolithic three-dimensional electrochemical energy storage system on aerogel or nanotube scaffold

DOEpatents

Farmer, Joseph C; Stadermann, Michael

2013-11-12

A monolithic three-dimensional electrochemical energy storage system is provided on an aerogel or nanotube scaffold. An anode, separator, cathode, and cathodic current collector are deposited on the aerogel or nanotube scaffold.

Monolithic three-dimensional electrochemical energy storage system on aerogel or nanotube scaffold

DOEpatents

Farmer, Joseph Collin; Stadermann, Michael

2014-07-15

A monolithic three-dimensional electrochemical energy storage system is provided on an aerogel or nanotube scaffold. An anode, separator, cathode, and cathodic current collector are deposited on the aerogel or nanotube scaffold.

Method of preparing porous, rigid ceramic separators for an electrochemical cell. [Patent application

DOEpatents

Bandyopadhyay, G.; Dusek, J.T.

Porous, rigid separators for electrochemical cells are prepared by first calcining particles of ceramic material at temperatures above about 1200/sup 0/C for a sufficient period of time to reduce the sinterability of the particles. A ceramic powder that has not been calcined is blended with the original powder to control the porosity of the completed separator. The ceramic blend is then pressed into a sheet of the desired shape and sintered at a temperature somewhat lower than the calcination temperature. Separator sheets of about 1 to 2.5 mm thickness and 30 to 70% porosity can be prepared by this technique. Ceramics such as yttria, magnesium oxide, and magnesium-aluminium oxide have advantageously been used to form separators by this method.

Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres

NASA Technical Reports Server (NTRS)

Hooker, M. W.; Rast, H. E.; Rogers, D. K.

1989-01-01

For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.

Sheet electrode for electrochemical systems

DOEpatents

Tsien, Hsue C.; Newby, Kenneth R.; Grimes, Patrick G.; Bellows, Richard J.

1983-04-12

An electrochemical cell construction features a novel co-extruded plastic electrode in an interleaved construction with a novel integral separator-spacer. Also featured is a leak and impact resistant construction for preventing the spill of corrosive materials in the event of rupture.

Strategies to optimize lithium-ion supercapacitors achieving high-performance: Cathode configurations, lithium loadings on anode, and types of separator

NASA Astrophysics Data System (ADS)

Cao, Wanjun; Li, Yangxing; Fitch, Brian; Shih, Jonathan; Doung, Tien; Zheng, Jim

2014-12-01

The Li-ion capacitor (LIC) is composed of a lithium-doped carbon anode and an activated carbon cathode, which is a half Li-ion battery (LIB) and a half electrochemical double-layer capacitor (EDLC). LICs can achieve much more energy density than EDLC without sacrificing the high power performance advantage of capacitors over batteries. LIC pouch cells were assembled using activated carbon (AC) cathode and hard carbon (HC) + stabilized lithium metal power (SLMP®) anode. Different cathode configurations, various SLMP loadings on HC anode, and two types of separators were investigated to achieve the optimal electrochemical performance of the LIC. Firstly, the cathode binders study suggests that the PTFE binder offers improved energy and power performances for LIC in comparison to PVDF. Secondly, the mass ratio of SLMP to HC is at 1:7 to obtain the optimized electrochemical performance for LIC among all the various studied mass ratios between lithium loading amounts and active anode material. Finally, compared to the separator Celgard PP 3501, cellulose based TF40-30 is proven to be a preferred separator for LIC.

Separator for electrochemical cells

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

Griffin, R.A.

1988-12-27

An electrochemical cell is described comprising a sealed casing; an anode, a cathode, a separator positioned between the anode and the cathode, and a non-aqueous electrolyte sealed in the casing; a pair of electrical terminals on the casing; means for electrically isolating the electrical terminals from each other; and means for electrically connecting the anode to one terminal and the cathode to the other terminal; wherein the anode is comprised of lithium foil, the cathode is comprised of manganese dioxide, and the separator consists essentially of a microporous polypropylene film having a thickness of about 1.5 mils and internal voidsmore » of about 60% by volume; wherein the anode, cathode, and separator are spirally wound together in a jelly roll configuration.« less

The effect of the carbon nanotube buffer layer on the performance of a Li metal battery

NASA Astrophysics Data System (ADS)

Zhang, Ding; Zhou, Yi; Liu, Changhong; Fan, Shoushan

2016-05-01

Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery.Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00465b

Core-shell structured ceramic nonwoven separators by atomic layer deposition for safe lithium-ion batteries

NASA Astrophysics Data System (ADS)

Shen, Xiu; Li, Chao; Shi, Chuan; Yang, Chaochao; Deng, Lei; Zhang, Wei; Peng, Longqing; Dai, Jianhui; Wu, Dezhi; Zhang, Peng; Zhao, Jinbao

2018-05-01

Safety is one of the most factors for lithium-ion batteries (LIBs). In this work, a novel kind of ceramic separator with high safety insurance is proposed. We fabricated the core-shell nanofiber separators for LIBs by atomic layer deposition (ALD) of 30 nm Al2O3 on the electrospinning nonwoven fiber of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP). The separators show a pretty high heat resistance up to 200 °C without any shrinkage, an excellent fire-resistant property and a wide electrochemical window. Besides, with higher uptake and ionic conductivity, cells assembled with the novel separator shows better electrochemical performance. The ALD produced separators exhibit great potential in elaborate products like 3C communications and in energy field with harsh requirements for safety such as electric vehicles. The application of ALD on polymer fiber membranes brings a new strategy and opportunity for improving the safety of the advanced LIBs.

Method of constructing an improved electrochemical cell

DOEpatents

Grimes, Patrick G.; Einstein, Harry

1984-10-09

An electrochemical cell construction features a novel co-extruded plastic electrode in an interleaved construction with a novel integral separator-spacer. Also featured is a leak and impact resistant construction for preventing the spill of corrosive materials in the event of rupture.

Separations of corticosteroids using electrochemically modulated liquid chromatography: Selectivity enhancements at a porous graphitic carbon stationary phase

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

Ting, E.Y.; Porter, M.D.

Electrochemically modulated liquid chromatography has been applied to the separation of a mixture of structurally similar corticosteroids (i.e., prednisone, prednisolone, cortisone, and hydrocortisone) using a porous graphitic carbon stationary phase. Changes in the voltage applied to the column markedly affected the efficiency as well as the elution order of the separation, with the mixture fully resolved at large negative values of applied potential. Mechanistic aspects in terms of the influence of changes in the applied voltage on the extent of the interactions between these analytes and the stationary phase are briefly discussed. 19 refs., 2 figs.

Method of preparing a powdered, electrically insulative separator for use in an electrochemical cell

DOEpatents

Cooper, Tom O.; Miller, William E.

1978-01-01

A secondary electrochemical cell includes electrodes separated by a layer of electrically insulative powder. The powder includes refractory materials selected from the oxides and nitrides of metals and metaloids. The powdered refractory material, blended with electrolyte particles, is compacted as layers onto an electrode to form an integral electrode structure and assembled into the cell. The assembled cell is heated to its operating temperature leaving porous layers of electrically insulative, refractory particles, containing molten electrolyte between the electrodes.

Electrochemical Quantification of Extracellular Local H2O2 Kinetics Originating from Single Cells.

PubMed

Bozem, Monika; Knapp, Phillip; Mirčeski, Valentin; Slowik, Ewa J; Bogeski, Ivan; Kappl, Reinhard; Heinemann, Christian; Hoth, Markus

2017-05-15

H 2 O 2 is produced by all eukaryotic cells under physiological and pathological conditions. Due to its enormous relevance for cell signaling at low concentrations and antipathogenic function at high concentrations, precise quantification of extracellular local H 2 O 2 concentrations ([H 2 O 2 ]) originating from single cells is required. Using a scanning electrochemical microscope and bare platinum disk ultramicroelectrodes, we established sensitive long-term measurements of extracellular [H 2 O 2 ] kinetics originating from single primary human monocytes (MCs) ex vivo. For the electrochemical techniques square wave voltammetry, cyclic and linear scan voltammetry, and chronoamperometry, detection limits for [H 2 O 2 ] were determined to be 5, 50, and 500 nM, respectively. Following phorbol ester stimulation, local [H 2 O 2 ] 5-8 μm above a single MC increased by 3.4 nM/s within the first 10 min before reaching a plateau. After extracellular addition of H 2 O 2 to an unstimulated MC, the local [H 2 O 2 ] decreased on average by 4.2 nM/s due to degradation processes of the cell. Using the scanning mode of the setup, we found that H 2 O 2 is evenly distributed around the producing cell and can still be detected up to 30 μm away from the cell. The electrochemical single-cell measurements were validated in MC populations using electron spin resonance spectroscopy and the Amplex ® UltraRed assay. Innovation and Conclusion: We demonstrate a highly sensitive, spatially, and temporally resolved electrochemical approach to monitor dynamics of production and degradation processes for H 2 O 2 separately. Local extracellular [H 2 O 2 ] kinetics originating from single cells is quantified in real time. Antioxid. Redox Signal. 00, 000-000.

Bio and nanomaterials in tribocorrosion systems

NASA Astrophysics Data System (ADS)

Benea, Lidia

2017-02-01

The growing attention that the scientific community has paid in the last decades to the corrosion phenomena, including tribocorrosion is related to the huge economic, social and environmental losses (3,5 % GDP in industrialized countries as USA, UK, Japan and Germany), that result from the spread of damage of several metal constructions and devices. Tribocorrosion is defined as the chemical-electrochemical-mechanical process leading to a degradation of materials in sliding, rolling or erosion contacts immersed in a corrosive environment or even in water. That degradation results from the combined action of corrosion and wear are higher compared with addition of corrosion and wear degradation separately. This synergism between chemical, electrochemical, and mechanical processes on materials in sliding, abrasive or erosive contacts immersed in a liquid requires a multi-disciplinary approach (material science, electrochemistry, tribology, mechanics, and surface engineering). This paper presents few summary results obtained by studying the materials degradation by complex tribocorrosion processes in terms of two broad categories of applications: tribocorrosion in industrial systems with improved behaviour of nanomaterials as hybrid and nanocomposite layers and tribocorrosion in living systems with improved behaviour by surface modifications of biomaterials applying electrochemical techniques. The purpose of this paper is to provide information on the surface conditions of materials in sliding contacts and also on the kinetics of reactions that control the corrosion component in the material loss during tribocorrosion tests.

Poly(vinyl Alcohol) Borate Gel Polymer Electrolytes Prepared by Electrodeposition and Their Application in Electrochemical Supercapacitors.

PubMed

Jiang, Mengjin; Zhu, Jiadeng; Chen, Chen; Lu, Yao; Ge, Yeqian; Zhang, Xiangwu

2016-02-10

Gel polymer electrolytes (GPEs) have been studied for preparing flexible and compact electrochemical energy storage devices. However, the preparation and use of GPEs are complex, and most GPEs prepared through traditional methods do not have good wettability with the electrodes, which retard them from achieving their performance potential. In this study, these problems are addressed by conceiving and implementing a simple, but effective, method of electrodepositing poly(vinyl alcohol) potassium borate (PVAPB) GPEs directly onto the surfaces of active carbon electrodes for electrochemical supercapacitors. PVAPB GPEs serve as both the electrolyte and the separator in the assembled supercapacitors, and their scale and shape are determined solely by the geometry of the electrodes. PVAPB GPEs have good bonding to the active electrode materials, leading to excellent and stable electrochemical performance of the supercapacitors. The electrochemical performance of PVAPB GPEs and supercapacitors can be manipulated simply by adjusting the concentration of KCl salt used during the electrodeposition process. With a 0.9 M KCl concentration, the as-prepared supercapacitors deliver a specific capacitance of 65.9 F g(-1) at a current density of 0.1 A g(-1) and retain more than 95% capacitance after 2000 charge/discharge cycles at a current density of 1 A g(-1). These supercapacitors also exhibit intelligent high voltage self-protection function due to the electrolysis-induced cross-linking effect of PVAPB GPEs.

Ion/proton-conducting apparatus and method

DOEpatents

Yates, Matthew; Xue, Wei

2014-12-23

A c-axis-oriented HAP thin film synthesized by seeded growth on a palladium hydrogen membrane substrate. An exemplary synthetic process includes electrochemical seeding on the substrate, and secondary and tertiary hydrothermal treatments under conditions that favor growth along c-axes and a-axes in sequence. By adjusting corresponding synthetic conditions, an HAP this film can be grown to a controllable thickness with a dense coverage on the underlying substrate. The thin films have relatively high proton conductivity under hydrogen atmosphere and high temperature conditions. The c-axis oriented films may be integrated into fuel cells for application in the intermediate temperature range of 200-600.degree. C. The electrochemical-hydrothermal deposition technique may be applied to create other oriented crystal materials having optimized properties, useful for separations and catalysis as well as electronic and electrochemical applications, electrochemical membrane reactors, and in chemical sensors. Additional high-density and gas-tight HAP film compositions may be deposited using a two-step deposition method that includes an electrochemical deposition method followed by a hydrothermal deposition method. The two-step method uses a single hydrothermal deposition solution composition. The method may be used to deposit HAP films including but not limited to at least doped HAP films, and more particularly including carbonated HAP films. In addition, the high-density and gas-tight HAP films may be used in proton exchange membrane fuel cells.

Metal-air flow batteries using oxygen enriched electrolyte

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

Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

Metal-air flow batteries using oxygen enriched electrolyte

DOEpatents

Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh; Chen, Xujie

2017-08-01

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

Fabrication and Characterization of a Nanocoax-Based Electrochemical Sensor

NASA Astrophysics Data System (ADS)

Rizal, Binod; Archibald, Michelle M.; Naughton, Jeffrey R.; Connolly, Timothy; Shepard, Stephen C.; Burns, Michael J.; Chiles, Thomas C.; Naughton, Michael J.

2014-03-01

We used an imprint lithography process to fabricate three dimensional electrochemical sensors comprising arrays of vertically-oriented coaxial electrodes, with the coax cores and shields serving as working and counter electrodes, respectively, and with nanoscale separation gaps.[2] Arrays of devices with different electrode gaps (coax annuli) were prepared, yielding increasing sensitivity with decreasing annulus thickness. A coax-based sensor with a 100 nm annulus was found to have sensitivity 100 times greater than that of a conventional planar sensor control, which had millimeter-scale electrode gap spacing. We suggest that this enhancement is due to an increase in the diffusion of molecules between electrodes, which improves the current per unit surface area compared to the planar device. Supported by NIH (National Cancer Institute and the National Institute of Allergy and Infectious Diseases).

Multiscale modeling and characterization for performance and safety of lithium-ion batteries

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

Pannala, Sreekanth; Turner, John A.; Allu, Srikanth

Lithium-ion batteries are highly complex electrochemical systems whose performance and safety are governed by coupled nonlinear electrochemical-electrical-thermal-mechanical processes over a range of spatiotemporal scales. In this paper we describe a new, open source computational framework for Lithium-ion battery simulations that is designed to support a variety of model types and formulations. This framework has been used to create three-dimensional cell and battery pack models that explicitly simulate all the battery components (current collectors, electrodes, and separator). The models are used to predict battery performance under normal operations and to study thermal and mechanical safety aspects under adverse conditions. The modelmore » development and validation are supported by experimental methods such as IR-imaging, X-ray tomography and micro-Raman mapping.« less

Multiscale modeling and characterization for performance and safety of lithium-ion batteries

DOE PAGES

Pannala, Sreekanth; Turner, John A.; Allu, Srikanth; ...

2015-08-19

Lithium-ion batteries are highly complex electrochemical systems whose performance and safety are governed by coupled nonlinear electrochemical-electrical-thermal-mechanical processes over a range of spatiotemporal scales. In this paper we describe a new, open source computational framework for Lithium-ion battery simulations that is designed to support a variety of model types and formulations. This framework has been used to create three-dimensional cell and battery pack models that explicitly simulate all the battery components (current collectors, electrodes, and separator). The models are used to predict battery performance under normal operations and to study thermal and mechanical safety aspects under adverse conditions. The modelmore » development and validation are supported by experimental methods such as IR-imaging, X-ray tomography and micro-Raman mapping.« less

Alternative Electrochemical Salt Waste Forms, Summary of FY11-FY12 Results

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

Riley, Brian J.; Mccloy, John S.; Crum, Jarrod V.

2014-01-17

The Fuel Cycle Research and Development Program, sponsored by the U.S. Department of Energy Office of Nuclear Energy, is currently investigating alternative waste forms for wastes generated from nuclear fuel processing. One such waste results from an electrochemical separations process, called the “Echem” process. The Echem process utilizes a molten KCl-LiCl salt to dissolve the fuel. This process results in a spent salt containing alkali, alkaline earth, lanthanide halides and small quantities of actinide halides, where the primary halide is chloride with a minor iodide fraction. Pacific Northwest National Laboratory (PNNL) is concurrently investigating two candidate waste forms for themore » Echem spent-salt: high-halide minerals (i.e., sodalite and cancrinite) and tellurite (TeO2)-based glasses. Both of these candidates showed promise in fiscal year (FY) 2009 and FY2010 with a simplified nonradioactive simulant of the Echem waste. Further testing was performed on these waste forms in FY2011 and FY2012 to assess the possibility of their use in a sustainable fuel cycle. This report summarizes the combined results from FY2011 and FY2012 efforts.« less

Management of processes of electrochemical dimensional processing

NASA Astrophysics Data System (ADS)

Akhmetov, I. D.; Zakirova, A. R.; Sadykov, Z. B.

2017-09-01

In different industries a lot high-precision parts are produced from hard-processed scarce materials. Forming such details can only be acting during non-contact processing, or a minimum of effort, and doable by the use, for example, of electro-chemical processing. At the present stage of development of metal working processes are important management issues electrochemical machining and its automation. This article provides some indicators and factors of electrochemical machining process.

Mediated electrochemical oxidation of organic wastes without electrode separators

DOEpatents

Farmer, Joseph C.; Wang, Francis T.; Hickman, Robert G.; Lewis, Patricia R.

1996-01-01

An electrochemical cell/electrolyte/mediator combination for the efficient destruction of organic contaminants using metal salt mediators in a sulfuric acid electrolyte, wherein the electrodes and mediator are chosen such that hydrogen gas is produced at the cathode and no cell membrane is required.

Cell structure for electrochemical devices and method of making same

DOEpatents

Kaun, Thomas D.

1993-01-01

An electrochemical device comprises a plurality of cells, each cell including a laminate cell membrane, made up of a separator/electrolyte means interposed between alternating positive and negative electrodes, each type of electrode being respectively in common contact to a single current collector.

Alkaline electrochemical cells and method of making

NASA Technical Reports Server (NTRS)

Hoyt, H. E.; Pfluger, H. L. (Inventor)

1970-01-01

Equilibrated cellulose ether membranes of increased electrolytic conductivity for use as separators in concentrated alkaline electrochemical cells are investigated. The method of making such membranes by equilibration to the degree desired in an aqueous alkali solution mantained at a temperature below about 10 C is described.

High-Density Droplet Microarray of Individually Addressable Electrochemical Cells.

PubMed

Zhang, Huijie; Oellers, Tobias; Feng, Wenqian; Abdulazim, Tarik; Saw, En Ning; Ludwig, Alfred; Levkin, Pavel A; Plumeré, Nicolas

2017-06-06

Microarray technology has shown great potential for various types of high-throughput screening applications. The main read-out methods of most microarray platforms, however, are based on optical techniques, limiting the scope of potential applications of such powerful screening technology. Electrochemical methods possess numerous complementary advantages over optical detection methods, including its label-free nature, capability of quantitative monitoring of various reporter molecules, and the ability to not only detect but also address compositions of individual compartments. However, application of electrochemical methods for the purpose of high-throughput screening remains very limited. In this work, we develop a high-density individually addressable electrochemical droplet microarray (eDMA). The eDMA allows for the detection of redox-active reporter molecules irrespective of their electrochemical reversibility in individual nanoliter-sized droplets. Orthogonal band microelectrodes are arranged to form at their intersections an array of three-electrode systems for precise control of the applied potential, which enables direct read-out of the current related to analyte detection. The band microelectrode array is covered with a layer of permeable porous polymethacrylate functionalized with a highly hydrophobic-hydrophilic pattern, forming spatially separated nanoliter-sized droplets on top of each electrochemical cell. Electrochemical characterization of single droplets demonstrates that the underlying electrode system is accessible to redox-active molecules through the hydrophilic polymeric pattern and that the nonwettable hydrophobic boundaries can spatially separate neighboring cells effectively. The eDMA technology opens the possibility to combine the high-throughput biochemical or living cell screenings using the droplet microarray platform with the sequential electrochemical read-out of individual droplets.

Safe Replacement For Asbestos In Nickel/Hydrogen Cells

NASA Technical Reports Server (NTRS)

Scott, William E.

1993-01-01

Polyethylene fibers and potassium titanate particles perform as well as asbestos. New material for separators of nickel-hydrogen electrochemical cells offers performance similar to that of asbestos separator material without adverse health effects. In one version, separator contains pure polyethylene fibers, and may or may not contain supplementary latices as bonding agents. In standard wet-laying papermaking process, fibers pressed into mat, then dried. Mat used as is or pressed further in hot calender stack to soften and fuse fibers at crossing points. Treatment reduces porosity and increases resistance of mat to passage of air bubbles under pressure. In alternative version, matrix of 20 to 40 percent polyethylene fibers and 60 to 80 percent potassium titanate particles formed on paper machine, then dried. It, too, can be treated by hot calendering.

Low-temperature thermally regenerative electrochemical system

DOEpatents

Loutfy, R.O.; Brown, A.P.; Yao, N.P.

1982-04-21

A thermally regenerative electrochemical system is described including an electrochemical cell with two water-based electrolytes separated by an ion exchange membrane, at least one of the electrolytes containing a complexing agent and a salt of a multivalent metal whose respective order of potentials for a pair of its redox couples is reversible by a change in the amount of the ocmplexing agent in the electrolyte, the complexing agent being removable by distillation to cause the reversal.

Low temperature thermally regenerative electrochemical system

DOEpatents

Loutfy, Raouf O.; Brown, Alan P.; Yao, Neng-Ping

1983-01-01

A thermally regenerative electrochemical system including an electrochemical cell with two water-based electrolytes separated by an ion exchange membrane, at least one of the electrolytes containing a complexing agent and a salt of a multivalent metal whose respective order of potentials for a pair of its redox couples is reversible by a change in the amount of the complexing agent in the electrolyte, the complexing agent being removable by distillation to cause the reversal.

Perovskite electrodes and method of making the same

DOEpatents

Seabaugh, Matthew M [Columbus, OH; Swartz, Scott L [Columbus, OH

2009-09-22

The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

Perovskite electrodes and method of making the same

DOEpatents

Seabaugh, Matthew M.; Swartz, Scott L.

2005-09-20

The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

Electrochemical-mechanical coupled modeling and parameterization of swelling and ionic transport in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Sauerteig, Daniel; Hanselmann, Nina; Arzberger, Arno; Reinshagen, Holger; Ivanov, Svetlozar; Bund, Andreas

2018-02-01

The intercalation and aging induced volume changes of lithium-ion battery electrodes lead to significant mechanical pressure or volume changes on cell and module level. As the correlation between electrochemical and mechanical performance of lithium ion batteries at nano and macro scale requires a comprehensive and multidisciplinary approach, physical modeling accounting for chemical and mechanical phenomena during operation is very useful for the battery design. Since the introduced fully-coupled physical model requires proper parameterization, this work also focuses on identifying appropriate mathematical representation of compressibility as well as the ionic transport in the porous electrodes and the separator. The ionic transport is characterized by electrochemical impedance spectroscopy (EIS) using symmetric pouch cells comprising LiNi1/3Mn1/3Co1/3O2 (NMC) cathode, graphite anode and polyethylene separator. The EIS measurements are carried out at various mechanical loads. The observed decrease of the ionic conductivity reveals a significant transport limitation at high pressures. The experimentally obtained data are applied as input to the electrochemical-mechanical model of a prismatic 10 Ah cell. Our computational approach accounts intercalation induced electrode expansion, stress generation caused by mechanical boundaries, compression of the electrodes and the separator, outer expansion of the cell and finally the influence of the ionic transport within the electrolyte.

Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

NASA Astrophysics Data System (ADS)

Malerød-Fjeld, Harald; Clark, Daniel; Yuste-Tirados, Irene; Zanón, Raquel; Catalán-Martinez, David; Beeaff, Dustin; Morejudo, Selene H.; Vestre, Per K.; Norby, Truls; Haugsrud, Reidar; Serra, José M.; Kjølseth, Christian

2017-11-01

Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 °C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.

High temperature seals between ceramic separation membranes and super-alloy housing

NASA Technical Reports Server (NTRS)

Honea, G.; Sridhar, K. R.

1991-01-01

One of the concepts for oxygen production from Martian atmospheric carbon dioxide involves the use of tubular electrochemical membranes for oxygen separation. The tubular configuration offers the advantage of being able to separate the oxygen at pressures of up to 500 psi, thereby eliminating the need for a pre-liquefaction oxygen compressor. A key technology that has to be developed in order for the electrochemical separator to combine as a compressor is a high temperature static seal between the ceramic separation cell and the nickel-based super-alloy tube. Equipment was designed and fabricated to test the seals. Efforts are under way to develop a finite element model to study the thermal stresses at the joints and on the seal, and the optimal shape of the seal. The choice of seal materials and the technique to be used to fabricate the seals are also being investigated.

Electrochemical heat engine

DOEpatents

Elliott, Guy R. B.; Holley, Charles E.; Houseman, Barton L.; Sibbitt, Jr., Wilmer L.

1978-01-01

Electrochemical heat engines produce electrochemical work, and mechanical motion is limited to valve and switching actions as the heat-to-work cycles are performed. The electrochemical cells of said heat engines use molten or solid electrolytes at high temperatures. One or more reactions in the cycle will generate a gas at high temperature which can be condensed at a lower temperature with later return of the condensate to electrochemical cells. Sodium, potassium, and cesium are used as the working gases for high temperature cells (above 600 K) with halogen gases or volatile halides being used at lower temperature. Carbonates and halides are used as molten electrolytes and the solid electrolyte in these melts can also be used as a cell separator.

Safeguard monitoring of direct electrolytic reduction

NASA Astrophysics Data System (ADS)

Jurovitzki, Abraham L.

Nuclear power is regaining global prominence as a sustainable energy source as the world faces the consequences of depending on limited fossil based, CO2 emitting fuels. A key component to achieving this sustainability is to implement a closed nuclear fuel cycle. Without achieving this goal, a relatively small fraction of the energy value in nuclear fuel is actually utilized. This involves recycling of spent nuclear fuel (SNF)---separating fissile actinides from waste products and using them to fabricate fresh fuel. Pyroprocessing is a viable option being developed for this purpose with a host of benefits compared to other recycling options, such as PUREX. Notably, pyroprocessing is ill suited to separate pure plutonium from spent fuel and thus has non-proliferation benefits. Pyroprocessing involves high temperature electrochemical and chemical processing of SNF in a molten salt electrolyte. During this batch process, several intermediate and final streams are produced that contain radioactive material. While pyroprocessing is ineffective at separating pure plutonium, there are various process misuse scenarios that could result in diversion of impure plutonium into one or more of these streams. This is a proliferation risk that should be addressed with innovative safeguards technology. One approach to meeting this challenge is to develop real time monitoring techniques that can be implemented in the hot cells and coupled with the various unit operations involved with pyroprocessing. Current state of the art monitoring techniques involve external chemical assaying which requires sample removal from these unit operations. These methods do not meet International Atomic Energy Agency's (IAEA) timeliness requirements. In this work, a number of monitoring techniques were assessed for their viability as online monitoring tools. A hypothetical diversion scenario for the direct electrolytic reduction process was experimentally verified (using Nd2O3 as a surrogate for PuO2). Electrochemical analysis was demonstrated to be effective at detecting even very dilute concentrations of actinides as evidence for a diversion attempt.

Ion Conduction in Microphase-Separated Block Copolymer Electrolytes

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

Kambe, Yu; Arges, Christopher G.; Patel, Shrayesh

2017-01-01

Microphase separation of block copolymers provides a promising route towards engineering a mechanically robust ion conducting film for electrochemical devices. The separation into two different nano-domains enables the film to simultaneously exhibit both high ion conductivity and mechanical robustness, material properties inversely related in most homopolymer and random copolymer electrolytes. To exhibit the maximum conductivity and mechanical robustness, both domains would span across macroscopic length scales enabling uninterrupted ion conduction. One way to achieve this architecture is through external alignment fields that are applied during the microphase separation process. In this review, we present the progress and challenges for aligningmore » the ionic domains in block copolymer electrolytes. A survey of alignment and characterization is followed by a discussion of how the nanoscale architecture affects the bulk conductivity and how alignment may be improved to maximize the number of participating conduction domains.« less

Fabrication of anti-protein-fouling poly(ethylene glycol) microfluidic chip electrophoresis by sandwich photolithography

PubMed Central

Cong, Hailin; Xu, Xiaodan; Yu, Bing; Liu, Huwei

2016-01-01

Microfluidic chip electrophoresis (MCE) is a powerful separation tool for biomacromolecule analysis. However, adsorption of biomacromolecules, particularly proteins onto microfluidic channels severely degrades the separation performance of MCE. In this paper, an anti-protein-fouling MCE was fabricated using a novel sandwich photolithography of poly(ethylene glycol) (PEG) prepolymers. Photopatterned microchannel with a minimum resolution of 10 μm was achieved. After equipped with a conventional online electrochemical detector, the device enabled baseline separation of bovine serum albumin, lysozyme (Lys), and cytochrome c (Cyt-c) in 53 s under a voltage of 200 V. Compared with a traditional polydimethylsiloxane MCE made by soft lithography, the PEG MCE made by the sandwich photolithography not only eliminated the need of a master mold and the additional modification process of the microchannel but also showed excellent anti-protein-fouling properties for protein separation. PMID:27493702

Fundamentals of electrochemical detection techniques for CE and MCE.

PubMed

Kubán, Pavel; Hauser, Peter C

2009-10-01

The electroanalytical techniques of amperometry, conductometry and potentiometry match well with the instrumental simplicity of CE. Indeed, all three detection approaches have been reported for electrophoretic separations. However, the characteristics of the three methods are quite distinct and these are not related to the optical methods more commonly employed. A detailed discussion of the underlying principles of each is given. The issue of possible effects of the separation voltage on the electrochemical detection techniques is considered in depth, and approaches to the elimination of such interferences are also discussed for each case.

Atmospheric-pressure plasma activation and surface characterization on polyethylene membrane separator

NASA Astrophysics Data System (ADS)

Tseng, Yu-Chien; Li, Hsiao-Ling; Huang, Chun

2017-01-01

The surface hydrophilic activation of a polyethylene membrane separator was achieved using an atmospheric-pressure plasma jet. The surface of the atmospheric-pressure-plasma-treated membrane separator was found to be highly hydrophilic realized by adjusting the plasma power input. The variations in membrane separator chemical structure were confirmed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Chemical analysis showed newly formed carbonyl-containing groups and high surface concentrations of oxygen-containing species on the atmospheric-pressure-plasma-treated polymeric separator surface. It also showed that surface hydrophilicity primarily increased from the polar component after atmospheric-pressure plasma treatment. The surface and pore structures of the polyethylene membrane separator were examined by scanning electron microscopy, revealing a slight alteration in the pore structure. As a result of the incorporation of polar functionalities by atmospheric-pressure plasma activation, the electrolyte uptake and electrochemical impedance of the atmospheric-pressure-plasma-treated membrane separator improved. The investigational results show that the separator surface can be controlled by atmospheric-pressure plasma surface treatment to tailor the hydrophilicity and enhance the electrochemical performance of lithium ion batteries.

Aqueous Dispersions of Graphene from Electrochemically Exfoliated Graphite.

PubMed

Sevilla, Marta; Ferrero, Guillermo A; Fuertes, Antonio B

2016-11-21

A facile and environmentally friendly synthetic strategy for the production of stable and easily processable dispersions of graphene in water is presented. This strategy represents an alternative to classical chemical exfoliation methods (for example the Hummers method) that are more complex, harmful, and dangerous. The process is based on the electrochemical exfoliation of graphite and includes three simple steps: 1) the anodic exfoliation of graphite in (NH 4 ) 2 SO 4 , 2) sonication to separate the oxidized graphene sheets, and 3) reduction of oxidized graphene to graphene. The procedure makes it possible to convert around 30 wt % of the initial graphite into graphene with short processing times and high yields. The graphene sheets are well dispersed in water, have a carbon/oxygen atomic ratio of 11.7, a lateral size of about 0.5-1 μm, and contain only a few graphene layers, most of which are bilayer sheets. The processability of this type of aqueous dispersion has been demonstrated in the fabrication of macroscopic graphene structures, such as graphene aerogels and graphene films, which have been successfully employed as absorbents or as electrodes in supercapacitors, respectively. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel duplex vapor electrochemical method for silicon solar cells

NASA Technical Reports Server (NTRS)

Kapur, V.; Sancier, K. M.; Sanjurjo, A.; Leach, S.; Westphal, S.; Bartlett, R.; Nanis, L.

1978-01-01

Progress in the development of low-cost solar arrays is reported. Topics covered include: (1) development of a simplified feed system for the Na used in the Na-SiF4 reactor; (2) production of high purity silicon through the reduction of sodium fluosilicate with sodium metal; (3) the leaching process for recovering silicon from the reaction products of the SiF4-Na reaction; and (4) silicon separation by the melting of the reaction product.

Aquagel electrode separator for use in batteries and supercapacitors

DOEpatents

Mayer, Steven T.; Kaschmitter, James L.; Pekala, Richard W.

1995-01-01

An electrode separator for electrochemical energy storage devices, such as a high energy density capacitor incorporating a variety of carbon foam electrodes. The separator is derived from an aquagel of resorcinol-formaldehyde and related polymers and containing ionically conducting electrolyte in the pores thereof.

Ceramic composite separators coated with moisturized ZrO(2) nanoparticles for improving the electrochemical performance and thermal stability of lithium ion batteries.

PubMed

Kim, Ki Jae; Kwon, Hyuk Kwon; Park, Min-Sik; Yim, Taeeun; Yu, Ji-Sang; Kim, Young-Jun

2014-05-28

We introduce a ceramic composite separator prepared by coating moisturized ZrO2 nanoparticles with a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-12wt%HFP) copolymer on a polyethylene separator. The effect of moisturized ZrO2 nanoparticles on the morphology and the microstructure of the polymeric coating layer is investigated. A large number of micropores formed around the embedded ZrO2 nanoparticles in the coating layer as a result of the phase inversion caused by the adsorbed moisture. The formation of micropores highly affects the ionic conductivity and electrolyte uptake of the ceramic composite separator and, by extension, the rate discharge properties of lithium ion batteries. In particular, thermal stability of the ceramic composite separators coated with the highly moisturized ZrO2 nanoparticles (a moisture content of 16 000 ppm) is dramatically improved without any degradation in electrochemical performance compared to the performance of pristine polyethylene separators.

Mediated electrochemical oxidation of organic wastes without electrode separators

DOEpatents

Farmer, J.C.; Wang, F.T.; Hickman, R.G.; Lewis, P.R.

1996-05-14

An electrochemical cell/electrolyte/mediator combination is described for the efficient destruction of organic contaminants using metal salt mediators in a sulfuric acid electrolyte, wherein the electrodes and mediator are chosen such that hydrogen gas is produced at the cathode and no cell membrane is required. 3 figs.

Electrochemical separation of uranium in the molten system LiF-NaF-KF-UF4

NASA Astrophysics Data System (ADS)

Korenko, M.; Straka, M.; Szatmáry, L.; Ambrová, M.; Uhlíř, J.

2013-09-01

This article is focused on the electrochemical investigation (cyclic voltammetry and related studies) of possible reduction of U4+ ions to metal uranium in the molten system LiF-NaF-KF(eut.)-UF4 that can provide basis for the electrochemical extraction of uranium from molten salts. Two-step reduction mechanism for U4+ ions involving one electron exchange in soluble/soluble U4+/U3+ system and three electrons exchange in the second step were found on the nickel working electrode. Both steps were found to be reversible and diffusion controlled. Based on cyclic voltammetry, the diffusion coefficients of uranium ions at 530 °C were found to be D(U4+) = 1.64 × 10-5 cm2 s-1 and D(U3+) 1.76 × 10-5 cm2 s-1. Usage of the nickel spiral electrode for electrorefining of uranium showed fairly good feasibility of its extraction. However some oxidant present during the process of electrorefining caused that the solid deposits contained different uranium species such as UF3, UO2 and K3UO2F5.

Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

PubMed Central

Zimpl, Milan; Skopalova, Jana; Jirovsky, David; Bartak, Petr; Navratil, Tomas; Sedonikova, Jana; Kotoucek, Milan

2012-01-01

Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds. PMID:22666117

The electrochemical fluorination of polymeric materials for high energy density aqueous and non-aqueous battery and fuel cell separators

NASA Technical Reports Server (NTRS)

Liu, C. C.

1983-01-01

A computerized system was established and the electrochemical fluorination of trichloroethylene, polyacrylic acid and polyvinyl alcohol in anhydrous hydrogen fluoride was attempted. Both solid substrates as well as membranes were used. Some difficulties were found in handling and analyzing the solid substrates and membranes. Further studies are needed in this area. A microprocessor aided electrochemical fluorination system capable of obtaining highly reproducible experimental results was established.

The effect of urea on microstructures of tin dioxide grown on Ti plate and its supercapacitor performance

NASA Astrophysics Data System (ADS)

Jinlong, Lv; Meng, Yang; Miura, Hideo

2017-02-01

The effects of urea on microstructures of SnO2 during hydrothermal process and its supercapacitor performance were investigated. The sphere SnO2 was formed on Ti plate in hydrothermal solution without urea, while the SnO2 micro-flowers were assembled by numerous few-layered nanopetals due to adding to urea during hydrothermal process. The separated SnO2 nanopetals arrays showed better electrochemical performance than sphere SnO2. The gap between SnO2 nanopetals promoted penetration of the electrolyte and induced high supercapacitive performance.

Anodized titanium and stainless steel in contact with CFRP: an electrochemical approach considering galvanic corrosion.

PubMed

Mueller, Yves; Tognini, Roger; Mayer, Joerg; Virtanen, Sannakaisa

2007-09-15

The combination of different materials in an implant gives the opportunity to better fulfill the requirements that are needed to improve the healing process. However, using different materials increases the risk of galvanic coupling corrosion. In this study, coupling effects of gold-anodized titanium, stainless steel for biomedical applications, carbon fiber reinforced polyetheretherketone (CFRP), and CFRP containing tantalum fibers are investigated electrochemically and by long-term immersion experiments in simulated body fluid (SBF). Potentiodynamic polarization experiments (i/E curves) and electrochemical impedance spectroscopy (EIS) of the separated materials showed a passive behavior of the metallic samples. Anodized titanium showed no corrosion attacks, whereas stainless steel is highly susceptibility for localized corrosion. On the other side, an active dissolution behavior of both of the CFRPs in the given environment could be determined, leading to delaminating of the carbon fibers from the matrix. Long-term immersion experiments were carried out using a set-up especially developed to simulate coupling conditions of a point contact fixator system (PC-Fix) in a biological environment. Electrochemical data were acquired in situ during the whole immersion time. The results of the immersion experiments correlate with the findings of the electrochemical investigation. Localized corrosion attacks were found on stainless steel, whereas anodized titanium showed no corrosion attacks. No significant differences between the two CFRP types could be found. Galvanic coupling corrosion in combination with crevice conditions and possible corrosion mechanisms are discussed. Copyright 2007 Wiley Periodicals, Inc.

On-demand oil-water separation via low-voltage wettability switching of core-shell structures on copper substrates

NASA Astrophysics Data System (ADS)

Kung, Chun Haow; Zahiri, Beniamin; Sow, Pradeep Kumar; Mérida, Walter

2018-06-01

A copper mesh with dendritic copper-oxide core-shell structure is prepared using an additive-free electrochemical deposition strategy for on-demand oil-water separation. Electrochemical manipulation of the oxidation state of the copper oxide shell phase results in opposite affinities towards water and oil. The copper mesh can be tuned to manifest both superhydrophobic and superoleophilic properties to enable oil-removal. Conversely, switching to superhydrophilic and underwater superoleophobic allows water-removal. These changes correspond to the application of small reduction voltages (<1.5 V) and subsequent air drying. In the oil-removal mode, heavy oil selectively passes through the mesh while water is retained; in water-removal mode, the mesh allows water to permeate but blocks light oil. The smart membrane achieved separation efficiencies higher than 98% for a series of oil-water mixtures. The separation efficiency remains high with less than 5% variation after 30 cycles of oil-water separation in both modes. The switchable wetting mechanism is demonstrated with the aid of microstructural and electrochemical analysis and based on the well-known Cassie-Baxter and Wenzel theories. The selective removal of water or oil from the oil-water mixtures is driven solely by gravity and yields high efficiency and recyclability. The potential applications for the relevant technologies include oil spills cleanup, fuel purification, and wastewater treatment.

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.

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

Closed Fuel Cycle Waste Treatment Strategy

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

Vienna, J. D.; Collins, E. D.; Crum, J. V.

This study is aimed at evaluating the existing waste management approaches for nuclear fuel cycle facilities in comparison to the objectives of implementing an advanced fuel cycle in the U.S. under current legal, regulatory, and logistical constructs. The study begins with the Global Nuclear Energy Partnership (GNEP) Integrated Waste Management Strategy (IWMS) (Gombert et al. 2008) as a general strategy and associated Waste Treatment Baseline Study (WTBS) (Gombert et al. 2007). The tenets of the IWMS are equally valid to the current waste management study. However, the flowsheet details have changed significantly from those considered under GNEP. In addition, significantmore » additional waste management technology development has occurred since the GNEP waste management studies were performed. This study updates the information found in the WTBS, summarizes the results of more recent technology development efforts, and describes waste management approaches as they apply to a representative full recycle reprocessing flowsheet. Many of the waste management technologies discussed also apply to other potential flowsheets that involve reprocessing. These applications are occasionally discussed where the data are more readily available. The report summarizes the waste arising from aqueous reprocessing of a typical light-water reactor (LWR) fuel to separate actinides for use in fabricating metal sodium fast reactor (SFR) fuel and from electrochemical reprocessing of the metal SFR fuel to separate actinides for recycle back into the SFR in the form of metal fuel. The primary streams considered and the recommended waste forms include; Tritium in low-water cement in high integrity containers (HICs); Iodine-129: As a reference case, a glass composite material (GCM) formed by the encapsulation of the silver Mordenite (AgZ) getter material in a low-temperature glass is assumed. A number of alternatives with distinct advantages are also considered including a fused silica waste form with encapsulated nano-sized AgI crystals; Carbon-14 immobilized as a CaCO3 in a cement waste form; Krypton-85 stored as a compressed gas; An aqueous reprocessing high-level waste (HLW) raffinate waste immobilized by the vitrification process; An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel either included in the borosilicate HLW glass or immobilized in the form of a metal alloy or titanate ceramics; Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware super-compacted for disposal or purified for reuse (or disposal as low-level waste, LLW) of Zr by reactive gas separations; Electrochemical process salt HLW incorporated into a glass bonded Sodalite waste form; and Electrochemical process UDS and SS cladding hulls melted into an iron based alloy waste form. Mass and volume estimates for each of the recommended waste forms based on the source terms from a representative flowsheet are reported. In addition to the above listed primary waste streams, a range of secondary process wastes are generated by aqueous reprocessing of LWR fuel, metal SFR fuel fabrication, and electrochemical reprocessing of SFR fuel. These secondary wastes have been summarized and volumes estimated by type and classification. The important waste management data gaps and research needs have been summarized for each primary waste stream and selected waste process.« less

Use of a Corona Discharge to Selectively Pattern a Hydrophilic/Hydrophobic Interface for Integrating Segmented Flow with Microchip Electrophoresis and Electrochemical Detection

PubMed Central

Filla, Laura A.; Kirkpatrick, Douglas C.; Martin, R. Scott

2011-01-01

Segmented flow in microfluidic devices involves the use of droplets that are generated either on- or off-chip. When used with off-chip sampling methods, segmented flow has been shown to prevent analyte dispersion and improve temporal resolution by periodically surrounding an aqueous flow stream with an immiscible carrier phase as it is transferred to the microchip. To analyze the droplets by methods such as electrochemistry or electrophoresis, a method to “desegment” the flow into separate aqueous and immiscible carrier phase streams is needed. In this paper, a simple and straightforward approach for this desegmentation process was developed by first creating an air/water junction in natively hydrophobic and perpendicular PDMS channels. The air-filled channel was treated with a corona discharge electrode to create a hydrophilic/hydrophobic interface. When a segmented flow stream encounters this interface, only the aqueous sample phase enters the hydrophilic channel, where it can be subsequently analyzed by electrochemistry or microchip-based electrophoresis with electrochemical detection. It is shown that the desegmentation process does not significantly degrade the temporal resolution of the system, with rise times as low as 12 s reported after droplets are recombined into a continuous flow stream. This approach demonstrates significant advantages over previous studies in that the treatment process takes only a few minutes, fabrication is relatively simple, and reversible sealing of the microchip is possible. This work should enable future studies where off-chip processes such as microdialysis can be integrated with segmented flow and electrochemical-based detection. PMID:21718004

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.

The electrochemical reduction processes of solid compounds in high temperature molten salts.

PubMed

Xiao, Wei; Wang, Dihua

2014-05-21

Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials.

Apparatus and method for constant flow oxidizing of organic materials

DOEpatents

Surma, Jeffrey E.; Nelson, Norvell; Steward, G. Anthony; Bryan, Garry H.

1999-01-01

The invention is a method and apparatus using high cerium concentration in the anolyte of an electrochemical cell to oxidize organic materials. The method and apparatus further use an ultrasonic mixer to enhance the oxidation rate of the organic material in the electrochemical cell. A reaction vessel provides an advantage of independent reaction temperature control and electrochemical cell temperature control. A separate or independent reaction vessel may be used without an ultrasonic mixer to oxidize gaseous phase organic materials.

Molten salt electrolyte separator

DOEpatents

Kaun, Thomas D.

1996-01-01

A molten salt electrolyte/separator for battery and related electrochemical systems including a molten electrolyte composition and an electrically insulating solid salt dispersed therein, to provide improved performance at higher current densities and alternate designs through ease of fabrication.

Redox‐Active Separators for Lithium‐Ion Batteries

PubMed Central

Pan, Ruijun; Ruan, Changqing; Edström, Kristina; Strømme, Maria

2017-01-01

Abstract A bilayered cellulose‐based separator design is presented that can enhance the electrochemical performance of lithium‐ion batteries (LIBs) via the inclusion of a porous redox‐active layer. The proposed flexible redox‐active separator consists of a mesoporous, insulating nanocellulose fiber layer that provides the necessary insulation between the electrodes and a porous, conductive, and redox‐active polypyrrole‐nanocellulose layer. The latter layer provides mechanical support to the nanocellulose layer and adds extra capacity to the LIBs. The redox‐active separator is mechanically flexible, and no internal short circuits are observed during the operation of the LIBs, even when the redox‐active layer is in direct contact with both electrodes in a symmetric lithium–lithium cell. By replacing a conventional polyethylene separator with a redox‐active separator, the capacity of the proof‐of‐concept LIB battery containing a LiFePO4 cathode and a Li metal anode can be increased from 0.16 to 0.276 mA h due to the capacity contribution from the redox‐active separator. As the presented redox‐active separator concept can be used to increase the capacities of electrochemical energy storage systems, this approach may pave the way for new types of functional separators. PMID:29593967

Redox-Active Separators for Lithium-Ion Batteries.

PubMed

Wang, Zhaohui; Pan, Ruijun; Ruan, Changqing; Edström, Kristina; Strømme, Maria; Nyholm, Leif

2018-03-01

A bilayered cellulose-based separator design is presented that can enhance the electrochemical performance of lithium-ion batteries (LIBs) via the inclusion of a porous redox-active layer. The proposed flexible redox-active separator consists of a mesoporous, insulating nanocellulose fiber layer that provides the necessary insulation between the electrodes and a porous, conductive, and redox-active polypyrrole-nanocellulose layer. The latter layer provides mechanical support to the nanocellulose layer and adds extra capacity to the LIBs. The redox-active separator is mechanically flexible, and no internal short circuits are observed during the operation of the LIBs, even when the redox-active layer is in direct contact with both electrodes in a symmetric lithium-lithium cell. By replacing a conventional polyethylene separator with a redox-active separator, the capacity of the proof-of-concept LIB battery containing a LiFePO 4 cathode and a Li metal anode can be increased from 0.16 to 0.276 mA h due to the capacity contribution from the redox-active separator. As the presented redox-active separator concept can be used to increase the capacities of electrochemical energy storage systems, this approach may pave the way for new types of functional separators.

Electrochemical monitoring of high-temperature molten-salt corrosion

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

Gao, G.; Stott, F.H.; Dawson, J.L.

1990-02-01

Hot molten-salt corrosion can cause serious metal degradation in boiler plant, incinerators, and furnaces. In this research, electrochemical-impedance and electrochemical-noise techniques have been evaluated for the monitoring of hot-corrosion processes in such plants. Tests have been carried out on Ni-1% Co and Alloy 800, a commercial material of interest to operators of industrial plants. Electrochemical-impedance and electrochemical-noise data were compared with the results of metallographic examination of the test alloys and showed reasonable correlation between the electrochemical data and the actual degradation processes. This preliminary work indicated that the electrochemical techniques show considerable promise as instruments for the monitoring ofmore » high-temperature corrosion processes.« less

Self-standing gel polymer electrolyte for improving supercapacitor thermal and electrochemical stability

NASA Astrophysics Data System (ADS)

Dagousset, Laure; Pognon, Grégory; Nguyen, Giao T. M.; Vidal, Frédéric; Jus, Sébastien; Aubert, Pierre-Henri

2018-07-01

Electrochemical energy storage is a very active research topic. However, the use of liquid electrolyte in such systems as supercacitors presents several drawbacks on security and packaging. One way to overcome these issues is to design supercapacitors using solid-state electrolytes. We report here the one-pot synthesis and the characterization of self-standing gel polymer electrolyte (SGPE) composed of semi-Interpenetrating Polymer Networks (semi-IPN) based on poly(ethylene oxide) (PEO) network and non cross-linked nitrile butadiene rubber (NBR), self-containing EMITFSI/γ-Butyrolactone (50/50 wt%/wt%) binary mixtures. The SGPE under the form of a thin film are then used as solid electrolyte and also as separator in supercapacitors with Single Wall Carbon Nanotubes (SWCNTs) bucky paper as electrodes. Thermal characterization revealed the suitability of all synthesized membrane in wide range of operating temperature. Electrochemical stabilities of SGPE were close to that of a cellulose separator system (ESW∼3.2-3.6 V) at 20 °C, and were relatively higher than a cellulose system at 100 °C: 2.1-2.5 V and 1.8 V respectively. Furthermore, floating experiments at 100 °C (holding voltage at 2 V) revealed the exceptionally high stability of SGPE, with a residual capacitance of 93% after 500 h. This high electrochemical performance demonstrated the potential of semi-IPN SGPE as separator/electrolyte for high performance supercapacitors.

Aquagel electrode separator for use in batteries and supercapacitors

DOEpatents

Mayer, S.T.; Kaschmitter, J.L.; Pekala, R.W.

1995-03-28

An electrode separator is described for electrochemical energy storage devices, such as a high energy density capacitor incorporating a variety of carbon foam electrodes. The separator is derived from an aquagel of resorcinol-formaldehyde and related polymers and containing ionically conducting electrolyte in the pores thereof. 9 figures.

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

Vienna, John D.; Todd, Terry A.; Gray, Kimberly D.

The U.S. Department of Energy, Office of Nuclear Energy has chartered an effort to develop technologies to enable safe and cost effective recycle of commercial used nuclear fuel (UNF) in the U.S. Part of this effort includes the evaluation of exiting waste management technologies for effective treatment of wastes in the context of current U.S. regulations and development of waste forms and processes with significant cost and/or performance benefits over those existing. This study summarizes the results of these ongoing efforts with a focus on the highly radioactive primary waste streams. The primary streams considered and the recommended waste formsmore » include: •Tritium separated from either a low volume gas stream or a high volume water stream. The recommended waste form is low-water cement in high integrity containers. •Iodine-129 separated from off-gas streams in aqueous processing. There are a range of potentially suitable waste forms. As a reference case, a glass composite material (GCM) formed by the encapsulation of the silver Mordenite (AgZ) getter material in a low-temperature glass is assumed. A number of alternatives with distinct advantages are also considered including a fused silica waste form with encapsulated nano-sized AgI crystals. •Carbon-14 separated from LWR fuel treatment off-gases and immobilized as a CaCO3 in a cement waste form. •Krypton-85 separated from LWR and SFR fuel treatment off-gases and stored as a compressed gas. •An aqueous reprocessing high-level waste (HLW) raffinate waste which is immobilized by the vitrification process in one of three forms: a single phase borosilicate glass, a borosilicate based glass ceramic, or a multi-phased titanate ceramic [e.g., synthetic rock (Synroc)]. •An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel that is either included in the borosilicate HLW glass or is immobilized in the form of a metal alloy in the case of glass ceramics or titanate ceramics. •Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware that are washed and super-compacted for disposal or as an alternative Zr purification and reuse (or disposal as low-level waste, LLW) by reactive gas separations. •Electrochemical process salt HLW which is immobilized in a glass bonded Sodalite waste form known as the ceramic waste form (CWF). •Electrochemical process UDS and SS cladding hulls which are melted into an iron based alloy waste form. Mass and volume estimates for each of the recommended waste forms based on the source terms from a representative flowsheet are reported.« less

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.

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.

Electrode for electrochemical cell

DOEpatents

Kaun, T.D.; Nelson, P.A.; Miller, W.E.

1980-05-09

An electrode structure for a secondary electrochemical cell includes an outer enclosure defining a compartment containing electrochemical active material. The enclosure includes a rigid electrically conductive metal sheet with perforated openings over major side surfaces. The enclosure can be assembled as first and second trays each with a rigid sheet of perforated electrically conductive metal at major side surfaces and normally extending flanges at parametric margins. The trays can be pressed together with moldable active material between the two to form an expandable electrode. A plurality of positive and negative electrodes thus formed are arranged in an alternating array with porous frangible interelectrode separators within the housing of the secondary electrochemical cell.

Electrode for electrochemical cell

DOEpatents

Kaun, Thomas D.; Nelson, Paul A.; Miller, William E.

1981-01-01

An electrode structure for a secondary electrochemical cell includes an outer enclosure defining a compartment containing electrochemical active material. The enclosure includes a rigid electrically conductive metal sheet with perforated openings over major side surfaces. The enclosure can be assembled as first and second trays each with a rigid sheet of perforated electrically conductive metal at major side surfaces and normally extending flanges at parametric margins. The trays can be pressed together with moldable active material between the two to form an expandable electrode. A plurality of positive and negative electrodes thus formed are arranged in an alternating array with porous frangible interelectrode separators within the housing of the secondary electrochemical cell.

Microscopic dynamics of charge separation at the aqueous electrochemical interface.

PubMed

Kattirtzi, John A; Limmer, David T; Willard, Adam P

2017-12-19

We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water-metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali-halide pair, Na + I - , or classical ions, and the products of water autoionization, H 3 O + OH - , or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water's collective role in the process, is conserved between the bulk liquid and the electrode interface. However, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free-energy barrier to charge separation and a smaller flux over that barrier at the interface result in a rate of dissociation that is 40 times slower relative to the bulk. For water ions, a slightly higher free-energy barrier is offset by a higher flux over the barrier from longer lived hydrogen-bonding patterns at the interface, resulting in a rate of association that is similar both at and away from the interface. We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface.

Microscopic dynamics of charge separation at the aqueous electrochemical interface

PubMed Central

Kattirtzi, John A.; Limmer, David T.; Willard, Adam P.

2017-01-01

We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water–metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali–halide pair, Na+I−, or classical ions, and the products of water autoionization, H3O+OH−, or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water’s collective role in the process, is conserved between the bulk liquid and the electrode interface. However, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free-energy barrier to charge separation and a smaller flux over that barrier at the interface result in a rate of dissociation that is 40 times slower relative to the bulk. For water ions, a slightly higher free-energy barrier is offset by a higher flux over the barrier from longer lived hydrogen-bonding patterns at the interface, resulting in a rate of association that is similar both at and away from the interface. We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface. PMID:28698368

Polyacrylonitrile Separator for High-Performance Aluminum Batteries with Improved Interface Stability.

PubMed

Elia, Giuseppe Antonio; Ducros, Jean-Baptiste; Sotta, Dane; Delhorbe, Virginie; Brun, Agnès; Marquardt, Krystan; Hahn, Robert

2017-11-08

Herein we report, for the first time, an overall evaluation of commercially available battery separators to be used for aluminum batteries, revealing that most of them are not stable in the highly reactive 1-ethyl-3-methylimidazolium chloride:aluminum trichloride (EMIMCl:AlCl 3 ) electrolyte conventionally employed in rechargeable aluminum batteries. Subsequently, a novel highly stable polyacrylonitrile (PAN) separator obtained by the electrospinning technique for application in high-performance aluminum batteries has been prepared. The developed PAN separator has been fully characterized in terms of morphology, thermal stability, and air permeability, revealing its suitability as a separator for battery applications. Furthermore, extremely good compatibility and improved aluminum interface stability in the highly reactive EMIMCl:AlCl 3 electrolyte were discovered. The use of the PAN separator strongly affects the aluminum dissolution/deposition process, leading to a quite homogeneous deposition compared to that of a glass fiber separator. Finally, the applicability of the PAN separator has been demonstrated in aluminum/graphite cells. The electrochemical tests evidence the full compatibility of the PAN separator in aluminum cells. Furthermore, the aluminum/graphite cells employing the PAN separator are characterized by a slightly higher delivered capacity compared to those employing glass fiber separators, confirming the superior characteristics of the PAN separator as a more reliable separator for the emerging aluminum battery technology.

Novel duplex vapor-electrochemical method for silicon solar cells

NASA Technical Reports Server (NTRS)

Nanis, L.; Sanjurjo, A.; Sancier, K. M.; Kapur, V. K.; Bartlett, R. W.; Westphal, S.

1980-01-01

A process was developed for the economic production of high purity Si from inexpensive reactants, based on the Na reduction of SiF4 gas. The products of reaction (NaF, Si) are separated by either aqueous leaching or by direct melting of the NaF-Si product mixture. Impurities known to degrade solar cell performance are all present at sufficiently low concentrations so that melt solidification (e.g., Czochralski) will provide a silicon material suitable for solar cells.

Electrochemical cell method

DOEpatents

Kaun, T.D.; Eshman, P.F.

1980-05-09

A secondary electrochemical cell is prepared by providing positive and negative electrodes having outer enclosures of rigid perforated electrically conductive material defining an internal compartment containing the electrode material in porous solid form. The electrodes are each immersed in molten electrolyte salt prior to cell assembly to incorporate the cell electrolyte. Following solidification of the electrolyte substantially throughout the porous volume of the electrode material, the electrodes are arranged in an alternating positive-negative array with interelectrode separators of porous frangible electrically insulative material. The completed array is assembled into the cell housing and sealed such that on heating the solidified electrolyte flows into the interelectrode separator.

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.

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.

Ultrasensitive electrochemical sensing platform based on graphene wrapping SnO2 nanocorals and autonomous cascade DNA duplication strategy.

PubMed

Chen, Ying-Xu; Huang, Ke-Jing; Lin, Feng; Fang, Lin-Xia

2017-12-01

In this work, a sensitive, universal and reusable electrochemical biosensor based on stannic oxide nanocorals-graphene hybrids (SnO 2 NCs-Gr) is developed for target DNA detection by using two kinds of DNA enzymes for signal amplification through an autonomous cascade DNA duplication strategy. A hairpin probe is designed composing of a projecting part at the 3'-end as identification sequence for target, a recognition site for nicking endonuclease, and an 18-carbon shim to stop polymerization process. The designed DNA duplication-incision-replacement process is handled by KF polymerase and endonuclease, then combining with gold nanoparticles as signal carrier for further signal amplification. In the detection system, the electrochemical-chemical-chemical procedure, which uses ferrocene methanol, tris(2-carboxyethyl)phosphine and l-ascorbic acid 2-phosphate as oxidoreduction neurogen, deoxidizer and zymolyte, separately, is applied to amplify detection signal. Benefiting from the multiple signal amplification mechanism, the proposed sensor reveals a good linear connection between the peak current and logarithm of analyte concentration in range of 0.0001-1 × 10 -11 molL -1 with a detection limit of 1.25 × 10 -17 molL -1 (S/N=3). This assay also opens one promising strategy for ultrasensitive determination of other biological molecules for bioanalysis and biomedicine diagnostics. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermal design of a Mars oxygen production plant

NASA Technical Reports Server (NTRS)

Sridhar, K. R.; Iyer, Venkatesh A.

1991-01-01

The optimal design of the thermal components of a system that uses carbon dioxide from the Martian atmosphere to produce oxygen for spacecraft propulsion and/or life support is discussed. The gases are pressurized, heated and passed through an electrochemical cell. Carbon dioxide is reduced to carbon monoxide and oxygen due to thermal dissociation and electrocatalysis. The oxygen thus formed is separated from the gas mixture by the electrochemical cell. The objective of the design is to optimize both the overall mass and the power consumption of the system. The analysis shows that at electrochemical cell efficiencies of about 50 percent and lower, the optimal system would require unspent carbon dioxide in the exhaust gases to be separated and recycled. Various methods of efficiently compressing the intake gases to system pressures of 0.1 MPa are investigated. The total power requirement for oxygen production rates of 1, 5, and 10 kg/day at various cell efficiencies are presented.

Next-Generation Electrochemical Energy Materials for Intermediate Temperature Molten Oxide Fuel Cells and Ion Transport Molten Oxide Membranes.

PubMed

Belousov, Valery V

2017-02-21

High temperature electrochemical devices such as solid oxide fuel cells (SOFCs) and oxygen separators based on ceramic materials are used for efficient energy conversion. These devices generally operate in the temperature range of 800-1000 °C. The high operating temperatures lead to accelerated degradation of the SOFC and oxygen separator materials. To solve this problem, the operating temperatures of these electrochemical devices must be lowered. However, lowering the temperature is accompanied by decreasing the ionic conductivity of fuel cell electrolyte and oxygen separator membrane. Therefore, there is a need to search for alternative electrolyte and membrane materials that have high ionic conductivity at lower temperatures. A great many opportunities exist for molten oxides as electrochemical energy materials. Because of their unique electrochemical properties, the molten oxide innovations can offer significant benefits for improving energy efficiency. In particular, the newly developed electrochemical molten oxide materials show high ionic conductivities at intermediate temperatures (600-800 °C) and could be used in molten oxide fuel cells (MOFCs) and molten oxide membranes (MOMs). The molten oxide materials containing both solid grains and liquid channels at the grain boundaries have advantages compared to the ceramic materials. For example, the molten oxide materials are ductile, which solves a problem of thermal incompatibility (difference in coefficient of thermal expansion, CTE). Besides, the outstanding oxygen selectivity of MOM materials allows us to separate ultrahigh purity oxygen from air. For their part, the MOFC electrolytes show the highest ionic conductivity at intermediate temperatures. To evaluate the potential of molten oxide materials for technological applications, the relationship between the microstructure of these materials and their transport and mechanical properties must be revealed. This Account summarizes the latest results on oxygen ion transport in potential MOM materials and MOFC electrolytes. In addition, we consider the rapid oxygen transport in a molten oxide scale formed on a metal surface during catastrophic oxidation and show that the same transport could be used beneficially in MOMs and MOFCs. A polymer model explaining the oxygen transport in molten oxides is also considered. Understanding the oxygen transport mechanisms in oxide melts is important for the development of new generation energy materials, which will contribute to more efficient operation of electrochemical devices at intermediate temperatures. Here we highlight the progress made in developing this understanding. We also show the latest advances made in search of alternative molten oxide materials having high mixed ion electronic and ionic conductivities for use in MOMs and MOFCs, respectively. Prospects for further research are presented.

Parallel Electrochemical Treatment System and Application for Identifying Acid-Stable Oxygen Evolution Electrocatalysts

DOE PAGES

Jones, Ryan J. R.; Shinde, Aniketa; Guevarra, Dan; ...

2015-01-05

There are many energy technologies require electrochemical stability or preactivation of functional materials. Due to the long experiment duration required for either electrochemical preactivation or evaluation of operational stability, parallel screening is required to enable high throughput experimentation. We found that imposing operational electrochemical conditions to a library of materials in parallel creates several opportunities for experimental artifacts. We discuss the electrochemical engineering principles and operational parameters that mitigate artifacts int he parallel electrochemical treatment system. We also demonstrate the effects of resistive losses within the planar working electrode through a combination of finite element modeling and illustrative experiments. Operationmore » of the parallel-plate, membrane-separated electrochemical treatment system is demonstrated by exposing a composition library of mixed metal oxides to oxygen evolution conditions in 1M sulfuric acid for 2h. This application is particularly important because the electrolysis and photoelectrolysis of water are promising future energy technologies inhibited by the lack of highly active, acid-stable catalysts containing only earth abundant elements.« less

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

Abdelaziz, Omar; Qu, Ming; Sun, Xiao-Guang

Separate sensible and latent cooling systems offer superior energy efficiency performance compared to conventional vapor compression air conditioning systems. In this paper we describe an innovative non-vapor compression system that uses electrochemical compressor (ECC) to pump hydrogen between 2-metal hydride reservoirs to provide the sensible cooling effect. The heat rejected during this process is used to regenerate the ionic liquid (IL) used for desiccant dehumidification. The overall system design is illustrated. The Xergy version 4C electrochemical compressor, while not designed as a high pressure system, develops in excess of 2 MPa (300 psia) and pressure ratios > 30. The projectedmore » base efficiency improvement of the electrochemical compressor is expected to be ~ 20% with higher efficiency when in low capacity mode due to being throttleable to lower capacity with improved efficiency. The IL was tailored to maximize the absorption/desorption rate of water vapor at moderate regeneration temperature. This IL, namely, [EMIm].OAc, is a hydrophilic IL with a working concentration range of 28.98% when operating between 25 75 C. The ECC metal hydride system is expected to show superior performance to typical vapor compression systems. As such, the combined efficiency gains from the use of ECC and separate and sensible cooling would offer significant potential savings to existing vapor compression cooling technology. A high efficiency Window Air Conditioner system is described based on this novel configuration. The system s schematic is provided. Models compared well with actual operating data obtained by running the prototype system. Finally, a model of an LiCl desiccant system in conjunction with the ECC-based metal hydride heat exchangers is provided.« less

Hybridizing energy conversion and storage in a mechanical-to-electrochemical process for self-charging power cell.

PubMed

Xue, Xinyu; Wang, Sihong; Guo, Wenxi; Zhang, Yan; Wang, Zhong Lin

2012-09-12

Energy generation and energy storage are two distinct processes that are usually accomplished using two separated units designed on the basis of different physical principles, such as piezoelectric nanogenerator and Li-ion battery; the former converts mechanical energy into electricity, and the latter stores electric energy as chemical energy. Here, we introduce a fundamental mechanism that directly hybridizes the two processes into one, in which the mechanical energy is directly converted and simultaneously stored as chemical energy without going through the intermediate step of first converting into electricity. By replacing the polyethylene (PE) separator as for conventional Li battery with a piezoelectric poly(vinylidene fluoride) (PVDF) film, the piezoelectric potential from the PVDF film as created by mechanical straining acts as a charge pump to drive Li ions to migrate from the cathode to the anode accompanying charging reactions at electrodes. This new approach can be applied to fabricating a self-charging power cell (SCPC) for sustainable driving micro/nanosystems and personal electronics.

Stacking Oxygen-Separation Cells

NASA Technical Reports Server (NTRS)

Schroeder, James E.

1991-01-01

Simplified configuration and procedure developed for assembly of stacks of solid-electrolyte cells separating oxygen from air electrochemically. Reduces number of components and thus reduces probability of such failures as gas leaks, breakdown of sensitive parts, and electrical open or short circuits. Previous, more complicated version of cell described in "Improved Zirconia Oxygen-Separation Cell" (NPO-16161).

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.

Electrospun montmorillonite modified poly(vinylidene fluoride) nanocomposite separators for lithium-ion batteries

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

Fang, Changjiang; Yang, Shuli; Zhao, Xinfei

2016-07-15

Highlights: • Composite separators of PVDF and MMT for lithium-ion batteries were electrospun. • Thermal dimensional stability and tensile property of composite separators get improved. • Presence of montmorillonite promotes electrical properties of PVDF fibrous separators. • Batteries consisting of PVDF/MMT-5% separator achieve the best performance. - Abstract: Composite separators of poly(vinylidene fluoride) (PVDF) with different contents of montmorillonite (MMT) for Li-ion batteries have been fabricated by electrospinning. The morphology, function group, crystallinity, and mechanical properties of membranes were investigated by scanning electron microscope (SEM), Fourier Transform infrared spectra (FT-IR), differential scanning calorimetry (DSC), and tensile test, respectively. Interlayer spacingmore » of MMT in polymer was characterized by X-ray diffraction (XRD). In addition, the results of electrochemical measurements suggest that PVDF/MMT-5% composite membrane has maximum ionic conductivity of 4.2 mS cm{sup −1}, minimum interfacial resistance of 97 Ω, and excellent electrochemical stability. The cell comprising PVDF/MMT-5% composite membrane shows higher capacity and more stable cycle performance than the one using commercial Celgard PP membrane.« less

Cell structure for electrochemical devices and method of making same

DOEpatents

Kaun, Thomas D.

2007-03-27

An electrochemical device comprising alternating layers of positive and negative electrodes separated from each other by separator layers. The electrode layers extend beyond the periphery of the separator layers providing superior contact between the electrodes and battery terminals, eliminating the need for welding the electrode to the terminal. Electrical resistance within the battery is decreased and thermal conductivity of the cell is increased allowing for superior heat removal from the battery and increased efficiency. Increased internal pressure within the battery can be alleviated without damaging or removing the battery from service while keeping the contents of the battery sealed off from the atmosphere by a pressure release system. Nonoperative cells within a battery assembly can also be removed from service by shorting the nonoperative cell thus decreasing battery life.

Electrochemical reduction of toluene to methylcyclohexane for use as an energy carrier

NASA Astrophysics Data System (ADS)

Matsuoka, Koji; Miyoshi, Kota; Sato, Yasushi

2017-03-01

The electrochemical reduction of liquid toluene to methylcyclohexane (MCH) was investigated using a membrane electrode assembly (MEA) and high active-area catalysts commonly used in proton exchange membrane fuel cells (PEMFC). The current density on Pt/C was higher than on PtRu/C, which was comparable to that of alkaline water electrolysis. The potential of hydrogen evolution was shifted negatively by the presence of toluene and MCH. Therefore, the toluene reduction reaction was almost perfectly separated from the hydrogen evolution reaction. Toluene was perfectly reduced to MCH at around 0 V vs. RHE on PtRu/C and no by-products were detected in the solutions after electrolysis. MCH was produced at a Faradaic efficiency of more than 96% by carefully keeping the potential above -30 mV vs. RHE. Through this electrolytic process, we were able to reduce the concentration of toluene from 100% to 7.6%.

Unusually Strong Long-Distance Metal-Metal Coupling in Bis(ferrocene)-Containing BOPHY: An Introduction to Organometallic BOPHYs.

PubMed

Rhoda, Hannah M; Chanawanno, Kullapa; King, Alexander J; Zatsikha, Yuriy V; Ziegler, Christopher J; Nemykin, Victor N

2015-12-07

The first organometallic BOPHY (BOPHY=bis(difluoroboron)-1,2-bis{(pyrrol-2-yl)methylene}hydrazine) containing two ferrocene substituents was prepared through a Knoevenagel condensation between tetramethyl substituted BOPHY and ferrocene carboxaldehyde. An unprecedentedly strong long-range (≈17.2 Å) metal-metal coupling in this new complex was investigated using electrochemical, spectroelectrochemical, and chemical oxidation methods. Electrochemical data is indicative of a 200 mV separation between the first and the second ferrocene-centered oxidation processes. Formation of the mixed-valence states and appearance and disappearance of two NIR bands were observed during stepwise oxidation of the first organometallic BOPHY. The electronic structure and the nature of the excited states in this new chromophore were studied by DFT and TDDFT calculations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Battery paste compositions and electrochemical cells for use therewith

DOEpatents

Olson, J.B.

1999-02-16

An improved battery paste composition and a lead-acid electrochemical cell which incorporates the composition are disclosed. The cell includes a positive current collector and a negative current collector which are each coated with a paste containing one or more lead-containing compositions and a paste vehicle to form a positive plate and a negative plate. An absorbent electrolyte-containing separator member may also be positioned between the positive and negative plates. The paste on the positive current collector, the negative current collector, or both further includes a special additive consisting of polyvinyl sulfonic acid or salts thereof which provides many benefits including improved battery cycle life, increased charge capacity, and enhanced overall stability. The additive also makes the pastes smoother and more adhesive, thereby improving the paste application process. The paste compositions of interest may be used in conventional flat-plate cells or in spirally wound batteries with equal effectiveness. 2 figs.

Battery paste compositions and electrochemical cells for use therewith

DOEpatents

Olson, John B.

1999-12-07

An improved battery paste composition and a lead-acid electrochemical cell which incorporates the composition. The cell includes a positive current collector and a negative current collector which are each coated with a paste containing one or more lead-containing compositions and a paste vehicle to form a positive plate and a negative plate. An absorbent electrolyte-containing separator member may also be positioned between the positive and negative plates. The paste on the positive current collector, the negative current collector, or both further includes a special additive consisting of polyvinylsulfonic acid or salts thereof which provides many benefits including improved battery cycle life, increased charge capacity, and enhanced overall stability. The additive also makes the pastes smoother and more adhesive, thereby improving the paste application process. The paste compositions of interest may be used in conventional flat-plate cells or in spirally wound batteries with equal effectiveness.

Battery paste compositions and electrochemical cells for use therewith

DOEpatents

Olson, John B.

1999-02-16

An improved battery paste composition and a lead-acid electrochemical cell which incorporates the composition. The cell includes a positive current collector and a negative current collector which are each coated with a paste containing one or more lead-containing compositions and a paste vehicle to form a positive plate and a negative plate. An absorbent electrolyte-containing separator member may also be positioned between the positive and negative plates. The paste on the positive current collector, the negative current collector, or both further includes a special additive consisting of polyvinylsulfonic acid or salts thereof which provides many benefits including improved battery cycle life, increased charge capacity, and enhanced overall stability. The additive also makes the pastes smoother and more adhesive, thereby improving the paste application process. The paste compositions of interest may be used in conventional flat-plate cells or in spirally wound batteries with equal effectiveness.

Three dimensional electrode for the electrolytic removal of contaminants from aqueous waste streams

DOEpatents

Spiegel, Ella F.; Sammells, Anthony F.

2001-01-01

Efficient and cost-effective electrochemical devices and processes for the remediation of aqueous waste streams. The invention provides electrolytic cells having a high surface area spouted electrode for removal of heavy metals and oxidation of organics from aqueous environments. Heavy metal ions are reduced, deposited on cathode particles of a spouted bed cathode and removed from solution. Organics are efficiently oxidized at anode particles of a spouted bed anode and removed from solution. The method of this inventions employs an electrochemical cell having an anolyte compartment and a catholyte compartment, separated by a microporous membrane, in and through which compartments anolyte and catholyte, respectively, are circulated. A spouted-bed electrode is employed as the cathode for metal deposition from contaminated aqueous media introduced as catholyte and as the anode for oxidation of organics from contaminated aqueous media introduced as anolyte.

Production of Titanium Metal by an Electrochemical Molten Salt Process

NASA Astrophysics Data System (ADS)

Fatollahi-Fard, Farzin

Titanium production is a long and complicated process. What we often consider to be the standard method of primary titanium production (the Kroll process), involves many complex steps both before and after to make a useful product from titanium ore. Thus new methods of titanium production, especially electrochemical processes, which can utilize less-processed feedstocks have the potential to be both cheaper and less energy intensive than current titanium production processes. This project is investigating the use of lower-grade titanium ores with the electrochemical MER process for making titanium via a molten salt process. The experimental work carried out has investigated making the MER process feedstock (titanium oxycarbide) with natural titanium ores--such as rutile and ilmenite--and new ways of using the MER electrochemical reactor to "upgrade" titanium ores or the titanium oxycarbide feedstock. It is feasible to use the existing MER electrochemical reactor to both purify the titanium oxycarbide feedstock and produce titanium metal.

Prawn Shell Derived Chitin Nanofiber Membranes as Advanced Sustainable Separators for Li/Na-Ion Batteries.

PubMed

Zhang, Tian-Wen; Shen, Bao; Yao, Hong-Bin; Ma, Tao; Lu, Lei-Lei; Zhou, Fei; Yu, Shu-Hong

2017-08-09

Separators, necessary components to isolate cathodes and anodes in Li/Na-ion batteries, are consumed in large amounts per year; thus, their sustainability is a concerning issue for renewable energy storage systems. However, the eco-efficient and environmentally friendly fabrication of separators with a high mechanical strength, excellent thermal stability, and good electrolyte wettability is still challenging. Herein, we reported the fabrication of a new type of separators for Li/Na-ion batteries through the self-assembly of eco-friendly chitin nanofibers derived from prawn shells. We demonstrated that the pore size in the chitin nanofiber membrane (CNM) separator can be tuned by adjusting the amount of pore generation agent (sodium dihydrogen citrate) in the self-assembly process of chitin nanofibers. By optimizing the pore size in CNM separators, the electrochemical performance of the LiFePO 4 /Li half-cell with a CNM separator is comparable to that with a commercialized polypropylene (PP) separator. More attractively, the CNM separator showed a much better performance in the LiFePO 4 /Li cell at 120 °C and Na 3 V 2 (PO 4 ) 3 /Na cell than the PP separator. The proposed fabrication of separators by using natural raw materials will play a significant contribution to the sustainable development of renewable energy storage systems.

Analysis of Protein-Phenolic Compound Modifications Using Electrochemistry Coupled to Mass Spectrometry.

PubMed

Kallinich, Constanze; Schefer, Simone; Rohn, Sascha

2018-01-29

In the last decade, electrochemical oxidation coupled with mass spectrometry has been successfully used for the analysis of metabolic studies. The application focused in this study was to investigate the redox potential of different phenolic compounds such as the very prominent chlorogenic acid. Further, EC/ESI-MS was used as preparation technique for analyzing adduct formation between electrochemically oxidized phenolic compounds and food proteins, e.g., alpha-lactalbumin or peptides derived from a tryptic digestion. In the first step of this approach, two reactant solutions are combined and mixed: one contains the solution of the digested protein, and the other contains the phenolic compound of interest, which was, prior to the mixing process, electrochemically transformed to several oxidation products using a boron-doped diamond working electrode. As a result, a Michael-type addition led to covalent binding of the activated phenolic compounds to reactive protein/peptide side chains. In a follow-up approach, the reaction mix was further separated chromatographically and finally detected using ESI-HRMS. Compound-specific, electrochemical oxidation of phenolic acids was performed successfully, and various oxidation and reaction products with proteins/peptides were observed. Further optimization of the reaction (conditions) is required, as well as structural elucidation concerning the final adducts, which can be phenolic compound oligomers, but even more interestingly, quite complex mixtures of proteins and oxidation products.

Influence of cobalt and manganese content on the dehydrogenation capacity and kinetics of air-exposed LaNi 5+ x-type alloys in solid gas and electrochemical reactions

NASA Astrophysics Data System (ADS)

Raekelboom, E.; Cuevas, F.; Knosp, B.; Percheron-Guégan, A.

The effect of cobalt and manganese content on the dehydrogenation properties of air-exposed MmB 5+ x-type (Mm = mischmetal; B = Ni, Al, Co and Mn) alloys was investigated both in solid gas and electrochemical reactions. The cobalt and manganese content were varied separately while keeping constant the plateau pressure of the hydrides. The increase of the cobalt content leads to a decrease of the hydrogen capacity whereas the manganese content has no much effect. In solid gas reactions, the kinetics were found to be limited by the hydrogen diffusion through the surface oxidation layer. As for the electrochemistry, the kinetics are limited by a corrosion layer formed in alkaline medium. The desorption rates for both processes increase as the cobalt or manganese content decreases. This is thought to be due to an enhancement of the hydrogen diffusivity through the oxidation layer. As a result, a low cobalt or manganese content in MmB 5+ x alloys is found to be beneficial for the hydrogen desorption kinetics in both processes.

Processing of spent Ni-MH batteries for the recovery of cobalt, nickel and rare earth elements bearing materials by means of a chemical and electrochemical sequential process

NASA Astrophysics Data System (ADS)

Delvasto, P.; Orta Rodríguez, R.; Blanco, S.

2016-02-01

Rechargeable Ni-MH batteries contain strategic metal values which are worth to be recovered. In the present work, a preliminary sequential chemical and electrochemical procedure is proposed, in order to reclaim materials bearing Ni, Co and rare earth elements (REE) from Ni-MH spent batteries. Initially, spent batteries are disassembled to separate the electrode materials (anode and cathode), which are then leached with an aqueous solution of 5w% sulphuric acid. The metal content of this solution is checked by atomic absorption spectrometry techniques. The obtained solution is pH-adjusted (with NaOH), until pH is between 4.0 and 4.3; then, it is heated up to 70°C to precipitate a rare earth elements sulphate (Nd, La, Pr, Ce), as determined by means of x-ray fluorescence techniques. The solids-free solution is then electrolyzed, in order to recover a Ni-Co alloy. The electrolysis conditions were established through a cyclic voltammetry technique.

Microfluidic electrochemical device and process for chemical imaging and electrochemical analysis at the electrode-liquid interface in-situ

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

Yu, Xiao-Ying; Liu, Bingwen; Yang, Li

2016-03-01

A microfluidic electrochemical device and process are detailed that provide chemical imaging and electrochemical analysis under vacuum at the surface of the electrode-sample or electrode-liquid interface in-situ. The electrochemical device allows investigation of various surface layers including diffuse layers at selected depths populated with, e.g., adsorbed molecules in which chemical transformation in electrolyte solutions occurs.

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.

Review on the progress in synthesis and application of magnetic carbon nanocomposites.

PubMed

Zhu, Maiyong; Diao, Guowang

2011-07-01

This review focuses on the synthesis and application of nanostructured composites containing magnetic nanostructures and carbon-based materials. Great progress in fabrication of magnetic carbon nanocomposites has been made by developing methods including filling process, template-based synthesis, chemical vapor deposition, hydrothermal/solvothermal method, pyrolysis procedure, sol-gel process, detonation induced reaction, self-assembly method, etc. The applications of magnetic carbon nanocomposites expanded to a wide range of fields such as environmental treatment, microwave absorption, magnetic recording media, electrochemical sensor, catalysis, separation/recognization of biomolecules and drug delivery are discussed. Finally, some future trends and perspectives in this research area are outlined.

Review on the progress in synthesis and application of magnetic carbon nanocomposites

NASA Astrophysics Data System (ADS)

Zhu, Maiyong; Diao, Guowang

2011-07-01

This review focuses on the synthesis and application of nanostructured composites containing magnetic nanostructures and carbon-based materials. Great progress in fabrication of magnetic carbon nanocomposites has been made by developing methods including filling process, template-based synthesis, chemical vapor deposition, hydrothermal/solvothermal method, pyrolysis procedure, sol-gel process, detonation induced reaction, self-assembly method, etc. The applications of magnetic carbon nanocomposites expanded to a wide range of fields such as environmental treatment, microwave absorption, magnetic recording media, electrochemical sensor, catalysis, separation/recognization of biomolecules and drug delivery are discussed. Finally, some future trends and perspectives in this research area are outlined.

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

NASA Technical Reports Server (NTRS)

Narayan, Sri; Haines, Brennan; Blosiu, Julian; Marzwell, Neville

2009-01-01

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Molten salt electrolyte separator

DOEpatents

Kaun, T.D.

1996-07-09

The patent describes a molten salt electrolyte/separator for battery and related electrochemical systems including a molten electrolyte composition and an electrically insulating solid salt dispersed therein, to provide improved performance at higher current densities and alternate designs through ease of fabrication. 5 figs.

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

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

McSkimming, Alex; Su, Jing; Cheisson, Thibault

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

DOE PAGES

McSkimming, Alex; Su, Jing; Cheisson, Thibault; ...

2018-03-23

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

An Electrochemical Quartz Crystal Microbalance Multisensor System Based on Phthalocyanine Nanostructured Films: Discrimination of Musts

PubMed Central

Garcia-Hernandez, Celia; Medina-Plaza, Cristina; Garcia-Cabezon, Cristina; Martin-Pedrosa, Fernando; del Valle, Isabel; de Saja, Jose Antonio; Rodríguez-Méndez, Maria Luz

2015-01-01

An array of electrochemical quartz crystal electrodes (EQCM) modified with nanostructured films based on phthalocyanines was developed and used to discriminate musts prepared from different varieties of grapes. Nanostructured films of iron, nickel and copper phthalocyanines were deposited on Pt/quartz crystals through the Layer by Layer technique by alternating layers of the corresponding phthalocyanine and poly-allylamine hydrochloride. Simultaneous electrochemical and mass measurements were used to study the mass changes accompanying the oxidation of electroactive species present in must samples obtained from six Spanish varieties of grapes (Juan García, Prieto Picudo, Mencía Regadío, Cabernet Sauvignon, Garnacha and Tempranillo). The mass and voltammetric outputs were processed using three-way models. Parallel Factor Analysis (PARAFAC) was successfully used to discriminate the must samples according to their variety. Multi-way partial least squares (N-PLS) evidenced the correlations existing between the voltammetric data and the polyphenolic content measured by chemical methods. Similarly, N-PLS showed a correlation between mass outputs and parameters related to the sugar content. These results demonstrated that electronic tongues based on arrays of EQCM sensors can offer advantages over arrays of mass or voltammetric sensors used separately. PMID:26610494

Method for manufacturing an electrochemical cell

DOEpatents

Kaun, Thomas D.; Eshman, Paul F.

1982-01-01

A secondary electrochemical cell is prepared by providing positive and negative electrodes having outer enclosures of rigid perforated electrically conductive material defining an internal compartment containing the electrode material in porous solid form. The electrodes are each immersed in molten electrolyte salt prior to cell assembly to incorporate the cell electrolyte. Following solidification of the electrolyte substantially throughout the porous volume of the electrode material, the electrodes are arranged in an alternating positive-negative array with interelectrode separators of porous frangible electrically insulative material. The completed array is assembled into the cell housing and sealed such that on heating the solidified electrolyte flows into the interelectrode separator.

Mesoporous Cladophora cellulose separators for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Pan, Ruijun; Cheung, Ocean; Wang, Zhaohui; Tammela, Petter; Huo, Jinxing; Lindh, Jonas; Edström, Kristina; Strømme, Maria; Nyholm, Leif

2016-07-01

Much effort is currently made to develop inexpensive and renewable materials which can replace the polyolefin microporous separators conventionally used in contemporary lithium-ion batteries. In the present work, it is demonstrated that mesoporous Cladophora cellulose (CC) separators constitute very promising alternatives based on their high crystallinity, good thermal stability and straightforward manufacturing. The CC separators, which are fabricated using an undemanding paper-making like process involving vacuum filtration, have a typical thickness of about 35 μm, an average pore size of about 20 nm, a Young's modulus of 5.9 GPa and also exhibit an ionic conductivity of 0.4 mS cm-1 after soaking with 1 M LiPF6 EC: DEC (1/1, v/v) electrolyte. The CC separators are demonstrated to be thermally stable at 150 °C and electrochemically inert in the potential range between 0 and 5 V vs. Li+/Li. A LiFePO4/Li cell containing a CC separator showed good cycling stability with 99.5% discharge capacity retention after 50 cycles at a rate of 0.2 C. These results indicate that the renewable CC separators are well-suited for use in high-performance lithium-ion batteries.

Development of an On-animal Separation-based Sensor for Monitoring Drug Metabolism in Freely Roaming Sheep

PubMed Central

Scott, David E.; Willis, Sean D.; Gabbert, Seth; Johnson, Dave A.; Naylor, Erik; Janle, Elsa M.; Krichevsky, Janice E.; Lunte, Craig E.; Lunte, Susan M.

2015-01-01

The development of an on-animal separation-based sensor that can be employed for monitoring drug metabolism in a freely roaming sheep is described. The system consists of microdialysis sampling coupled directly to microchip electrophoresis with electrochemical detection (MD-ME-EC). Separations were accomplished using an all-glass chip with integrated platinum working and reference electrodes. Discrete samples from the microdialysis flow were introduced into the electrophoresis chip using a flow-gated injection approach. Electrochemical detection was accomplished in-channel using a two-electrode isolated potentiostat. Nitrite was separated by microchip electrophoresis using reverse polarity and a run buffer consisting of 50 mM phosphate at pH 7.4. The entire system was under telemetry control. The system was first tested with rats to monitor the production of nitrite following introduction of nitroglycerin into the subdermal tissue using a linear probe. The data acquired using the on-line MD-ME-EC system was compared to that obtained off-line analysis by liquid chromatography with electrochemical detection (LC-EC), using a second microdialysis probe implanted parallel to the first probe in the same animal. The MD-ME-EC device was then used on-animal to monitor the subdermal metabolism of nitroglycerin in sheep. The ultimate goal is to use this device to simultaneously monitor drug metabolism and behavior in a freely roaming animal. PMID:25697221

Scanning Tunneling Microscopy and Infrared Spectroscopy as Combined In- Situ Probes of Electrochemical Adlayer Structure: Cyanide on PT(111)

DTIC Science & Technology

1994-02-01

electrochemically etched in near- saturated CaC1 2 and coated with a thermosetting plastic[13]. The quasi-reference electrode was a gold wire. The Pt(lll...annealing procedure, display arrays of small (ca 3-5 nm) terrace domains, these being separated from each other by monoatomic steps running in various

Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

DOEpatents

Borglum, Brian P.; Bessette, Norman F.

2000-01-01

An electrochemical cell is made having a porous fuel electrode (16) and a porous air electrode (13), with solid oxide electrolyte (15) therebetween, where the air electrode surface opposing the electrolyte has a separate, attached, dense, continuous layer (14) of a material containing cerium oxide, and where electrolyte (16) contacts the continuous oxide layer (14), without contacting the air electrode (13).

Sensitive electrochemical immunoassay for 2,4,6-trinitrotoluene based on functionalized silica nanoparticle labels

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

Wang, Jun; Liu, Guodong; Wu, Hong

2008-03-03

We present a poly(guanine)-functionalized silica nanoparticle (NP) label-based electrochemical immunoassay for sensitively detecting 2,4,6-trinitrotoluene (TNT). This immunoassay takes advantage of magnetic bead–based platform for competitive displacement immunoreactions and separation, and use electroactive nanoparticles as labels for signal amplification. For this assay, anti-TNT-coated magnetic beads interacted with TNT analog-conjugated poly(guanine)-silica NPs and formed analog-anti-TNT immunocomplexes on magnetic beads. The immunocomplexes coated magnetic beads were exposed to TNT samples, which resulted in displacing the analog conjugated poly(guanine) silica NPs into solution by TNT. In contrast, there are no guanine residues releasing into the solution in the absence of TNT. The reaction solutionmore » was then separated from the magnetic beads and transferred to the electrode surface for electrochemical measurements of guanine oxidation with Ru(bpy)32+ as mediator. The sensitivity of this TNT assay was greatly enhanced through dual signal amplifications: 1) a large amount of guanine residues on silica nanoparticles is introduced into the test solution by displacement immunoreactions and 2) a Ru(bpy)32+-induced guanine catalytic oxidation further enhances the electrochemical signal. Some experimental parameters for the nanoparticle label-based electrochemical immunoassay were studied and the performance of this assay was evaluated. The method is found to be very sensitive and the detection limit of this assay is ~ 0.1 ng mL-1 TNT. The electrochemical immunoassay based on the poly[guanine]-functionalized silica NP label offers a new approach for sensitive detection of explosives.« less

High-rate overcharge-protection separators for rechargeable lithium-ion batteries and the method of making the same

DOEpatents

Chen, Guoying; Richardson, Thomas J.

2016-12-20

This invention relates to low-cost, electroactive-polymer incorporated fine-fiber composite membranes for use as overcharge and/or overdischarge protection separators in non-aqueous electrochemical cells and the methods for making such membranes.

Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes

DOE PAGES

Yang, Sangmo; Paranthaman, Mariappan Parans; Noh, Tae Won; ...

2016-01-08

The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When themore » grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag +/Ag redox reaction to Ag +-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.« less

Source-separated urine opens golden opportunities for microbial electrochemical technologies.

PubMed

Ledezma, Pablo; Kuntke, Philipp; Buisman, Cees J N; Keller, Jürg; Freguia, Stefano

2015-04-01

The food security of a booming global population demands a continuous and sustainable supply of fertilisers. Their current once-through use [especially of the macronutrients nitrogen (N), phosphorus (P), and potassium (K)] requires a paradigm shift towards recovery and reuse. In the case of source-separated urine, efficient recovery could supply 20% of current macronutrient usage and remove 50-80% of nutrients present in wastewater. However, suitable technology options are needed to allow nutrients to be separated from urine close to the source. Thus far none of the proposed solutions has been widely implemented due to intrinsic limitations. Microbial electrochemical technologies (METs) have proved to be technically and economically viable for N recovery from urine, opening the path for novel decentralised systems focused on nutrient recovery and reuse. Copyright © 2015 Elsevier Ltd. All rights reserved.

In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

PubMed

Chen, Daqun; Hu, Weihua

2017-04-18

Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

Heat transfer enhancement in a lithium-ion cell through improved material-level thermal transport

NASA Astrophysics Data System (ADS)

Vishwakarma, Vivek; Waghela, Chirag; Wei, Zi; Prasher, Ravi; Nagpure, Shrikant C.; Li, Jianlin; Liu, Fuqiang; Daniel, Claus; Jain, Ankur

2015-12-01

While Li-ion cells offer excellent electrochemical performance for several applications including electric vehicles, they also exhibit poor thermal transport characteristics, resulting in reduced performance, overheating and thermal runaway. Inadequate heat removal from Li-ion cells originates from poor thermal conductivity within the cell. This paper identifies the rate-limiting material-level process that dominates overall thermal conduction in a Li-ion cell. Results indicate that thermal characteristics of a Li-ion cell are largely dominated by heat transfer across the cathode-separator interface rather than heat transfer through the materials themselves. This interfacial thermal resistance contributes around 88% of total thermal resistance in the cell. Measured value of interfacial resistance is close to that obtained from theoretical models that account for weak adhesion and large acoustic mismatch between cathode and separator. Further, to address this problem, an amine-based chemical bridging of the interface is carried out. This is shown to result in in four-times lower interfacial thermal resistance without deterioration in electrochemical performance, thereby increasing effective thermal conductivity by three-fold. This improvement is expected to reduce peak temperature rise during operation by 60%. By identifying and addressing the material-level root cause of poor thermal transport in Li-ion cells, this work may contributes towards improved thermal performance of Li-ion cells.

Preparation, Modification, Characterization, and Biosensing Application of Nanoporous Gold Using Electrochemical Techniques

PubMed Central

Neupane, Dharmendra; Nepal, Bishal; Mikhaylov, Vasilii; Stine, Keith J.

2018-01-01

Nanoporous gold (np-Au), because of its high surface area-to-volume ratio, excellent conductivity, chemical inertness, physical stability, biocompatibility, easily tunable pores, and plasmonic properties, has attracted much interested in the field of nanotechnology. It has promising applications in the fields of catalysis, bio/chemical sensing, drug delivery, biomolecules separation and purification, fuel cell development, surface-chemistry-driven actuation, and supercapacitor design. Many chemical and electrochemical procedures are known for the preparation of np-Au. Recently, researchers are focusing on easier and controlled ways to tune the pores and ligaments size of np-Au for its use in different applications. Electrochemical methods have good control over fine-tuning pore and ligament sizes. The np-Au electrodes that are prepared using electrochemical techniques are robust and are easier to handle for their use in electrochemical biosensing. Here, we review different electrochemical strategies for the preparation, post-modification, and characterization of np-Au along with the synergistic use of both electrochemistry and np-Au for applications in biosensing. PMID:29547580

Preparation, Modification, Characterization, and Biosensing Application of Nanoporous Gold Using Electrochemical Techniques.

PubMed

Bhattarai, Jay K; Neupane, Dharmendra; Nepal, Bishal; Mikhaylov, Vasilii; Demchenko, Alexei V; Stine, Keith J

2018-03-16

Nanoporous gold (np-Au), because of its high surface area-to-volume ratio, excellent conductivity, chemical inertness, physical stability, biocompatibility, easily tunable pores, and plasmonic properties, has attracted much interested in the field of nanotechnology. It has promising applications in the fields of catalysis, bio/chemical sensing, drug delivery, biomolecules separation and purification, fuel cell development, surface-chemistry-driven actuation, and supercapacitor design. Many chemical and electrochemical procedures are known for the preparation of np-Au. Recently, researchers are focusing on easier and controlled ways to tune the pores and ligaments size of np-Au for its use in different applications. Electrochemical methods have good control over fine-tuning pore and ligament sizes. The np-Au electrodes that are prepared using electrochemical techniques are robust and are easier to handle for their use in electrochemical biosensing. Here, we review different electrochemical strategies for the preparation, post-modification, and characterization of np-Au along with the synergistic use of both electrochemistry and np-Au for applications in biosensing.

Electrochemical Properties of LLTO/Fluoropolymer-Shell Cellulose-Core Fibrous Membrane for Separator of High Performance Lithium-Ion Battery

PubMed Central

Huang, Fenglin; Liu, Wenting; Li, Peiying; Ning, Jinxia; Wei, Qufu

2016-01-01

A superfine Li0.33La0.557TiO3 (LLTO, 69.4 nm) was successfully synthesized by a facile solvent-thermal method to enhance the electrochemical properties of the lithium-ion battery separator. Co-axial nanofiber of cellulose and Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was prepared by a co-axial electrospinning technique, in which the shell material was PVDF-HFP and the core was cellulose. LLTO superfine nanoparticles were incorporated into the shell of the PVDF-HFP. The core–shell composite nanofibrous membrane showed good wettability (16.5°, contact angle), high porosity (69.77%), and super electrolyte compatibility (497%, electrolyte uptake). It had a higher ionic conductivity (13.897 mS·cm−1) than those of pure polymer fibrous membrane and commercial separator. In addition, the rate capability (155.56 mAh·g−1) was also superior to the compared separator. These excellent performances endowed LLTO composite nanofibrous membrane as a promising separator for high-performance lithium-ion batteries. PMID:28787873

Production Of High Specific Activity Copper-67

DOEpatents

Jamriska, Sr., David J.; Taylor, Wayne A.; Ott, Martin A.; Fowler, Malcolm; Heaton, Richard C.

2002-12-03

A process for the selective production and isolation of high specific activity cu.sup.67 from proton-irradiated enriched Zn.sup.70 target comprises target fabrication, target irradiation with low energy (<25 MeV) protons, chemical separation of the Cu.sup.67 product from the target material and radioactive impurities of gallium, cobalt, iron, and stable aluminum via electrochemical methods or ion exchange using both anion and cation organic ion exchangers, chemical recovery of the enriched Zn.sup.70 target material, and fabrication of new targets for re-irradiation is disclosed.

Production Of High Specific Activity Copper-67

DOEpatents

Jamriska, Sr., David J.; Taylor, Wayne A.; Ott, Martin A.; Fowler, Malcolm; Heaton, Richard C.

2003-10-28

A process for the selective production and isolation of high specific activity Cu.sup.67 from proton-irradiated enriched Zn.sup.70 target comprises target fabrication, target irradiation with low energy (<25 MeV) protons, chemical separation of the Cu.sup.67 product from the target material and radioactive impurities of gallium, cobalt, iron, and stable aluminum via electrochemical methods or ion exchange using both anion and cation organic ion exchangers, chemical recovery of the enriched Zn.sup.70 target material, and fabrication of new targets for re-irradiation is disclosed.

Microchip electrophoresis with electrochemical detection for the determination of analytes in the dopamine metabolic pathway

PubMed Central

Saylor, Rachel A.; Reid, Erin A.; Lunte, Susan M.

2016-01-01

A method for the separation and detection of analytes in the dopamine metabolic pathway was developed using microchip electrophoresis with electrochemical detection. The microchip consisted of a 5 cm PDMS separation channel in a simple-t configuration. Analytes in the dopamine metabolic pathway were separated using a background electrolyte composed of 15 mM phosphate at pH 7.4, 15 mM SDS, and 2.5 mM boric acid. Two different microchip substrates using different electrode materials were compared for the analysis: a PDMS/PDMS device with a carbon fiber electrode and a PDMS/glass hybrid device with a pyrolyzed photoresist film carbon electrode. While the PDMS/PDMS device generated high separation efficiencies and good resolution, more reproducible migration times were obtained with the PDMS/glass hybrid device, making it a better choice for biological applications. Lastly, the optimized method was used to monitor L-DOPA metabolism in a rat brain slice. PMID:25958983

Fundamentals, achievements and challenges in the electrochemical sensing of pathogens.

PubMed

Monzó, Javier; Insua, Ignacio; Fernandez-Trillo, Francisco; Rodriguez, Paramaconi

2015-11-07

Electrochemical sensors are powerful tools widely used in industrial, environmental and medical applications. The versatility of electrochemical methods allows for the investigation of chemical composition in real time and in situ. Electrochemical detection of specific biological molecules is a powerful means for detecting disease-related markers. In the last 10 years, highly-sensitive and specific methods have been developed to detect waterborne and foodborne pathogens. In this review, we classify the different electrochemical techniques used for the qualitative and quantitative detection of pathogens. The robustness of electrochemical methods allows for accurate detection even in heterogeneous and impure samples. We present a fundamental description of the three major electrochemical sensing methods used in the detection of pathogens and the advantages and disadvantages of each of these methods. In each section, we highlight recent breakthroughs, including the utilisation of microfluidics, immunomagnetic separation and multiplexing for the detection of multiple pathogens in a single device. We also include recent studies describing new strategies for the design of future immunosensing systems and protocols. The high sensitivity and selectivity, together with the portability and the cost-effectiveness of the instrumentation, enhances the demand for further development in the electrochemical detection of microbes.

Electrochemical regeneration of phenol-saturated activated carbon - proposal of a reactor.

PubMed

Zanella, Odivan; Bilibio, Denise; Priamo, Wagner Luiz; Tessaro, Isabel Cristina; Féris, Liliana Amaral

2017-03-01

An electrochemical process was used to investigate the activated carbon regeneration efficiency (RE) saturated with aromatics. For this purpose, an electrochemical reactor was developed and the operational conditions of this equipment were investigated, which is applied in activated carbon regeneration process. The influence of regeneration parameters such as processing time, the current used, the polarity and the processing fluid (electrolyte) were studied. The performance of electrochemical regeneration was evaluated by adsorption tests, using phenol as adsorbate. The increase in current applied and the process time was found to enhance the RE. Another aspect that indicated a better reactor performance was the type of electrolyte used, showing best results for NaCl. The polarity showed the highest influence on the process, when the cathodic regeneration was more efficient. The electrochemical regeneration process developed in this study presented regeneration capacities greater than 100% when the best process conditions were used, showing that this form of regeneration for activated carbon saturated with aromatics is very promising.

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.

Simultaneous determination of hydroxylamine and phenol using a nanostructure-based electrochemical sensor.

PubMed

Moghaddam, Hadi Mahmoudi; Beitollahi, Hadi; Tajik, Somayeh; Malakootian, Mohammad; Maleh, Hassan Karimi

2014-11-01

The electrochemical oxidation of hydroxylamine on the surface of a carbon paste electrode modified with carbon nanotubes and 2,7-bis(ferrocenyl ethyl)fluoren-9-one is studied. The electrochemical response characteristics of the modified electrode toward hydroxylamine and phenol were investigated. The results showed an efficient catalytic activity of the electrode for the electro-oxidation of hydroxylamine, which leads to lowering its overpotential. The modified electrode exhibits an efficient electron-mediating behavior together with well-separated oxidation peaks for hydroxylamine and phenol. Also, the modified electrode was used for determination of hydroxylamine and phenol in some real samples.

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

Spacecraft nitrogen generation. [liquid hydrazine

NASA Technical Reports Server (NTRS)

Marshall, R. D.; Carlson, J. N.; Powell, J. D.; Kacholia, K. K.

1974-01-01

Two spacecraft nitrogen (N2) generation systems based on the catalytic dissociation of hydrazine (N2H4) were evaluated. In the first system, liquid N2H4 is catalytically dissociated to yield an N2 and hydrogen (H2) gas mixture. Separation of the N2/H2 gas mixture to yield N2 and a supply of H2 is accomplished using a polymer-electrochemical N2/H2 separator. In the second system, the N2/H2 gas mixture is separated in a two-stage palladium/silver (Pd/Ag) N2/H2 separator. The program culminated in the successful design, fabrication, and testing of a N2H4 catalytic dissociator, a polymer-electrochemical N2/H2 separator, and a two-stage Pd/Ag N2/H2 separator. The hardware developed was sized for an N2 delivery rate of 6.81 kg/d (15lb/day). Experimental results demonstrated that both spacecraft N2 generation systems are capable of producing 6.81 kg/d (15lb/day) of 99.9% pure N2 at a pressure greater than or equal to 1035 kN/m(2) (150 psia).

Method of forming components for a high-temperature secondary electrochemical cell

DOEpatents

Mrazek, Franklin C.; Battles, James E.

1983-01-01

A method of forming a component for a high-temperature secondary electrochemical cell having a positive electrode including a sulfide selected from the group consisting of iron sulfides, nickel sulfides, copper sulfides and cobalt sulfides, a negative electrode including an alloy of aluminum and an electrically insulating porous separator between said electrodes. The improvement comprises forming a slurry of solid particles dispersed in a liquid electrolyte such as the lithium chloride-potassium chloride eutetic, casting the slurry into a form having the shape of one of the components and smoothing the exposed surface of the slurry, cooling the cast slurry to form the solid component, and removing same. Electrodes and separators can be thus formed.

Conducting polymers: Synthesis and industrial applications

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

Gottesfeld, S.

1997-04-01

The Conducting Polymer project funded by the AIM Program has developed new methods for the synthesis of conducting polymers and evaluated new industrial applications for these materials which will result in significant reductions in energy usage or industrial waste. The applications specifically addressed during FY 1996 included two ongoing efforts on membranes for gas separation and on electrochemical capacitors and a third new application: electrochemical reactors (ECRs) based on polymeric electrolytes. As a gas separation membrane, conducting polymers offer high selectivity and the potential to chemically or electrically adapt the membrane for specific gas combinations. Potential energy savings in themore » US for this application are estimated at 1 to 3 quads/yr. As an active material in electrochemical capacitors, electronically conducting polymers have the potential of storing large amounts of electric energy in low cost materials. Potential energy savings estimated at 1 quad/yr would result from introduction of electrochemical capacitors as energy storage devices in power trains of electric and hybrid vehicles, once such vehicles reach 20% of the total transportation market in the US. In the chlor-alkali industry, electrochemical reactors based on polymer electrolyte membranes consume around 1 % of the total electric power in the US. A new activity, started in FY 1996, is devoted to energy efficient ECRs. In the case of the chlor-alkali industry, energy savings as high as 50% seem possible with the novel ECR technology demonstrated by the author in 1996.« less

Pore size engineering applied to starved electrochemical cells and batteries

NASA Technical Reports Server (NTRS)

Abbey, K. M.; Thaller, L. H.

1982-01-01

To maximize performance in starved, multiplate cells, the cell design should rely on techniques which widen the volume tolerance characteristics. These involve engineering capillary pressure differences between the components of an electrochemical cell and using these forces to promote redistribution of electrolyte to the desired optimum values. This can be implemented in practice by prescribing pore size distributions for porous back-up plates, reservoirs, and electrodes. In addition, electrolyte volume management can be controlled by incorporating different pore size distributions into the separator. In a nickel/hydrogen cell, the separator must contain pores similar in size to the small pores of both the nickel and hydrogen electrodes in order to maintain an optimum conductive path for the electrolyte. The pore size distributions of all components should overlap in such a way as to prevent drying of the separator and/or flooding of the hydrogen electrode.

I-NERI Annual Technical Progress Report 2007-004-K Development and Characterization of New High-Level Waste Forms for Achieving Waste Minimization from Pyroprocessing

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

S. Frank

The current method for the immobilization of fission products that accumulate in electrorefiner salt during the electrochemical processing of used metallic nuclear fuel is to encapsulate the electrorefiner salt in a glass-bonded sodalite ceramic waste form. This process was developed by Argonne National Laboratory in the USA and is currently performed at the Idaho National Laboratory for the treatment of Experimental Breeder Reactor-II (EBR-II) used fuel. This process utilizes a “once-through” option for the disposal of spent electrorefiner salt; where, after the treatment of the EBR-II fuel, the electrorefiner salt containing the active fission products will be disposed of inmore » the ceramic waste form (CWF). The CWF produced will have low fission product loading of approximately 2 to 5 weight percent due to the limited fuel inventory currently being processed. However; the design and implementation of advanced electrochemical processing facilities to treat used fuel would process much greater quantities fuel. With an advanced processing facility, it would be necessary to selectively remove fission products from the electrorefiner salt for salt recycle and to concentrate the fission products to reduce the volume of high-level waste from the treatment facility. The Korean Atomic Energy Research Institute and the Idaho National Laboratory have been collaborating on I-NERI research projects for a number of years to investigate both aspects of selective fission product separation from electrorefiner salt, and to develop advanced waste forms for the immobilization of the collected fission products. The first joint KAERI/INL I-NERI project titled: 2006-002-K, Separation of Fission Products from Molten LiCl-KCl Salt Used for Electrorefining of Metal Fuels, was successfully completed in 2009 by concentrating and isolating fission products from actual electrorefiner salt used for the treated used EBR-II fuel. Two separation methods were tested and from these tests were produced concentrated salt products that acted as the feed material for development of advanced waste forms investigated in this proposal. Accomplishments from the first year activities associated with this I-NERI project included the down selection of candidate waste forms to immobilize fission products separated from electrorefiner salt, and the design of equipment to fabricate actual waste forms in the Hot Fuels Examination Facility (HFEF) at the INL. Reported in this document are accomplishments from the second year (FY10) work performed at the INL, and includes the testing of waste form fabrication equipment, repeating the fission product precipitation experiment, and initial waste form fabrication efforts.« less

Process for electrochemically gasifying coal using electromagnetism

DOEpatents

Botts, Thomas E.; Powell, James R.

1987-01-01

A process for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution.

Bio-electrochemical characterization of air-cathode microbial fuel cells with microporous polyethylene/silica membrane as separator.

PubMed

Kircheva, Nina; Outin, Jonathan; Perrier, Gérard; Ramousse, Julien; Merlin, Gérard; Lyautey, Emilie

2015-12-01

The aim of this work was to study the behavior over time of a separator made of a low-cost and non-selective microporous polyethylene membrane (RhinoHide®) in an air-cathode microbial fuel cell with a reticulated vitreous carbon foam bioanode. Performances of the microporous polyethylene membrane (RhinoHide®) were compared with Nafion®-117 as a cationic exchange membrane. A non-parametric test (Mann-Whitney) done on the different sets of coulombic or energy efficiency data showed no significant difference between the two types of tested membrane (p<0.05). Volumetric power densities were ranging from 30 to 90 W·m(-3) of RVC foam for both membranes. Similar amounts of biomass were observed on both sides of the polyethylene membrane illustrating bacterial permeability of this type of separator. A monospecific denitrifying population on cathodic side of RhinoHide® membrane has been identified. Electrochemical impedance spectroscopy (EIS) was used at OCV conditions to characterize electrochemical behavior of MFCs by equivalent electrical circuit fitted on both Nyquist and Bode plots. Resistances and pseudo-capacitances from EIS analyses do not differ in such a way that the nature of the membrane could be considered as responsible. Copyright © 2015 Elsevier B.V. All rights reserved.

Facile electrochemical pretreatment of multiwalled carbon nanotube - Polydimethylsiloxane paste electrode for enhanced detection of dopamine and uric acid

NASA Astrophysics Data System (ADS)

Buenaventura, Angelo Gabriel E.; Yago, Allan Christopher C.

2018-05-01

A facile electrochemical pretreatment via anodization was done on Carbon Paste Electrodes (CPEs) composed of Multiwalled Carbon Nanotubes (MWCNTs) and Polydimethylsiloxane (PDMS) binder to produce `anodized' CPEs (ACPE). Cyclic Voltammetry (CV) technique was used to anodize the CPEs. The anodization step, performed in various solutions (0.2 M NaOH(aq), 0.06 M BR Buffer at pH 7.0, and 0.2 M HNO3(aq)), were found to enhance the electrochemical properties of the ACPEs compared to non-anodized CPE. Electrochemical Impedance Spectroscopy (EIS) measurements revealed a significantly lower charge transfer resistance (Rct) for the ACPEs (4.01-6.25 kΩ) as compared to CPE (25.9 kΩ). Comparison of the reversibility analysis for Fe(CN)63-/4- redox couple showed that the ACPEs have peak current ratio (Ia/Ic) at range of 0.97-1.10 while 1.92 for the CPE; this result indicated better electrochemical reversible behaviors for Fe(CN)63-/4- redox couple using the ACPEs. CV Anodization process was further optimized by varying solution and CV parameters (i.e. pH, composition, number of cycles, and potential range), and the resulting optimized ACPE was used for enhanced detection of Dopamine (DA) and Uric Acid (UA) in the presence of excess Ascorbic Acid (AA). Employing Differential Pulse Voltammetry technique, enhanced voltammetric signal for DA and significant peak separation between DA and UA was obtained. The anodic peak currents for the oxidation of DA and UA appeared at 0.263V and 0.414 V, respectively, and it was observed to be linearly increasing with increasing concentrations of biomolecules (25-100 µM). The detection limit was determined to be 3.86 µM for DA and 5.61 µM for UA. This study showed a quick and cost-effective pretreatment for CPEs based on MWCNT-PDMS composite which lead to significant enhancement on its electrochemical properties.

The evaluation of the pyrochemistry for the treatment of Gen IV nuclear fuels Inert matrix chlorination studies in the gas phase or molten chloride salts

NASA Astrophysics Data System (ADS)

Bourg, S.; Péron, F.; Lacquement, J.

2007-01-01

The structure of the fuels for the future Gen IV nuclear reactors will be totally different from those of PWR, especially for the GFR concept including a closed cycle. In these reactors, fissile materials (carbides or nitrides of actinides) should be surrounded by an inert matrix. In order to build a reprocessing process scheme, the behavior of the potential inert matrices (silicon carbide, titanium nitride, and zirconium carbide and nitride) was studied by hydro- and pyrometallurgy. This paper deals with the chlorination results at high temperature by pyrometallurgy. For the first time, the reactivity of the matrix towards chlorine gas was assessed in the gas phase. TiN, ZrN and ZrC are very reactive from 400 °C whereas it is necessary to be over 900 °C for SiC to be as fast. In molten chloride melts, the bubbling of chlorine gas is less efficient than in gas phase but it is possible to attack the matrices. Electrochemical methods were also used to dissolve the refractory materials, leading to promising results with TiN, ZrN and ZrC. The massive SiC samples used were not conductive enough to be studied and in this case specific SiC-coated carbon electrodes were used. The key point of these studies was to find a method to separate the matrix compounds from the fissile material in order to link the head to the core of the process (electrochemical separation or liquid-liquid reductive extraction in the case of a pyrochemical reprocessing).

Integration of Microchip Electrophoresis with Electrochemical Detection Using an Epoxy-Based Molding Method to Embed Multiple Electrode Materials

PubMed Central

Johnson, Alicia S.; Selimovic, Asmira; Martin, R. Scott

2012-01-01

This paper describes the use of epoxy-encapsulated electrodes to integrate microchip-based electrophoresis with electrochemical detection. Devices with various electrode combinations can easily be developed. This includes a palladium decoupler with a downstream working electrode material of either gold, mercury/gold, platinum, glassy carbon, or a carbon fiber bundle. Additional device components such as the platinum wires for the electrophoresis separation and the counter electrode for detection can also be integrated into the epoxy base. The effect of the decoupler configuration was studied in terms of the separation performance, detector noise, and the ability to analyze samples of a high ionic strength. The ability of both glassy carbon and carbon fiber bundle electrodes to analyze a complex mixture was demonstrated. It was also shown that a PDMS-based valving microchip can be used along with the epoxy embedded electrodes to integrate microdialysis sampling with microchip electrophoresis and electrochemical detection, with the microdialysis tubing also being embedded in the epoxy substrate. This approach enables one to vary the detection electrode material as desired in a manner where the electrodes can be polished and modified in a similar fashion to electrochemical flow cells used in liquid chromatography. PMID:22038707

Treatment of an azo dye effluent by peroxi-coagulation and its comparison to traditional electrochemical advanced processes.

PubMed

do Vale-Júnior, Edilson; da Silva, Djalma R; Fajardo, Ana S; Martínez-Huitle, Carlos A

2018-08-01

Peroxi-coagulation (PC) is an interesting new process that has not been widely studied in the literature. This work presents the application of this technology to treat an azo dye synthetic effluent, studying the effect of different parameters including initial pH, current density (j), initial dye concentration and supporting electrolyte. The two former variables significantly affected the colour removal of the wastewater, followed by the initial dye concentration and the kind of electrolyte, in a lesser extent. The optimum operating conditions achieved were initial pH of 3.0, j = 33.3 mA cm -2 , 100 mg L -1 of methyl orange (MO) and Na 2 SO 4 as supporting electrolyte. The performance of PC was also compared to other electrochemical advanced processes, under similar experimental conditions. Results indicate that the kinetic decay of the MO increases in the following order: electrocoagulation (EC) < electrochemical oxidation (EO) with electrogenerated H 2 O 2 < PC < electro-Fenton (EF). This behaviour is given to the high oxidant character of the homogenous OH radicals generated by EF and PC approaches. The EO process with production of H 2 O 2 (EO-H 2 O 2 ) is limited by mass transport and the EC, as a separation method, takes longer times to achieve similar removal results. Energy requirements about 0.06 kWh g COD -1 , 0.09 kWh g COD -1 , 0.7 kWh g COD -1 and 0.1 kWh g COD -1 were achieved for PC, EF, EO-H 2 O 2 and EC, respectively. Degradation intermediates were monitored and carboxylic acids were detected for PC and EF processes, being rapidly removed by the former technology. PC emerges as a promising and competitive alternative for wastewaters depollution, among other oxidative approaches. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

Yang, Sangmo; Paranthaman, Mariappan Parans; Noh, Tae Won

The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When themore » grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag +/Ag redox reaction to Ag +-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.« less

Multi-modular, tris(triphenylamine) zinc porphyrin-zinc phthalocyanine-fullerene conjugate as a broadband capturing, charge stabilizing, photosynthetic 'antenna-reaction center' mimic.

PubMed

Kc, Chandra B; Lim, Gary N; D'Souza, Francis

2015-04-21

A broadband capturing, charge stabilizing, photosynthetic antenna-reaction center model compound has been newly synthesized and characterized. The model compound is comprised of a zinc porphyrin covalently linked to three units of triphenylamine entities and a zinc phthalocyanine entity. The absorption and fluorescence spectra of zinc porphyrin complemented that of zinc phthalocyanine offering broadband coverage. Stepwise energy transfer from singlet excited triphenylamine to zinc porphyrin, and singlet excited zinc porphyrin to zinc phthalocyanine (kENT ∼ 10(11) s(-1)) was established from spectroscopic and time-resolved transient absorption techniques. Next, an electron acceptor, fullerene was introduced via metal-ligand axial coordination to both zinc porphyrin and zinc phthalocyanine centers, and they were characterized by spectroscopic and electrochemical techniques. An association constant of 4.9 × 10(4) M(-1) for phenylimidazole functionalized fullerene binding to zinc porphyrin, and 5.1 × 10(4) M(-1) for it binding to zinc phthalocyanine was obtained. An energy level diagram for the occurrence of different photochemical events within the multi-modular donor-acceptor conjugate was established from spectral and electrochemical data. Unlike the previous zinc porphyrin-zinc phthalocyanine-fullerene conjugates, the newly assembled donor-acceptor conjugate has been shown to undergo the much anticipated initial charge separation from singlet excited zinc porphyrin to the coordinated fullerene followed by a hole shift process to zinc phthalocyanine resulting in a long-lived charge separated state as revealed by femto- and nanosecond transient absorption spectroscopic techniques. The lifetime of the final charge separated state was about 100 ns.

STEP wastewater treatment: a solar thermal electrochemical process for pollutant oxidation.

PubMed

Wang, Baohui; Wu, Hongjun; Zhang, Guoxue; Licht, Stuart

2012-10-01

A solar thermal electrochemical production (STEP) pathway was established to utilize solar energy to drive useful chemical processes. In this paper, we use experimental chemistry for efficient STEP wastewater treatment, and suggest a theory based on the decreasing stability of organic pollutants (hydrocarbon oxidation potentials) with increasing temperature. Exemplified by the solar thermal electrochemical oxidation of phenol, the fundamental model and experimental system components of this process outline a general method for the oxidation of environmentally stable organic pollutants into carbon dioxide, which is easily removed. Using thermodynamic calculations we show a sharply decreasing phenol oxidation potential with increasing temperature. The experimental results demonstrate that this increased temperature can be supplied by solar thermal heating. In combination this drives electrochemical phenol removal with enhanced oxidation efficiency through (i) a thermodynamically driven decrease in the energy needed to fuel the process and (ii) improved kinetics to sustain high rates of phenol oxidation at low electrochemical overpotential. The STEP wastewater treatment process is synergistic in that it is performed with higher efficiency than either electrochemical or photovoltaic conversion process acting alone. STEP is a green, efficient, safe, and sustainable process for organic wastewater treatment driven solely by solar energy. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemically controlled iron isotope fractionation

NASA Astrophysics Data System (ADS)

Black, Jay R.; Young, Edward D.; Kavner, Abby

2010-02-01

Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

The Effects of Voltage and Concentration of Sodium Bicarbonate on Electrochemical Synthesis of Ethanol from Carbon Dioxide Using Brass as Cathode

NASA Astrophysics Data System (ADS)

Ramadan, Septian; Fariduddin, Sholah; Rizki Aminudin, Afianti; Kurnia Hayatri, Antisa; Riyanto

2017-11-01

The effects of voltage and concentration of sodium bicarbonate were investigated to determine the optimum conditions of the electrochemical synthesis process to convert carbon dioxide into ethanol. The conversion process is carried out using a sodium bicarbonate electrolyte solution in an electrochemical synthesis reactor equipped with a cathode and anode. As the cathode was used brass, while as the anode carbon was utilized. Sample of the electrochemical synthesis process was analyzed by gas chromatography to determine the content of the compounds produced. The optimum electrochemical synthesis conditions to convert carbon dioxide into ethanol are voltage and concentration of sodium bicarbonate are 3 volts and 0.4 M with ethanol concentration of 1.33%.

Nano-Electrochemistry and Nano-Electrografting with an Original Combined AFM-SECM

PubMed Central

Ghorbal, Achraf; Grisotto, Federico; Charlier, Julienne; Palacin, Serge; Goyer, Cédric; Demaille, Christophe; Ben Brahim, Ammar

2013-01-01

This study demonstrates the advantages of the combination between atomic force microscopy and scanning electrochemical microscopy. The combined technique can perform nano-electrochemical measurements onto agarose surface and nano-electrografting of non-conducting polymers onto conducting surfaces. This work was achieved by manufacturing an original Atomic Force Microscopy-Scanning ElectroChemical Microscopy (AFM-SECM) electrode. The capabilities of the AFM-SECM-electrode were tested with the nano-electrografting of vinylic monomers initiated by aryl diazonium salts. Nano-electrochemical and technical processes were thoroughly described, so as to allow experiments reproducing. A plausible explanation of chemical and electrochemical mechanisms, leading to the nano-grafting process, was reported. This combined technique represents the first step towards improved nano-processes for the nano-electrografting. PMID:28348337

Gas permeable electrode for electrochemical system

DOEpatents

Ludwig, Frank A.; Townsend, Carl W.

1989-01-01

An electrode apparatus adapted for use in electrochemical systems having an anode compartment and a cathode compartment in which gas and ions are produced and consumed in the compartments during generation of electrical current. The electrode apparatus includes a membrane for separating the anode compartment from the cathode compartment wherein the membrane is permeable to both ions and gas. The cathode and anode for the assembly are provided on opposite sides of the membrane. During use of the membrane-electrode apparatus in electrochemical cells, the gas and ions generated at the cathode or anode migrate through the membrane to provide efficient transfer of gas and ions between the anode and cathode compartments.

The effect of the carbon nanotube buffer layer on the performance of a Li metal battery.

PubMed

Zhang, Ding; Zhou, Yi; Liu, Changhong; Fan, Shoushan

2016-06-07

Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery.

Electrochemistry coupled to (LC-)MS for the simulation of oxidative biotransformation reactions of PAHs.

PubMed

Wigger, Tina; Seidel, Albrecht; Karst, Uwe

2017-06-01

Electrochemistry coupled to liquid chromatography and mass spectrometry was used for simulating the biological and environmental fate of polycyclic aromatic hydrocarbons (PAHs) as well as for studying the PAH degradation behavior during electrochemical remediation. Pyrene and benzo[a]pyrene were selected as model compounds and oxidized within an electrochemical thin-layer cell equipped with boron-doped diamond electrode. At potentials of 1.2 and 1.6 V vs. Pd/H 2 , quinones were found to be the major oxidation products for both investigated PAHs. These quinones belong to a large group of PAH derivatives referred to as oxygenated PAHs, which have gained increasing attention in recent years due to their high abundance in the environment and their significant toxicity. Separation of oxidation products allowed the identification of two pyrene quinone and three benzo[a]pyrene quinone isomers, all of which are known to be formed via photooxidation and during mammalian metabolism. The good correlation between electrochemically generated PAH quinones and those formed in natural processes was also confirmed by UV irradiation experiments and microsomal incubations. At potentials higher than 2.0 V, further degradation of the initial oxidation products was observed which highlights the capability of electrochemistry to be used as remediation technique. Copyright © 2017 Elsevier Ltd. All rights reserved.

POM-assisted electrochemical delignification and bleaching of chemical pulp

Treesearch

Helene Laroche; Mohini Sain; Carl Houtman; Claude Daneault

2001-01-01

A polyoxometalate-catalyzed electrochemical process has shown good selectivity in delignifying pulp. This breakthrough in redox catalysis shows promise for the development of a new environmentally benign technology for pulp bleaching. The electrochemical process, applied with a mildly alkaline electrolyte solution containing trace amounts of a vanadium-based...

The Effect of Voltage Charging on the Transport Properties of Gold Nanotube Membranes.

PubMed

Experton, Juliette; Martin, Charles R

2018-05-01

Porous membranes are used in chemical separations and in many electrochemical processes and devices. Research on the transport properties of a unique class of porous membranes that contain monodisperse gold nanotubes traversing the entire membrane thickness is reviewed here. These gold nanotubes can act as conduits for ionic and molecular transports through the membrane. Because the tubes are electronically conductive, they can be electrochemically charged by applying a voltage to the membrane. How this "voltage charging" affects the transport properties of gold nanotube membranes is the subject of this Review. Experiments showing that voltage charging can be used to reversibly switch the membrane between ideally cation- and anion-transporting states are reviewed. Voltage charging can also be used to enhance the ionic conductivity of gold nanotube membranes. Finally, voltage charging to accomplish electroporation of living bacteria as they pass through gold nanotube membranes is reviewed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of the chemical and electrochemical coal cleaning process

NASA Astrophysics Data System (ADS)

Basilio, C. I.; Yoon, Roe-Hoan

The continuous testing of the Chemical and Electrochemical Coal Cleaning (CECC) was completed successfully using Middle Wyodak and Elkhorn No. 3 coal samples. The CECC unit was run under the optimum conditions established for these coal samples. For the Middle Wyodak coal, the ash content was reduced from 6.96 percent to as low 1.61 percent, corresponding to an ash rejection (by weight) of about 83 percent. The ash and sulfur contents of the Elkhorn No. 3 coal were reduced to as low as 1.8 percent and 0.9 percent. The average ash and sulfur rejections were calculated to be around 84 percent and 47 percent. The CECC continuous unit was used to treat -325 mesh Elkhorn No. 3 coal samples and gave ash and sulfur rejection values of as high as 77 percent and 66 percent. In these test, the clean -325 mesh coal particles were separated from the liberated mineral matter through microbubble column flotation, instead of wet-screening.

Characterization of physiochemical properties of polymeric and electrochemical materials for aerospace flight

NASA Technical Reports Server (NTRS)

Rock, M.; Kunigahalli, V.; Khan, S.; Mcnair, A.

1984-01-01

Nickel-cadmium rechargeable batteries are a vital and reliable energy storage source for aerospace applications. As the demand for longer life and more reliable space batteries increases, the understanding and solving of cell aging factors and mechanisms become essential. Over the years, many cell designs and manufacturing process changes have been developed and implemented. Cells fabricated with various design features were life cycled in a simulated low-Earth orbit regime. Following the test program, a comprehensive electrochemical analysis of cell components was undertaken to study cell degradation mechanisms. Discharge voltage degradation or voltage plateau has been observed during orbit cycling, but, its cause and explanation have been the subject of much discussion. A Hg/HgO reference electrode was used to monitor the reference versus each electrode potential during the discharge of a cycled cell. The results indicate that the negative electrode was responsible for the voltage plateau. Cell analysis revealed large crystals of cadmium hydroxide on the surface of the negative electrode and throughout the separator.

An electro-amalgamation approach to isolate no-carrier-added 177Lu from neutron irradiated Yb for biomedical applications.

PubMed

Chakravarty, Rubel; Das, Tapas; Dash, Ashutosh; Venkatesh, Meera

2010-10-01

A novel two-step separation process for the production of no-carrier-added (NCA) (177)Lu from neutron irradiated Yb target through an electrochemical pathway employing mercury-pool cathode has been developed. A two-cycle electrolysis procedure was adopted for separation of (177)Lu from (177)Lu/Yb mixture in lithium citrate medium. The influence of different experimental parameters on the separation process was investigated and optimized for the quantitative deposition of Yb in presence of (177)Lu. The first electrolysis was performed for 50 min in the (177)Lu/Yb feed solution at pH 6 applying a potential of 8 V using platinum electrode as anode and mercury as the cathode. The second electrolysis was performed under the same conditions using fresh electrodes. The radionuclidic and chemical purity of (177)Lu was determined by using gamma ray spectrometry and atomic absorption spectrometry. The suitability of (177)Lu for biomedical applications was ascertained by labeling 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid D-Phe(1)-Tyr(3)-octreotate(DOTA-TATE) with (177)Lu. This process could provide NCA (177)Lu with >99.99% radionuclidic purity and an overall separation yield of ∼99% was achieved within 3-4 h. The Hg content in the product was determined to be <1 ppm. Radiolabeling yield of >98% was obtained with DOTA-TATE under the optimized reaction conditions. An efficient strategy for the separation of NCA (177)Lu, suitable for biomedical applications, has been developed. Copyright © 2010 Elsevier Inc. All rights reserved.

Process for electrochemically gasifying coal

DOEpatents

Botts, T.E.; Powell, J.R.

1985-10-25

A process is claimed for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution. 7 figs.

Determination of morphine and codeine in urine using poly(dimethylsiloxane) microchip electrophoresis with electrochemical detection.

PubMed

Zhang, Qian-Li; Xu, Jing-Juan; Li, Xiang-Yun; Lian, Hong-Zhen; Chen, Hong-Yuan

2007-01-04

In this paper, a poly(dimethylsiloxane) (PDMS) microchip with electrochemical (EC) detection was developed for rapid separation and detection of morphine and codeine. It was found that morphine and codeine were well separated within 140 s in phosphate buffer solution (PBS) (pH 6.6, 40 mM)-beta-cyclodextrin (beta-CD) (20 mM)-acetonitrile (30%, v/v). The detection limit was 0.2 microM for morphine and 1 microM for codeine. The protocol was successfully applied to monitoring the amount of morphine and codeine in human urine. Compared with the conventional methods, the presented method had many advantages such as lower instrument cost, less reagent consumption and shorter analysis time.

Electrochemical cell design

DOEpatents

Arntzen, John D.

1978-01-01

An electrochemical cell includes two outer electrodes and a central electrode of opposite polarity, all nested within a housing having two symmetrical halves which together form an offset configuration. The outer electrodes are nested within raised portions within the side walls of each housing half while the central electrode sealingly engages the perimetric margins of the side-wall internal surfaces. Suitable interelectrode separators and electrical insulating material electrically isolate the central electrode from the housing and the outer electrodes. The outer electrodes are electrically connected to the internal surfaces of the cell housing to provide current collection. The nested structure minimizes void volume that would otherwise be filled with gas or heavy electrolyte and also provides perimetric edge surfaces for sealing and supporting at the outer margins of frangible interelectrode separator layers.

Method of forming components for a high-temperature secondary electrochemical cell

DOEpatents

Mrazek, F.C.; Battles, J.E.

1981-05-22

A method of forming a component for a high-temperature secondary electrochemical cell having a positive electrode including a sulfide selected from the group consisting of iron sulfides, nickel sulfides, copper sulfides and cobalt sulfides, a negative electrode including an alloy of aluminum and an electrically insulating porous separator between said electrodes is described. The improvement comprises forming a slurry of solid particles dispersed in a liquid electrolyte such as the lithium chloride-potassium chloride eutectic, casting the slurry into a form having the shape of one of the components and smoothing the exposed surface of the slurry, cooling the cast slurry to form the solid component, and removing same. Electrodes and separators can be thus formed.

Non-Faradaic electrochemical promotion of catalytic methane reforming for methanol production

DOEpatents

Fan, Qinbai

2016-11-22

A method of converting methane to methanol at low temperatures utilizes a reactor including an anode, a cathode, a membrane separator between the anode and cathode, a metal oxide catalyst at the anode and a hydrogen recovery catalyst at the cathode. The method can convert methane to methanol at as rate exceeding the theoretical Faradaic rate due to the contribution of an electrochemical reaction occurring in tandem with a Faradaic reaction.

Electrochemical cell

DOEpatents

Redey, Laszlo I.; Vissers, Donald R.; Prakash, Jai

1994-01-01

An electrochemical cell having an alkali metal negative electrode such as sodium and a positive electrode including Ni or transition metals, separated by a .beta." alumina electrolyte and NaAlCl.sub.4 or other compatible material. Various concentrations of a bromine, iodine and/or sulfur containing additive and pore formers are disclosed, which enhance cell capacity and power. The pore formers may be the ammonium salts of carbonic acid or a weak organic acid or oxamide or methylcellulose.

Electrochemical advanced oxidation processes: today and tomorrow. A review.

PubMed

Sirés, Ignasi; Brillas, Enric; Oturan, Mehmet A; Rodrigo, Manuel A; Panizza, Marco

2014-01-01

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical ((•)OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which (•)OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which (•)OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.

Quantum modeling of ultrafast photoinduced charge separation

NASA Astrophysics Data System (ADS)

Rozzi, Carlo Andrea; Troiani, Filippo; Tavernelli, Ivano

2018-01-01

Phenomena involving electron transfer are ubiquitous in nature, photosynthesis and enzymes or protein activity being prominent examples. Their deep understanding thus represents a mandatory scientific goal. Moreover, controlling the separation of photogenerated charges is a crucial prerequisite in many applicative contexts, including quantum electronics, photo-electrochemical water splitting, photocatalytic dye degradation, and energy conversion. In particular, photoinduced charge separation is the pivotal step driving the storage of sun light into electrical or chemical energy. If properly mastered, these processes may also allow us to achieve a better command of information storage at the nanoscale, as required for the development of molecular electronics, optical switching, or quantum technologies, amongst others. In this Topical Review we survey recent progress in the understanding of ultrafast charge separation from photoexcited states. We report the state-of-the-art of the observation and theoretical description of charge separation phenomena in the ultrafast regime mainly focusing on molecular- and nano-sized solar energy conversion systems. In particular, we examine different proposed mechanisms driving ultrafast charge dynamics, with particular regard to the role of quantum coherence and electron-nuclear coupling, and link experimental observations to theoretical approaches based either on model Hamiltonians or on first principles simulations.

Ultrastrong Polyoxyzole Nanofiber Membranes for Dendrite-Proof and Heat-Resistant Battery Separators.

PubMed

Hao, Xiaoming; Zhu, Jian; Jiang, Xiong; Wu, Haitao; Qiao, Jinshuo; Sun, Wang; Wang, Zhenhua; Sun, Kening

2016-05-11

Polymeric nanomaterials emerge as key building blocks for engineering materials in a variety of applications. In particular, the high modulus polymeric nanofibers are suitable to prepare flexible yet strong membrane separators to prevent the growth and penetration of lithium dendrites for safe and reliable high energy lithium metal-based batteries. High ionic conductance, scalability, and low cost are other required attributes of the separator important for practical implementations. Available materials so far are difficult to comply with such stringent criteria. Here, we demonstrate a high-yield exfoliation of ultrastrong poly(p-phenylene benzobisoxazole) nanofibers from the Zylon microfibers. A highly scalable blade casting process is used to assemble these nanofibers into nanoporous membranes. These membranes possess ultimate strengths of 525 MPa, Young's moduli of 20 GPa, thermal stability up to 600 °C, and impressively low ionic resistance, enabling their use as dendrite-suppressing membrane separators in electrochemical cells. With such high-performance separators, reliable lithium-metal based batteries operated at 150 °C are also demonstrated. Those polyoxyzole nanofibers would enrich the existing library of strong nanomaterials and serve as a promising material for large-scale and cost-effective safe energy storage.

Fossil fuel combined cycle power system

DOEpatents

Labinov, Solomon Davidovich; Armstrong, Timothy Robert; Judkins, Roddie Reagan

2006-10-10

A system for converting fuel energy to electricity includes a reformer for converting a higher molecular weight gas into at least one lower molecular weight gas, at least one turbine to produce electricity from expansion of at least one of the lower molecular weight gases, and at least one fuel cell. The system can further include at least one separation device for substantially dividing the lower molecular weight gases into at least two gas streams prior to the electrochemical oxidization step. A nuclear reactor can be used to supply at least a portion of the heat the required for the chemical conversion process.

Pulse electrochemical meso/micro/nano ultraprecision machining technology.

PubMed

Lee, Jeong Min; Kim, Young Bin; Park, Jeong Woo

2013-11-01

This study demonstrated meso/micro/nano-ultraprecision machining through electrochemical reactions using intermittent DC pulses. The experiment focused on two machining methods: (1) pulse electrochemical polishing (PECP) of stainless steel, and (2) pulse electrochemical nano-patterning (PECNP) on a silicon (Si) surface, using atomic force microscopy (AFM) for fabrication. The dissolution reaction at the stainless steel surface following PECP produced a very clean, smooth workpiece. The advantages of the PECP process included improvements in corrosion resistance, deburring of the sample surface, and removal of hydrogen from the stainless steel surface as verified by time-of-flight secondary-ion mass spectrometry (TOF-SIMS). In PECNP, the electrochemical reaction generated within water molecules produced nanoscale oxide textures on a Si surface. Scanning probe microscopy (SPM) was used to evaluate nanoscale-pattern processing on a Si wafer surface produced by AFM-PECNP For both processes using pulse electrochemical reactions, three-dimensional (3-D) measurements and AFM were used to investigate the changes on the machined surfaces. Preliminary results indicated the potential for advancing surface polishing techniques and localized micro/nano-texturing technology using PECP and PECNP processes.

A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

NASA Technical Reports Server (NTRS)

Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

1980-01-01

The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

Stick slip, charge separation and decay

USGS Publications Warehouse

Lockner, D.A.; Byerlee, J.D.; Kuksenko, V.S.; Ponomarev, A.V.

1986-01-01

Measurements of charge separation in rock during stable and unstable deformation give unexpectedly large decay times of 50 sec. Time-domain induced polarization experiments on wet and dry rocks give similar decay times and suggest that the same decay mechanisms operate in the induced polarization response as in the relaxation of charge generated by mechanical deformation. These large decay times are attributed to electrochemical processes in the rocks, and they require low-frequency relative permittivity to be very large, in excess of 105. One consequence of large permittivity, and therefore long decay times, is that a significant portion of any electrical charge generated during an earthquake can persist for tens or hundreds of seconds. As a result, electrical disturbances associated with earthquakes should be observable for these lengths of time rather than for the milliseconds previously suggested. ?? 1986 Birka??user Verlag.

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.

Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid

PubMed Central

Zhao, Zongya; Zhang, Mingming; Chen, Xiang; Li, Youjun; Wang, Jue

2015-01-01

In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO), HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR) possessed the highest electrocatalytic activity toward dopamine (DA). As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA) and uric acid (UA) using the differential pulse voltammetry (DPV) technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3). The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples. PMID:26184200

Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid.

PubMed

Zhao, Zongya; Zhang, Mingming; Chen, Xiang; Li, Youjun; Wang, Jue

2015-07-09

In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO), HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR) possessed the highest electrocatalytic activity toward dopamine (DA). As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA) and uric acid (UA) using the differential pulse voltammetry (DPV) technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3). The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples.

Advances toward industrialization of novel molten salt electrochemical processes.

PubMed

Ito, Yasuhiko; Nishikiori, Tokujiro; Tsujimura, Hiroyuki

2016-08-15

We have invented various novel molten salt electrochemical processes, that can be put to practical use in the fields of energy and materials. These processes are promising from both technological and commercial viewpoints, and they are currently under development for industrial application. To showcase current developments in work toward industrialization, we focus here on three of these processes: (1) electrolytic synthesis of ammonia from water and nitrogen under atmospheric pressure, (2) electrochemical formation of carbon film, and (3) plasma-induced discharge electrolysis to produce nanoparticles.

Heat transfer enhancement in a lithium-ion cell through improved material-level thermal transport

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

Vishwakarma, Vivek; Waghela, Chirag; Wei, Zi

2016-09-25

We report that while Li-ion cells offer excellent electrochemical performance for several applications including electric vehicles, they also exhibit poor thermal transport characteristics, resulting in reduced performance, overheating and thermal runaway. Inadequate heat removal from Li-ion cells originates from poor thermal conductivity within the cell. This paper identifies the rate-limiting material-level process that dominates overall thermal conduction in a Li-ion cell. Results indicate that thermal characteristics of a Li-ion cell are largely dominated by heat transfer across the cathode-separator interface rather than heat transfer through the materials themselves. This interfacial thermal resistance contributes around 88% of total thermal resistance inmore » the cell. Measured value of interfacial resistance is close to that obtained from theoretical models that account for weak adhesion and large acoustic mismatch between cathode and separator. Further, to address this problem, an amine-based chemical bridging of the interface is carried out. This is shown to result in in four-times lower interfacial thermal resistance without deterioration in electrochemical performance, thereby increasing effective thermal conductivity by three-fold. This improvement is expected to reduce peak temperature rise during operation by 60%. Finally, by identifying and addressing the material-level root cause of poor thermal transport in Li-ion cells, this work may contribute towards improved thermal performance of Li-ion cells.« less

Facile preparation of ion-imprinted composite film for selective electrochemical removal of nickel(II) ions.

PubMed

Du, Xiao; Zhang, Hao; Hao, Xiaogang; Guan, Guoqing; Abudula, Abuliti

2014-06-25

A facile unipolar pulse electropolymerization (UPEP) technique is successfully applied for the preparation of ion-imprinted composite film composed of ferricyanide-embedded conductive polypyrrole (FCN/PPy) for the selective electrochemical removal of heavy metal ions from wastewater. The imprinted heavy metal ions are found to be easily removed in situ from the growing film only by tactfully applying potential oscillation due to the unstable coordination of FCN to the imprinted ions. The obtained Ni(2+) ion-imprinted FCN/PPy composite film shows fast uptake/release ability for the removal of Ni(2+) ions from aqueous solution, and the adsorption equilibrium time is less than 50 s. The ion exchange capacity reaches 1.298 mmol g(-1) and retains 93.5% of its initial value even after 1000 uptake/release cycles. Separation factors of 6.3, 5.6, and 6.2 for Ni(2+)/Ca(2+), Ni(2+)/K(+), and Ni(2+)/Na(+), respectively, are obtained. These characteristics are attributed to the high identification capability of the ion-imprinted composite film for the target ions and the dual driving forces resulting from both PPy and FCN during the redox process. It is expected that the present method can be used for simple preparation of other ion-imprinted composite films for the separation and recovery of target heavy metal ions as well.

Photo-electrochemical properties of graphene wrapped hierarchically branched nanostructures obtained through hydrothermally transformed TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Rambabu, Y.; Jaiswal, Manu; Roy, Somnath C.

2017-10-01

Hierarchically structured nanomaterials play an important role in both light absorption and separation of photo-generated charges. In the present study, hierarchically branched TiO2 nanostructures (HB-MLNTs) are obtained through hydrothermal transformation of electrochemically anodized TiO2 multi-leg nanotubes (MLNT) arrays. Photo-anodes based on HB-MLNTs demonstrated 5 fold increase in applied bias to photo-conversion efficiency (%ABPE) over that of TiO2 MLNTs without branches. Further, such nanostructures are wrapped with reduced graphene oxide (rGO) films to enhance the charge separation, which resulted in ∼6.5 times enhancement in %ABPE over that of bare MLNTs. We estimated charge transport (η tr) and charge transfer (η ct) efficiencies by analyzing the photo-current data. The ultra-fine nano branches grown on the MLNTs are effective in increasing light absorption through multiple scattering and improving charge transport/transfer efficiencies by enlarging semiconductor/electrolyte interface area. The charge transfer resistance, interfacial capacitance and electron decay time have been estimated through electrochemical impedance measurements which correlate with the results obtained from photocurrent measurements.

Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

PubMed

Ordeig, Olga; Banks, Craig E; Davies, Trevor J; del Campo, F Javier; Muñoz, Francesc Xavier; Compton, Richard G

2006-05-01

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.

Problems, pitfalls and probes: Welcome to the jungle of electrochemical noise technology

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

Edgemon, G.L.

1998-02-19

The rise in electrochemical noise (EN) as a corrosion monitoring technique has resulted in unique problems associated with the field application of this method. Many issues relate to the design of the EN probe electrodes. The ability of an electrochemical noise monitoring system to identify and discriminate between localized corrosion mechanisms is related primarily to the capability of the probe to separate the corrosion cell anode from the corresponding cathode. Effectiveness of this separation is largely determined by the details of and the proper design of the probe that is in the environment of interest. No single probe design ormore » geometry can be effectively use in every situation to monitor all types of corrosion. In this paper the authors focus on a case study and probe development history related to monitoring corrosion in an extremely hostile environment using EN. While the ultimate application of EN was and continues to be successful, the case study shows that patience and persistence was necessary to meet and properly implement the monitoring program. Other possible source of problems and frustration with implementing EN are also discussed.« less

Inert gas rejection device for zinc-halogen battery systems

DOEpatents

Hammond, Michael J.; Arendell, Mark W.

1981-01-01

An electrolytic cell for separating chlorine gas from other (foreign) gases, having an anode, a cathode assembly, an aqueous electrolyte, a housing, and a constant voltage power supply. The cathode assembly is generally comprised of a dense graphite electrode having a winding channel formed in the face opposing the anode, a gas impermeable (but liquid permeable) membrane sealed into the side of the cathode electrode over the channel, and a packing of graphite particles contained in the channel of the cathode electrode. The housing separates and parallelly aligns the anode and cathode assembly, and provides a hermetic seal for the cell. In operation, a stream of chlorine and foreign gases enters the cell at the beginning of the cathode electrode channel. The chlorine gas is dissolved into the electrolyte and electrochemically reduced into chloride ions. The chloride ions disfuse through the gas impermeable membrane, and are electrochemically oxidized at the anode into purified chlorine gas. The foreign gases do not participate in the above electrochemical reactions, and are vented from the cell at the end of the cathode electrode channel.

Enhanced Microchip Electrophoresis Separations Combined with Electrochemical Detection Utilizing a Capillary Embedded in Polystyrene.

PubMed

Mehl, Benjamin T; Martin, R Scott

2018-01-07

The ability to use microchip-based electrophoresis for fast, high-throughput separations provides researchers with a tool for close-to real time analysis of biological systems. While PDMS-based electrophoresis devices are popular, the separation efficiency is often an issue due to the hydrophobic nature of PDMS. In this study, a hybrid microfluidic capillary device was fabricated to utilize the positive features of PDMS along with the electrophoretic performance of fused silica. A capillary loop was embedded in a polystyrene base that can be coupled with PDMS microchannels at minimal dead volume interconnects. A method for cleaning out the capillaries after a wet-polishing step was devised through the use of 3D printed syringe attachment. By comparing the separation efficiency of fluorescein and CBI-glycine with both a PDMS-based serpentine device and the embedded capillary loop device, it was shown that the embedded capillary loop device maintained higher theoretical plates for both analytes. A Pd decoupler with a carbon or Pt detection electrode were embedded along with the loop allowing integration of the electrophoretic separation with electrochemical detection. A series of catecholamines were separated to show the ability to resolve similar analytes and detect redox active species. The release of dopamine and norepinephrine from PC 12 cells was also analyzed showing the compatibility of these improved microchip separations with high ionic cell buffers associated with cell culture.

Electric field effects on current–voltage relationships in microfluidic channels presenting multiple working electrodes in the weak-coupling limit

DOE PAGES

Contento, Nicholas M.; Bohn, Paul W.

2014-05-23

While electrochemical methods are well suited for lab-on-a-chip applications, reliably coupling multiple, electrode-controlled processes in a single microfluidic channel remains a considerable challenge, because the electric fields driving electrokinetic flow make it difficult to establish a precisely known potential at the working electrode(s). The challenge of coupling electrochemical detection with microchip electrophoresis is well known; however, the problem is general, arising in other multielectrode arrangements with applications in enhanced detection and chemical processing. Here, we study the effects of induced electric fields on voltammetric behavior in a microchannel containing multiple in-channel electrodes, using a Fe(CN) 6 3/4- model system. Whenmore » an electric field is induced by applying a cathodic potential at one inchannel electrode, the half-wave potential (E 1/2) for the oxidation of ferrocyanide at an adjacent electrode shifts to more negative potentials. The E 1/2 value depends linearly on the electric field current at a separate in-channel electrode. The observed shift in E 1/2 is quantitatively described by a model, which accounts for the change in solution potential caused by the iR drop along the length of the microchannel. The model, which reliably captures changes in electrode location and solution conductivity, apportions the electric field potential between iR drop and electrochemical potential components, enabling the study of microchannel electric field magnitudes at low applied potentials. In the system studied, the iR component of the electric field potential increases exponentially with applied current before reaching an asymptotic value near 80 % of the total applied potential. The methods described will aid in the development and interpretation of future microchip electrochemistry methods, particularly those that benefit from the coupling of electrokinetic and electrochemical phenomena at low voltages.« less

Biochemical capacitance of Geobacter sulfurreducens biofilms.

PubMed

Bueno, Paulo R; Schrott, Germán D; Bonanni, Pablo S; Simison, Silvia N; Busalmen, Juan P

2015-08-10

An electrical model able to decouple the electron pathway from microbial cell machinery impedance terms is introduced. In this context, capacitance characteristics of the biofilm are clearly resolved. In other words, the model allows separating, according to the advantage of frequency and spectroscopic response approach, the different terms controlling the performance of the microbial biofilm respiratory process and thus the directly related electricity production process. The model can be accurately fitted to voltammetry measurements obtained under steady-state conditions and also to biofilm discharge amperometric measurements. The implications of biological aspects of the electrochemical or redox capacitance are discussed theoretically in the context of current knowledge with regard to structure and physiological activity of microbial Geobacter biofilms. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical ion transfer mediated by a lipophilic Os(ii)/Os(iii) dinonyl bipyridyl probe incorporated in thin film membranes.

PubMed

Jansod, Sutida; Wang, Lu; Cuartero, Maria; Bakker, Eric

2017-09-28

A new lipophilic dinonyl bipyridyl Os(ii)/Os(iii) complex successfully mediates ion transfer processes across voltammetric thin membranes. An added lipophilic cation-exchanger may impose voltammetric anion or cation transfer waves of Gaussian shape that are reversible and repeatable. The peak potential is found to shift with the ion concentration in agreement with the Nernst equation. The addition of tridodecylmethylammonium nitrate to the polymeric film dramatically reduces the peak separation from 240 mV to 65 mV, and the peak width to a near-theoretical value of 85 mV, which agrees with a surface confined process. It is suggested that the cationic additive serves as a phase transfer catalyst.

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.

Simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid based on graphene anchored with Pd-Pt nanoparticles.

PubMed

Yan, Jun; Liu, Shi; Zhang, Zhenqin; He, Guangwu; Zhou, Ping; Liang, Haiying; Tian, Lulu; Zhou, Xuemin; Jiang, Huijun

2013-11-01

Pd-Pt bimetallic nanoparticles anchored on functionalized reduced graphene oxide (RGO) nanomaterials were synthesized via a one-step in situ reduction process, in which Pt and Pd ions were first attached to poly(diallyldimethylammonium chloride) (PDDA) functionalized graphene oxide (GO) sheets, and then the encased metal ions and GO were subjected to simultaneous reduction by ethylene glycol. The as-prepared Pd3Pt1/PDDA-RGO nanocomposites were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and electrochemical methods. In addition, an electrochemical sensor based on the graphene nanocomposites was fabricated for the simultaneous detection of ascorbic acid (AA), dopamine (DA) and uric acid (UA) in their ternary mixture. Three well-separated voltammetric peaks along with remarkable increasing electro-oxidation currents were obtained in differential pulse voltammetry (DPV) measurements. Under the optimized conditions, there were linear relationships between the peak currents and the concentrations in the range of 40-1200 μM for AA, 4-200 μM for DA and 4-400 μM for UA, with the limit of detection (LOD) (based on S/N=3) of 0.61, 0.04 and 0.10 μM for AA, DA and UA, respectively. This improved electrochemical performance can be attributed to the synergistic effect of metallic nanoparticles and RGO and the combination of the bimetallic nanoparticles. Furthermore, the practical electroanalytical utility of the sensor was demonstrated by the determination of AA, DA and together with UA in human urine and blood serum samples with satisfactory results. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Electrochemical power-producing cell. [Li/Se

DOEpatents

Cairns, E.J.; Chilenskas, A.A.; Steunenberg, R.K.; Shimotake, H.

1972-05-30

An electrochemical power-producing cell including a molten lithium metal anode, a molten selenium metal cathode, a paste electrolyte separating the anode from the cathode, an anode current collector, and a single layer of niobium expanded metal formed in corrugated shape as cathode current collector is described. In addition, means are provided for sealing the anode and the cathode from loss of lithium and selenium, respectively, and an insulator is provided between the anode housing and the paste electrolyte disk.

Electrochemical cell

DOEpatents

Redey, L.I.; Vissers, D.R.; Prakash, J.

1994-08-23

An electrochemical cell is described having an alkali metal negative electrode such as sodium and a positive electrode including Ni or transition metals, separated by a [beta] alumina electrolyte and NaAlCl[sub 4] or other compatible material. Various concentrations of a bromine, iodine and/or sulfur containing additive and pore formers are disclosed, which enhance cell capacity and power. The pore formers may be the ammonium salts of carbonic acid or a weak organic acid or oxamide or methylcellulose. 6 figs.

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.

Phase-Separated Polyaniline/Graphene Composite Electrodes for High-Rate Electrochemical Supercapacitors.

PubMed

Wu, Jifeng; Zhang, Qin'e; Zhou, An'an; Huang, Zhifeng; Bai, Hua; Li, Lei

2016-12-01

Polyaniline/graphene hydrogel composites with a macroscopically phase-separated structure are prepared. The composites show high specific capacitance and excellent rate performance. Further investigation demonstrates that polyaniline inside the graphene hydrogel has low rate performance, thus a phase-separated structure, in which polyaniline is mainly outside the graphene hydrogel matrix, can enhance the rate performance of the composites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical magneto-actuated biosensor for CD4 count in AIDS diagnosis and monitoring.

PubMed

Carinelli, S; Xufré Ballesteros, C; Martí, M; Alegret, S; Pividori, M I

2015-12-15

The counting of CD4(+) T lymphocytes is a clinical parameter used for AIDS diagnosis and follow-up. As this disease is particularly prevalent in developing countries, simple and affordable CD4 cell counting methods are urgently needed in resource-limited settings. This paper describes an electrochemical magneto-actuated biosensor for CD4 count in whole blood. The CD4(+) T lymphocytes were isolated, preconcentrated and labeled from 100 μL of whole blood by immunomagnetic separation with magnetic particles modified with antiCD3 antibodies. The captured cells were labeled with a biotinylated antiCD4 antibody, followed by the reaction with the electrochemical reporter streptavidin-peroxidase conjugate. The limit of detection for the CD4 counting magneto-actuated biosensor in whole blood was as low as 44 cells μL(-1) while the logistic range was found to be from 89 to 912 cells μL(-1), which spans the whole medical interest range for CD4 counts in AIDS patients. The electrochemical detection together with the immunomagnetic separation confers high sensitivity, resulting in a rapid, inexpensive, robust, user-friendly method for CD4 counting. This approach is a promising alternative for the costly standard flow cytometry and suitable as diagnostic tool at decentralized practitioner sites in low resource settings, especially in less developed countries. Copyright © 2015 Elsevier B.V. All rights reserved.

Gas permeable electrode for electrochemical system

DOEpatents

Ludwig, F.A.; Townsend, C.W.

1989-09-12

An electrode apparatus is described which is adapted for use in electrochemical systems having an anode compartment and a cathode compartment in which gas and ions are produced and consumed in the compartments during generation of electrical current. The electrode apparatus includes a membrane for separating the anode compartment from the cathode compartment wherein the membrane is permeable to both ions and gas. The cathode and anode for the assembly are provided on opposite sides of the membrane. During use of the membrane-electrode apparatus in electrochemical cells, the gas and ions generated at the cathode or anode migrate through the membrane to provide efficient transfer of gas and ions between the anode and cathode compartments. 3 figs.

Microbial electrochemical separation of CO2 for biogas upgrading.

PubMed

Kokkoli, Argyro; Zhang, Yifeng; Angelidaki, Irini

2018-01-01

Biogas upgrading to natural gas quality has been under focus the recent years for increasing the utilization potential of biogas. Conventional methods for CO 2 removal are expensive and have environmental challenges, such as increased emissions of methane in the atmosphere with serious greenhouse impact. In this study, an innovative microbial electrochemical separation cell (MESC) was developed to in-situ separate and regenerate CO 2 via alkali and acid regeneration. The MESC was tested under different applied voltages, inlet biogas rates and electrolyte concentrations. Pure biomethane was obtained at 1.2V, inlet biogas rate of 0.088mL/h/mL reactor and NaCl concentration of 100mM at a 5-day operation. Meanwhile, the organic matter of the domestic wastewater in the anode was almost completely removed at the end. The study demonstrated a new sustainable way to simultaneously upgrade biogas and treat wastewater which can be used as proof of concept for further investigation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical performance of a thermally rearranged polybenzoxazole nanocomposite membrane as a separator for lithium-ion batteries at elevated temperature

NASA Astrophysics Data System (ADS)

Lee, Moon Joo; Hwang, Jun-Ki; Kim, Ji Hoon; Lim, Hyung-Seok; Sun, Yang-Kook; Suh, Kyung-Do; Lee, Young Moo

2016-02-01

Shape-tunable hydroxyl copolyimide (HPI) nanoparticles are fabricated by a re-precipitation method and are coated onto electrospun HPI membranes, followed by heat treatment to prepare thermally rearranged polybenzoxazole (TR-PBO) composite membranes. The morphology of HPI nanoparticles consisted of sphere and sea-squirt structures, which is controlled by changing the concentration of the stabilizer. The morphological characteristics of TR-PBO nanoparticles convert from HPI nanoparticles by heat treatment and their composite membranes is confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (ATR-IR), thermogravimetric analysis (TGA) analysis, and contact angle measurements. TGA and DSC measurements confirm the excellent thermal stability compared to Celgard, a commercial PP separator for lithium-ion batteries (LIBs). Further, TR-PBO nano-composite membranes used in coin-cell type LIBs as a separator show excellent high power density performance as compared to Celgard. This is due to the fact that sea-squirt structured nanoparticles have better electrochemical properties than sphere structured nanoparticles at high temperature.

The Redox flow system for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Odonnell, P.; Gahn, R. F.

1976-01-01

A new method of storage was applied to a solar photovoltaic system. The storage method is a redox flow system which utilizes the oxidation-reduction capability of two soluble electrochemical redox couples for its storage capacity. The particular variant described separates the charging and discharging function of the system such that the electrochemical couples are simultaneously charged and discharged in separate parts of the system. The solar array had 12 solar cells; wired in order to give a range of voltages and currents. The system stored the solar energy so that a load could be run continually day and night. The main advantages of the redox system are that it can accept a charge in the low voltage range and produce a relatively constant output regardless of solar activity.

Boron-doped diamond microdisc arrays: electrochemical characterisation and their use as a substrate for the production of microelectrode arrays of diverse metals (Ag, Au, Cu)via electrodeposition.

PubMed

Simm, Andrew O; Banks, Craig E; Ward-Jones, Sarah; Davies, Trevor J; Lawrence, Nathan S; Jones, Timothy G J; Jiang, Li; Compton, Richard G

2005-09-01

A novel boron-doped diamond (BDD) microelectrode array is characterised with electrochemical and atomic force microscopic techniques. The array consists of 40 micron-diameter sized BDD discs which are separated by 250 microns from their nearest neighbour in a hexagonal arrangement. The conducting discs can be electroplated to produce arrays of copper, silver or gold for analytical purposes in addition to operating as an array of BDD-microelectrodes. Proof-of-concept is shown for four separate examples; a gold plated array for arsenic detection, a copper plated array for nitrate analysis, a silver plated array for hydrogen peroxide monitoring and last, cathodic stripping voltammetry for lead at the bare BDD-array.

Tailored Core Shell Cathode Powders for Solid Oxide Fuel Cells

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

Swartz, Scott

2015-03-23

In this Phase I SBIR project, a “core-shell” composite cathode approach was evaluated for improving SOFC performance and reducing degradation of lanthanum strontium cobalt ferrite (LSCF) cathode materials, following previous successful demonstrations of infiltration approaches for achieving the same goals. The intent was to establish core-shell cathode powders that enabled high performance to be obtained with “drop-in” process capability for SOFC manufacturing (i.e., rather than adding an infiltration step to the SOFC manufacturing process). Milling, precipitation and hetero-coagulation methods were evaluated for making core-shell composite cathode powders comprised of coarse LSCF “core” particles and nanoscale “shell” particles of lanthanum strontiummore » manganite (LSM) or praseodymium strontium manganite (PSM). Precipitation and hetero-coagulation methods were successful for obtaining the targeted core-shell morphology, although perfect coverage of the LSCF core particles by the LSM and PSM particles was not obtained. Electrochemical characterization of core-shell cathode powders and conventional (baseline) cathode powders was performed via electrochemical impedance spectroscopy (EIS) half-cell measurements and single-cell SOFC testing. Reliable EIS testing methods were established, which enabled comparative area-specific resistance measurements to be obtained. A single-cell SOFC testing approach also was established that enabled cathode resistance to be separated from overall cell resistance, and for cathode degradation to be separated from overall cell degradation. The results of these EIS and SOFC tests conclusively determined that the core-shell cathode powders resulted in significant lowering of performance, compared to the baseline cathodes. Based on the results of this project, it was concluded that the core-shell cathode approach did not warrant further investigation.« less

An electrochemical rebalance cell for Redox systems

NASA Technical Reports Server (NTRS)

Acevedo, J. C.; Stalnaker, D. K.

1983-01-01

An electrochemical rebalance cell for maintaining electrochemical balance, at the system level, of the acidified aqueous iron chloride and chromium chloride reactant solutions in the redox energy storage system was constructed and evaluated. The electrochemical reaction for the cathode is Fe(+3) + e(-) yields Fe(+2), and that for the anode is 1/2H2 yields H(+) + e(-). The iron (carbon felt) electrode and the hydrogen (platinized carbon) electrode are separated by an anion exchange membrane. The performance of the rebalance cell is discussed as well as the assembly of a single rebalance cell and multicell stacks. Various cell configurations were tested and the results are presented and discussed. The rebalance cell was also used to demonstrate its ability, as a preparative tool, for making high purity solutions of soluble reduced metal ionic species. Preparations of titanium, copper, vanadium and chromium ions in acidified solutions were evaluated.

Electrochemical Reconstitution of Biomolecules for Applications as Electrocatalysts for the Bionanofuel Cell

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Watt, Gerald D.; Chu, Sang-Hyon; Park, Yeonjoon; Thibeault, Sheila

2004-01-01

Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.

Electrochemical process and production of novel complex hydrides

DOEpatents

Zidan, Ragaiy

2013-06-25

A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

Methods for and products of processing nanostructure nitride, carbonitride and oxycarbonitride electrode power materials by utilizing sol gel technology for supercapacitor applications

DOEpatents

Huang, Yuhong; Wei, Oiang; Chu, Chung-tse; Zheng, Haixing

2001-01-01

Metal nitride, carbonitride, and oxycarbonitride powder with high surface area (up to 150 m.sup.2 /g) is prepared by using sol-gel process. The metal organic precursor, alkoxides or amides, is synthesized firstly. The metal organic precursor is modified by using unhydrolyzable organic ligands or templates. A wet gel is formed then by hydrolysis and condensation process. The solvent in the wet gel is then be removed supercritically to form porous amorphous hydroxide. This porous hydroxide materials is sintered to 725.degree. C. under the ammonia flow and porous nitride powder is formed. The other way to obtain high surface area nitride, carbonitride, and oxycarbonitride powder is to pyrolyze polymerized templated metal amides aerogel in an inert atmosphere. The electrochemical capacitors are prepared by using sol-gel prepared nitride, carbonitride, and oxycarbonitride powder. Two methods are used to assemble the capacitors. Electrode is formed either by pressing the mixture of nitride powder and binder to a foil, or by depositing electrode coating onto metal current collector. The binder or coating is converted into a continuous network of electrode material after thermal treatment to provide enhanced energy and power density. Liquid electrolyte is soaked into porous electrode. The electrochemical capacitor assembly further has a porous separator layer between two electrodes/electrolyte and forming a unit cell.

High Power Electrochemical Capacitors

DTIC Science & Technology

2012-03-23

electrochemical properties of vanadium oxide aerogels prepared by a freeze-drying process. Journal of the Electrochemical Society, 2004. 151(5): p...Electrochemical Society, 2002. 149(1): p. A26-A30. 12. Rolison, D.R. and B. Dunn, Electrically conductive oxide aerogels : new materials in...surface area vanadium oxide aerogels . Electrochemical and Solid-State Letters, 2000. 3(10): p. 457-459. 14. Shembel, E., et al., Synthesis, investigation

The mechanisms of pyrite oxidation and leaching: A fundamental perspective

NASA Astrophysics Data System (ADS)

Chandra, A. P.; Gerson, A. R.

2010-09-01

Pyrite is the earth's most abundant sulfide mineral. Its frequent undesirable association with minerals of economic value such as sphalerite, chalcopyrite and galena, and precious metals such as gold necessitates costly separation processes such as leaching and flotation. Additionally pyrite oxidation is a major contributor to the environmental problem of acid rock drainage. The surface oxidation reactions of pyrite are therefore important both economically and environmentally. Significant variations in electrical properties resulting from lattice substitution of minor and trace elements into the lattice structure exist between pyrite from different geographical locations. Furthermore the presence of low coordination surface sites as a result of conchoidal fracture causes a reduction in the band gap at the surface compared to the bulk thus adding further electrochemical variability. Given the now general acceptance after decades of research that electrochemistry dominates the oxidation process, the geographical location, elemental composition and semi-conductor type (n or p) of pyrite are important considerations. Aqueous pyrite oxidation results in the production of sulfate and ferrous iron. However other products such as elemental sulfur, polysulfides, hydrogen sulfide, ferric hydroxide, iron oxide and iron(III) oxyhydroxide may also form. Intermediate species such as thiosulfate, sulfite and polythionates are also proposed to occur. Oxidation and leach rates are generally influenced by solution Eh, pH, oxidant type and concentration, hydrodynamics, grain size and surface area in relation to solution volume, temperature and pressure. Of these, solution Eh is most critical as expected for an electrochemically controlled process, and directly correlates with surface area normalised rates. Studies using mixed mineral systems further indicate the importance of electrochemical processes during the oxidation process. Spatially resolved surface characterisation of fresh and reacted pyrite surfaces is needed to identify site specific chemical processes. Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) are two synchrotron based surface spectromicroscopic and microspectroscopic techniques that use XPS- and XANES-imaging to correlate chemistry with topography at a submicron scale. Recent data collected with these two techniques suggests that species are heterogeneously distributed on the surface and oxidation to be highly site specific.

Nanoscale electrochemical patterning reveals the active sites for catechol oxidation at graphite surfaces.

PubMed

Patel, Anisha N; McKelvey, Kim; Unwin, Patrick R

2012-12-19

Graphite-based electrodes (graphite, graphene, and nanotubes) are used widely in electrochemistry, and there is a long-standing view that graphite step edges are needed to catalyze many reactions, with the basal surface considered to be inert. In the present work, this model was tested directly for the first time using scanning electrochemical cell microscopy reactive patterning and shown to be incorrect. For the electro-oxidation of dopamine as a model process, the reaction rate was measured at high spatial resolution across a surface of highly oriented pyrolytic graphite. Oxidation products left behind in a pattern defined by the scanned electrochemical cell served as surface-site markers, allowing the electrochemical activity to be correlated directly with the graphite structure on the nanoscale. This process produced tens of thousands of electrochemical measurements at different locations across the basal surface, unambiguously revealing it to be highly electrochemically active, with step edges providing no enhanced activity. This new model of graphite electrodes has significant implications for the design of carbon-based biosensors, and the results are additionally important for understanding electrochemical processes on related sp(2)-hybridized materials such as pristine graphene and nanotubes.

Study on the Carbonation Behavior of Cement Mortar by Electrochemical Impedance Spectroscopy

PubMed Central

Dong, Biqin; Qiu, Qiwen; Xiang, Jiaqi; Huang, Canjie; Xing, Feng; Han, Ningxu

2014-01-01

A new electrochemical model has been carefully established to explain the carbonation behavior of cement mortar, and the model has been validated by the experimental results. In fact, it is shown by this study that the electrochemical impedance behavior of mortars varies in the process of carbonation. With the cement/sand ratio reduced, the carbonation rate reveals more remarkable. The carbonation process can be quantitatively accessed by a parameter, which can be obtained by means of the electrochemical impedance spectroscopy (EIS)-based electrochemical model. It has been found that the parameter is a function of carbonation depth and of carbonation time. Thereby, prediction of carbonation depth can be achieved. PMID:28788452

Study on the Carbonation Behavior of Cement Mortar by Electrochemical Impedance Spectroscopy.

PubMed

Dong, Biqin; Qiu, Qiwen; Xiang, Jiaqi; Huang, Canjie; Xing, Feng; Han, Ningxu

2014-01-03

A new electrochemical model has been carefully established to explain the carbonation behavior of cement mortar, and the model has been validated by the experimental results. In fact, it is shown by this study that the electrochemical impedance behavior of mortars varies in the process of carbonation. With the cement/sand ratio reduced, the carbonation rate reveals more remarkable. The carbonation process can be quantitatively accessed by a parameter, which can be obtained by means of the electrochemical impedance spectroscopy (EIS)-based electrochemical model. It has been found that the parameter is a function of carbonation depth and of carbonation time. Thereby, prediction of carbonation depth can be achieved.

[Study on electrochemical mechanism of coronary stent used austenitic stainless steel in flowing artificial body fluid].

PubMed

Liang, Chenghao; Guo, Liang; Chen, Wan; Wang, Hua

2005-08-01

The electrochemical mechanism of austenitic stainless steel (SUS316L and SUS317L) coronary stents in flowing artificial body fluid has been investigated with electrochemical technologies. The results indicated that the flowing medium coursed the samples' pitting potential Eb shift negatively, increased the pitting corrosion sensitivity, accelerated its anodic dissolution, but had little effects on repassivated potential. The flowing environment had great effects on cathodic process. The oxygen reaction on the samples' surface became faster as the cathodic process was not controlled by oxygen diffusion but by mixed diffusion and electrochemical process. With the increase of velocity of solution, the pitting corrosion becomes liable to occur under this circumstance.

Deterministic analysis of processes at corroding metal surfaces and the study of electrochemical noise in these systems

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

Latanision, R.M.

1990-12-01

Electrochemical corrosion is pervasive in virtually all engineering systems and in virtually all industrial circumstances. Although engineers now understand how to design systems to minimize corrosion in many instances, many fundamental questions remain poorly understood and, therefore, the development of corrosion control strategies is based more on empiricism than on a deep understanding of the processes by which metals corrode in electrolytes. Fluctuations in potential, or current, in electrochemical systems have been observed for many years. To date, all investigations of this phenomenon have utilized non-deterministic analyses. In this work it is proposed to study electrochemical noise from a deterministicmore » viewpoint by comparison of experimental parameters, such as first and second order moments (non-deterministic), with computer simulation of corrosion at metal surfaces. In this way it is proposed to analyze the origins of these fluctuations and to elucidate the relationship between these fluctuations and kinetic parameters associated with metal dissolution and cathodic reduction reactions. This research program addresses in essence two areas of interest: (a) computer modeling of corrosion processes in order to study the electrochemical processes on an atomistic scale, and (b) experimental investigations of fluctuations in electrochemical systems and correlation of experimental results with computer modeling. In effect, the noise generated by mathematical modeling will be analyzed and compared to experimental noise in electrochemical systems. 1 fig.« less

Rate- and Temperature-Dependent Material Behavior of a Multilayer Polymer Battery Separator

NASA Astrophysics Data System (ADS)

Avdeev, Ilya; Martinsen, Michael; Francis, Alex

2014-01-01

Designing battery packs for safety in automotive applications requires multiscale modeling, as macroscopic deformations due to impact cause the mechanical failure of individual cells on a sub-millimeter level. The separator material plays a critical role in this process, as the thinning or perforating of the separator can lead to thermal runaway and catastrophic failure of an entire battery pack. The electrochemical properties of various polymer separators have been extensively investigated; however, the dependency of mechanical properties of these thin films on various factors, such as high temperature and strain rate, has not been sufficiently characterized. In this study, the macroscopic mechanical properties of a multilayer polymer thin film used as a battery separator are studied experimentally at various temperatures, strain rates, and solvent saturations. Due to the anisotropy of the material, material testing was conducted in two perpendicular directions (machine and transverse directions). Material samples were tested in both dry and saturated conditions at several temperatures, and it was found that temperature and strain rate have a nearly linear effect on the stress experienced by the material. Additionally, saturating the separator material in a common lithium-ion solvent had softened it and had a positive effect on its toughness. The experimental results obtained in this study can be used to develop mathematical constitutive models of the multilayer separator material for subsequent numerical simulations and design.

Fabrication of advanced electrochemical energy materials using sol-gel processing techniques

NASA Technical Reports Server (NTRS)

Chu, C. T.; Chu, Jay; Zheng, Haixing

1995-01-01

Advanced materials play an important role in electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. They are being used as both electrodes and electrolytes. Sol-gel processing is a versatile solution technique used in fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. The application of sol-gel processing in the fabrication of advanced electrochemical energy materials will be presented. The potentials of sol-gel derived materials for electrochemical energy applications will be discussed along with some examples of successful applications. Sol-gel derived metal oxide electrode materials such as V2O5 cathodes have been demonstrated in solid-slate thin film batteries; solid electrolytes materials such as beta-alumina for advanced secondary batteries had been prepared by the sol-gel technique long time ago; and high surface area transition metal compounds for capacitive energy storage applications can also be synthesized with this method.

Porous siliconformation and etching process for use in silicon micromachining

DOEpatents

Guilinger, Terry R.; Kelly, Michael J.; Martin, Jr., Samuel B.; Stevenson, Joel O.; Tsao, Sylvia S.

1991-01-01

A reproducible process for uniformly etching silicon from a series of micromechanical structures used in electrical devices and the like includes providing a micromechanical structure having a silicon layer with defined areas for removal thereon and an electrochemical cell containing an aqueous hydrofluoric acid electrolyte. The micromechanical structure is submerged in the electrochemical cell and the defined areas of the silicon layer thereon are anodically biased by passing a current through the electrochemical cell for a time period sufficient to cause the defined areas of the silicon layer to become porous. The formation of the depth of the porous silicon is regulated by controlling the amount of current passing through the electrochemical cell. The micromechanical structure is then removed from the electrochemical cell and submerged in a hydroxide solution to remove the porous silicon. The process is subsequently repeated for each of the series of micromechanical structures to achieve a reproducibility better than 0.3%.

ELECTRICALLY ACTUATED, PRESSURE-DRIVEN LIQUID CHROMATOGRAPHY SEPARATIONS IN MICROFABRICATED DEVICES

PubMed Central

Fuentes, Hernan V.; Woolley, Adam T.

2012-01-01

Electrolysis-based micropumps integrated with microfluidic channels in micromachined glass substrates are presented. Photolithography combined with wet chemical etching and thermal bonding enabled the fabrication of multi-layer devices containing electrically actuated micropumps interfaced with sample and mobile phase reservoirs. A stationary phase was deposited on the microchannel walls by coating with 10% (w/w) chlorodimethyloctadecylsilane in toluene. Pressure-balanced injection was implemented by controlling the electrolysis time and voltage applied in the two independent micropumps. Current fluctuations in the micropumps due to the stochastic formation of bubbles on the electrode surfaces were determined to be the main cause of variation between separations. On-chip electrochemical pumping enabled the loading of pL samples with no dead volume between injection and separation. A mobile phase composed of 70% acetonitrile and 30% 50 mM acetate buffer (pH 5.45) was used for the chromatographic separation of three fluorescently labeled amino acids in <40 s with an efficiency of >3000 theoretical plates in a 2.5-cm-long channel. Our results demonstrate the potential of electrochemical micropumps integrated with microchannels to perform rapid chromatographic separations in a microfabricated platform. Importantly, these devices represent a significant step toward the development of miniaturized and fully integrated liquid chromatography systems. PMID:17960281

Electrically actuated, pressure-driven liquid chromatography separations in microfabricated devices.

PubMed

Fuentes, Hernan V; Woolley, Adam T

2007-11-01

Electrolysis-based micropumps integrated with microfluidic channels in micromachined glass substrates are presented. Photolithography combined with wet chemical etching and thermal bonding enabled the fabrication of multi-layer devices containing electrically actuated micropumps interfaced with sample and mobile phase reservoirs. A stationary phase was deposited on the microchannel walls by coating with 10% (w/w) chlorodimethyloctadecylsilane in toluene. Pressure-balanced injection was implemented by controlling the electrolysis time and voltage applied in the two independent micropumps. Current fluctuations in the micropumps due to the stochastic formation of bubbles on the electrode surfaces were determined to be the main cause of variation between separations. On-chip electrochemical pumping enabled the loading of pL samples with no dead volume between injection and separation. A mobile phase composed of 70% acetonitrile and 30% 50 mM acetate buffer (pH 5.45) was used for the chromatographic separation of three fluorescently labeled amino acids in <40 s with an efficiency of >3000 theoretical plates in a 2.5 cm-long channel. Our results demonstrate the potential of electrochemical micropumps integrated with microchannels to perform rapid chromatographic separations in a microfabricated platform. Importantly, these devices represent a significant step toward the development of miniaturized and fully integrated liquid chromatography systems.

Microchip Capillary Electrophoresis with Electrochemical Detection for Monitoring Environmental Pollutants

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

Chen, Gang; Lin, Yuehe; Wang, Joseph

2006-01-15

This invited paper reviews recent advances and the key strategies in microchip capillary electrophoresis (CE) with electrochemical detection (ECD) for separating and detecting a variety of environmental pollutants. The subjects covered include the fabrication of microfluidic chips, sample pretreatments, ECD, typical applications of microchip CE with ECD in environmental analysis, and future prospects. It is expected that microchip CE-ECD will become a powerful tool in the environmental field and will lead to the creation of truly portable devices.

Flow injection trace gas analysis method for on-site determination of organoarsenicals

DOEpatents

Aldstadt, III, Joseph H.

1997-01-01

A method for real-time determination of the concentration of Lewisite in the ambient atmosphere, the method includes separating and collecting a Lewisite sample from the atmosphere in a collection chamber, converting the collected Lewisite to an arsenite ion solution sample, pumping the arsenite ion containing sample to an electrochemical detector connected to the collection chamber, and electrochemically detecting the converted arsenite ions in the sample, whereby the concentration of arsenite ions detected is proportional to the concentration of Lewisite in the atmosphere.

Feedback‐amplified electrochemical dual‐plate boron‐doped diamond microtrench detector for flow injection analysis

PubMed Central

Lewis, Grace E. M.; Gross, Andrew J.; Kasprzyk‐Hordern, Barbara; Lubben, Anneke T.

2015-01-01

An electrochemical flow cell with a boron‐doped diamond dual‐plate microtrench electrode has been developed and demonstrated for hydroquinone flow injection electroanalysis in phosphate buffer pH 7. Using the electrochemical generator‐collector feedback detector improves the sensitivity by one order of magnitude (when compared to a single working electrode detector). The diffusion process is switched from an analyte consuming “external” process to an analyte regenerating “internal” process with benefits in selectivity and sensitivity. PMID:25735831

Fundamental Studies Connected with Electrochemical Energy Storage

NASA Technical Reports Server (NTRS)

Buck, E.; Sen, R.

1974-01-01

Papers are presented which deal with electrochemical research activities. Emphasis is placed on electrochemical energy storage devices. Topics discussed include: adsorption of dendrite inhibitors on zinc; proton discharge process; electron and protron transfer; quantum mechanical formulation of electron transfer rates; and theory of electrochemical kinetics in terms of two models of activation; thermal and electrostatic.

High quality self-separated GaN crystal grown on a novel nanoporous template by HVPE.

PubMed

Huo, Qin; Shao, Yongliang; Wu, Yongzhong; Zhang, Baoguo; Hu, Haixiao; Hao, Xiaopeng

2018-02-16

In this study, a novel nanoporous template was obtained by a two-step etching process from MOCVD-GaN/Al 2 O 3 (MGA) with electrochemical etching sequentially followed by chemical wet etching. The twice-etched MOCVD-GaN/Al 2 O 3 (TEMGA) templates were utilized to grow GaN crystals by hydride vapor phase epitaxy (HVPE) method. The GaN crystals were separated spontaneously from the TEMGA template with the assistance of voids formed by the etched nanopores. Several techniques were utilized to characterize the quality of the free-standing GaN crystals obtained from the TEMGA template. Results showed that the quality of the as-obtained GaN crystals was improved obviously compared with those grown on the MGA. This convenient technique can be applied to grow high-quality free-standing GaN crystals.

Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes.

PubMed

Yang, Yue; Xu, Shengming; He, Yinghe

2017-06-01

A novel process for extracting transition metals, recovering lithium and regenerating cathode materials based on facile co-extraction and co-precipitation processes has been developed. 100% manganese, 99% cobalt and 85% nickel are co-extracted and separated from lithium by D2EHPA in kerosene. Then, Li is recovered from the raffinate as Li 2 CO 3 with the purity of 99.2% by precipitation method. Finally, organic load phase is stripped with 0.5M H 2 SO 4 , and the cathode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 is directly regenerated from stripping liquor without separating metal individually by co-precipitation method. The regenerative cathode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 is miro spherical morphology without any impurities, which can meet with LiNi 1/3 Co 1/3 Mn 1/3 O 2 production standard of China and exhibits good electrochemical performance. Moreover, a waste battery management model is introduced to guarantee the material supply for spent battery recycling. Copyright © 2017 Elsevier Ltd. All rights reserved.

In situ, simultaneous thermal imaging and infrared molecular emission studies of solid oxide fuel cell electrodes

NASA Astrophysics Data System (ADS)

Kirtley, J. D.; Qadri, S. N.; Steinhurst, D. A.; Owrutsky, J. C.

2016-12-01

Various in situ probes of solid oxide fuel cells (SOFCs) have advanced recently to provide detailed, real time data regarding materials and chemical processes that relate to device performance and degradation. These techniques offer insights into complex fuel chemistry at the anode in particular, especially in the context of model predictions. However, cell-to-cell variations can hinder mechanistic interpretations of measurements from separate, independent techniques. The present study describes an in situ technique that for the first time simultaneously measures surface temperature changes using near infrared thermal imaging and gas species using Fourier-transform infrared emission spectra at the anodes of operating SOFCs. Electrolyte-supported SOFCs with Ni-based anodes are operated at 700 °C with internal, dry-reformed methane at 75% maximum current and at open circuit voltage (OCV) while electrochemical and optical measurements are collected. At OCV, more cooling is observed coincident with more CO reforming products. Under load, CO decreases while the anode cools less, especially near the current collectors. The extent of cooling is more sensitive to polarization for electrolyte-supported cells because their anodes are thinner relative to anode-supported cells. This study exemplifies how this duplex technique can be a useful probe of electrochemical processes in SOFCs.

Renewable hydrogen production via thermochemical/electrochemical coupling

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

Ambrosini, Andrea; Babiniec, Sean Michael; Miller, James E.

A coupled electrochemical/thermochemical cycle was investigated to produce hydrogen from renewable resources. Like a conventional thermochemical cycle, this cycle leverages chemical energy stored in a thermochemical working material that is reduced thermally by solar energy. However, in this concept, the stored chemical energy only needs to be partially, but not fully, capable of splitting steam to produce hydrogen. To complete the process, a proton-conducting membrane is driven to separate hydrogen as it is produced, thus shifting the thermodynamics toward further hydrogen production. This novel coupled-cycle concept provides several benefits. First, the required oxidation enthalpy of the reversible thermochemical material ismore » reduced, enabling the process to occur at lower temperatures. Second, removing the requirement for spontaneous steam-splitting widens the scope of materials compositions, allowing for less expensive/more abundant elements to be used. Lastly, thermodynamics calculations suggest that this concept can potentially reach higher efficiencies than photovoltaic-to-electrolysis hydrogen production methods. This Exploratory Express LDRD involved assessing the practical feasibility of the proposed coupled cycle. A test stand was designed and constructed and proton-conducting membranes were synthesized. While the full proof of concept was not achieved, the individual components of the experiment were validated and new capabilities that can be leveraged by a variety of programs were developed.« less

Separator Membrane from Crosslinked Poly(Vinyl Alcohol) and Poly(Methyl Vinyl Ether-alt-Maleic Anhydride)

PubMed Central

Rohatgi, Charu Vashisth; Dutta, Naba K.; Choudhury, Namita Roy

2015-01-01

In this work, we report separator membranes from crosslinking of two polymers, such as poly vinyl alcohol (PVA) with an ionic polymer poly(methyl vinyl ether-alt-maleic anhydride) (PMVE-MA). Such interpolymer-networked systems were extensively used for biomedical and desalination applications but they were not examined for their potential use as membranes or separators for batteries. Therefore, the chemical interactions between these two polymers and the influence of such crosslinking on physicochemical properties of the membrane are systematically investigated through rheology and by critical gel point study. The hydrogen bonding and the chemical interaction between PMVE-MA and PVA resulted in highly cross-linked membranes. Effect of the molecular weight of PVA on the membrane properties was also examined. The developed membranes were extensively characterized by studying their physicochemical properties (water uptake, swelling ratio, and conductivity), thermal and electrochemical properties using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermo-gravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS). The DSC study shows the presence of a single Tg in the membranes indicating compatibility of the two polymers in flexible and transparent films. The membranes show good stability and ion conductivity suitable for separator applications. PMID:28347019

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

Simultaneous determination of diclofenac and oxybuprocaine in human aqueous humor with HPLC and electrochemical detection.

PubMed

Kuhlmann, O; Stoldt, G; Struck, H G; Krauss, G J

1998-09-01

A sensitive and selective bioanalytical method for simultaneous determination of diclofenac and oxybuprocaine in human aqueous humor using reversed-phase HPLC and electrochemical detection is described. Chromatographic separation was achieved by using a Regis SPS 100 RP-8 column (5 microns; 150 x 4.6 mm I.D.). This support is coated with a hydrophilic polyoxyethylenepolymer. It allows protein-containing samples to be injected directly onto the column. The electrochemical detector permit a detection limit of 500 pg diclofenac per ml (daily relative standard deviation 6.3%) and 50 ng oxybuprocaine per ml (daily R.S.D. 2.6%), respectively. Results of administered and measured drug-concentrations in time dependent decrease are presented.

Continuous-feed electrochemical cell with nonpacking particulate electrode

DOEpatents

Cooper, John F.

1995-01-01

An electrochemical cell providing full consumption of electrochemically active particles in a nonpacking, electrolyte-permeable bed has a tapered cell cavity bounded by two nonparallel surfaces separated by a distance that promotes bridging of particles across the cavity. The gap/particle size ratio is maintained as the particles are consumed, decrease in size, and travel from the point of entry to the narrower end of the cell. A cell of this configuration supports a bed of low packing density maintained in a dynamic steady state by alternate formation and collapse of particle bridges across the gap and associated voids over the entire active area of the cell. The cell design can be applied to refuelable zinc/air cells and zinc/ferrocyanide storage batteries.

Continuous-feed electrochemical cell with nonpacking particulate electrode

DOEpatents

Cooper, J.F.

1995-07-18

An electrochemical cell providing full consumption of electrochemically active particles in a nonpacking, electrolyte-permeable bed has a tapered cell cavity bounded by two nonparallel surfaces separated by a distance that promotes bridging of particles across the cavity. The gap/particle size ratio is maintained as the particles are consumed, decrease in size, and travel from the point of entry to the narrower end of the cell. A cell of this configuration supports a bed of low packing density maintained in a dynamic steady state by alternate formation and collapse of particle bridges across the gap and associated voids over the entire active area of the cell. The cell design can be applied to refuelable zinc/air cells and zinc/ferrocyanide storage batteries. 6 figs.

Crystallization of Photosystem II for Time-Resolved Structural Studies Using an X-ray Free Electron Laser

PubMed Central

Coe, Jesse; Kupitz, Christopher; Basu, Shibom; Conrad, Chelsie E.; Roy-Chowdhury, Shatabdi; Fromme, Raimund; Fromme, Petra

2015-01-01

Photosystem II (PSII) is a membrane protein supercomplex that executes the initial reaction of photosynthesis in higher plants, algae, and cyanobacteria. It captures the light from the sun to catalyze a transmembrane charge separation. In a series of four charge separation events, utilizing the energy from four photons, PSII oxidizes two water molecules to obtain dioxygen, four protons, and four electrons. The light reactions of photosystems I and II (PSI and PSII) result in the formation of an electrochemical transmembrane proton gradient that is used for the production of ATP. Electrons that are subsequently transferred from PSI via the soluble protein ferredoxin to ferredoxin-NADP+ reductase that reduces NADP+ to NADPH. The products of photosynthesis and the elemental oxygen evolved sustain all higher life on Earth. All oxygen in the atmosphere is produced by the oxygen-evolving complex in PSII, a process that changed our planet from an anoxygenic to an oxygenic atmosphere 2.5 billion years ago. In this chapter, we provide recent insight into the mechanisms of this process and methods used in probing this question. PMID:25950978

Mechanisms responsible for two possible electrochemical reactions in Li1.2Ni0.13Mn0.54Co0.13O2 used for lithium ion batteries

NASA Astrophysics Data System (ADS)

Konishi, Hiroaki; Hirano, Tatsumi; Takamatsu, Daiko; Gunji, Akira; Feng, Xiaoliang; Furutsuki, Sho; Okumura, Takefumi; Terada, Shohei; Tamura, Kazuhisa

2018-02-01

Two electrochemical reactions are possible in regard to Li1.2Ni0.13Mn0.54Co0.13O2 (0.5Li2MnO3-0.5LiNi0.33Mn0.33Co0.33O2), viz, Li2MnO3-like and LiNi0.33Mn0.33Co0.33O2-like reactions. The open circuit potential (OCP) and changes in crystal structure during the charge-discharge process of Li1.2Ni0.13Mn0.54Co0.13O2 were investigated to clarify the mechanism responsible for the two reactions. Li2MnO3 and LiNi0.33Mn0.33Co0.33O2 were separately prepared for the investigation, and the OCPs and crystal structures in these cathodes were measured and then compared with those for Li1.2Ni0.13Mn0.54Co0.13O2. The results obtained using X-ray diffraction (XRD) indicated that two phases existed in Li1.2Ni0.13Mn0.54Co0.13O2. The changes in crystal structure of the two phases during the charge-discharge process were similar to those in Li2MnO3 and LiNi0.33Mn0.33Co0.33O2. This indicated that two phases, viz, Li2MnO3-like and LiNi0.33Mn0.33Co0.33O2-like, existed in Li1.2Ni0.13Mn0.54Co0.13O2. Li2MnO3-like, LiNi0.33Mn0.33Co0.33O2-like, and Li2MnO3-like phases were found to contribute mainly to electrochemical reactions in the low, middle, and high state of charge (SOC) ranges during the charge process from the results obtained using XRD and electrochemical measurements carried out on Li1.2Ni0.13Mn0.54Co0.13O2. In contrast, the Li2MnO3-like and LiNi0.33Mn0.33Co0.33O2-like phases mainly contributed to electrochemical reactions in the low and high SOC ranges during the discharge process. Furthermore, the high polarization and potential decay during the charge-discharge cycling of Li1.2Ni0.13Mn0.54Co0.13O2 were mainly attributed to the Li2MnO3-like phase.

Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry.

PubMed

Durham, Jessica L; Poyraz, Altug S; Takeuchi, Esther S; Marschilok, Amy C; Takeuchi, Kenneth J

2016-09-20

Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and mass of the final system. Material multifunctionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cations can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multimechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM'O) or phosphorus oxides (MM'PO) where M = Ag and M' = V or Fe. One discharge process can be described as reduction-displacement where Ag(+) is reduced to Ag(0) and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the kinetically and thermodynamically preferred reduction processes at various states of discharge is critical to elucidating the mechanism. Specific advanced in situ and ex situ characterization techniques are conducive to gaining insight regarding the electrochemical behavior of these multifunctional materials over multiple length scales. At the material level, optical microscopy, scanning electron microscopy, and local conductivity measurement via a nanoprobe can track the discharge mechanism of an isolated single particle. At the mesoscale electrode level, in situ data from synchrotron based energy dispersive X-ray diffraction (EDXRD) within fully intact steel batteries can be used to spatially map the distribution of silver metal generated through reduction displacement as a function of discharge depth and discharge rate. As illustrated here, appropriate design of materials with multiple electrochemically active metal centers and properties tuned through strategically conceptualized materials synthesis may provide a path toward the next generation of high energy content electroactive materials and systems. Full understanding of the multiple electrochemical mechanisms can be achieved only by utilizing advanced characterization tools over multiple length scales.

Modeling of Electrochemical Process for the Treatment of Wastewater Containing Organic Pollutants

NASA Astrophysics Data System (ADS)

Rodrigo, Manuel A.; Cañizares, Pablo; Lobato, Justo; Sáez, Cristina

Electrocoagulation and electrooxidation are promising electrochemical technologies that can be used to remove organic pollutants contained in wastewaters. To make these technologies competitive with the conventional technologies that are in use today, a better understanding of the processes involved must be achieved. In this context, the development of mathematical models that are consistent with the processes occurring in a physical system is a relevant advance, because such models can help to understand what is happening in the treatment process. In turn, a more detailed knowledge of the physical system can be obtained, and tools for a proper design of the processes, or for the analysis of operating problems, are attained. The modeling of these technologies can be carried out using single-variable or multivariable models. Likewise, the position dependence of the model species can be described with different approaches. In this work, a review of the basics of the modeling of these processes and a description of several representative models for electrochemical oxidation and coagulation are carried out. Regarding electrooxidation, two models are described: one which summarizes the pollution of a wastewater in only one model species and that considers a macroscopic approach to formulate the mass balances and other that considers more detailed profile of concentration to describe the time course of pollutants and intermediates through a mixed maximum gradient/macroscopic approach. On the topic of electrochemical coagulation, two different approaches are also described in this work: one that considers the hydrodynamic conditions as the main factor responsible for the electrochemical coagulation processes and the other that considers the chemical interaction of the reagents and the pollutants as the more significant processes in the description of the electrochemical coagulation of organic compounds. In addition, in this work it is also described a multivariable model for the electrodissolution of anodes (first stage in electrocoagulation processes). This later model use a mixed macroscopic/maximum gradient approach to describe the chemical and electrochemical processes and it also assumes that the rates of all processes are very high, and that they can be successfully modeled using pseudoequilibrium approaches.

A Demonstration of Simultaneous Electrochemiluminescence

ERIC Educational Resources Information Center

Ibanez, Jorge G.; Zavala-Araiza, Daniel; Sotomayor-Martinez Barranco, Biaani; Torres-Perez, Jonatan; Camacho-Zuniga, Claudia; Bohrmann-Linde, Claudia; Tausch, Michael W.

2013-01-01

Paired (simultaneous) electrochemical processes can increase energy savings in selected cases by using the reactions at both electrodes of an electrochemical cell to perform a desired process, as is the case in the commercially successful chlor-alkali process. In the demonstration described herein, simultaneous blue electrochemiluminescence (ECL)…

Analytical methods for determination of free metal ion concentration, labile species fraction and metal complexation capacity of environmental waters: a review.

PubMed

Pesavento, Maria; Alberti, Giancarla; Biesuz, Raffaela

2009-01-12

Different experimental approaches have been suggested in the last few decades to determine metal species in complex matrices of unknown composition as environmental waters. The methods are mainly focused on the determination of single species or groups of species. The more recent developments in trace elements speciation are reviewed focusing on methods for labile and free metal determination. Electrochemical procedures with low detection limit as anodic stripping voltammetry (ASV) and the competing ligand exchange with adsorption cathodic stripping voltammetry (CLE-AdCSV) have been widely employed in metal distribution studies in natural waters. Other electrochemical methods such as stripping chronopotentiometry and AGNES seem to be promising to evaluate the free metal concentration at the low levels of environmental samples. Separation techniques based on ion exchange (IE) and complexing resins (CR), and micro separation methods as the Donnan membrane technique (DMT), diffusive gradients in thin-film gels (DGT) and the permeation liquid membrane (PLM), are among the non-electrochemical methods largely used in this field and reviewed in the text. Under appropriate conditions such techniques make possible the evaluation of free metal ion concentration.

Review on landfill leachate treatment by electrochemical oxidation: Drawbacks, challenges and future scope.

PubMed

Mandal, Pubali; Dubey, Brajesh K; Gupta, Ashok K

2017-11-01

Various studies on landfill leachate treatment by electrochemical oxidation have indicated that this process can effectively reduce two major pollutants present in landfill leachate; organic matter and ammonium nitrogen. In addition, the process is able to enhance the biodegradability index (BOD/COD) of landfill leachate, which make mature or stabilized landfill leachate suitable for biological treatment. The elevated concentration of ammonium nitrogen especially observed in bioreactor landfill leachate can also be reduced by electrochemical oxidation. The pollutant removal efficiency of the system depends upon the mechanism of oxidation (direct or indirect oxidation) which depends upon the property of anode material. Applied current density, pH, type and concentration of electrolyte, inter-electrode gap, mass transfer mode, total anode area to volume of effluent to be treated ratio, temperature, flow rate or flow velocity, reactor geometry, cathode material and lamp power during photoelectrochemical oxidation may also influence the system performance. In this review paper, past and present scenarios of landfill leachate treatment efficiencies and costs of various lab scale, pilot scale electrochemical oxidation studies asa standalone system or integrated with biological and physicochemical processes have been reviewed with the conclusion that electrochemical oxidation can be employed asa complementary treatment system with biological process for conventional landfill leachate treatment as well asa standalone system for ammonium nitrogen removal from bioreactor landfill leachate. Furthermore, present drawbacks of electrochemical oxidation process asa landfill leachate treatment system and relevance of incorporating life cycle assessment into the decision-making process besides process efficiency and cost, have been discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solar promoted azo dye degradation and energy production in the bio-photoelectrochemical system with a g-C3N4/BiOBr heterojunction photocathode

NASA Astrophysics Data System (ADS)

Hou, Yanping; Gan, Yuanyuan; Yu, Zebin; Chen, Xixi; Qian, Lun; Zhang, Boge; Huang, Lirong; Huang, Jun

2017-12-01

In this study, a single-chamber bio-photoelectrochemical system (BPES), integrating advantages of bioelectrochemical system and photocatalysis process, is developed using a g-C3N4/BiOBr heterojunction photocathode for methyl orange (MO) degradation and simultaneous energy recovery. Photocatalytic activities of g-C3N4/BiOBr, g-C3N4 and BiOBr are characterized by UV-vis diffuse reflectance spectra (UV-vis DRS) and Photoluminescence (PL) spectra; and electrochemical activities of photocathodes are examined by linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Results show that with an applied voltage of 0.8 V and under simulated solar irradiation, MO decolorization with g-C3N4/BiOBr photocathode reaches 97.8% within 4 h, higher than those with g-C3N4 (85.3%) and BiOBr (87.3%) photocathodes. Likewise, higher hydrogen production rate (143.8 L m-3d-1) is observed using g-C3N4/BiOBr photocathode; while values for g-C3N4 and BiOBr photocathodes are 124.3 L m-3d-1 and 117.1 L m-3d-1, respectively. PL and EIS reveal that superior performance of g-C3N4/BiOBr photocathode can be attributed to more efficient separation of photogenerated electron-hole pairs, lower resistance and better charge transfer. Synergistic effect occurs among biological, electrochemical and photocatalytic processes in illuminated BPES for MO removal. Photocathode optimization and system stability evaluation are conducted. This study demonstrates that the BPES holds great potential for efficient refractory organics degradation and energy production.

Seeing through walls at the nanoscale: Microwave microscopy of enclosed objects and processes in liquids

DOE PAGES

Velmurugan, Jeyavel; Kalinin, Sergei V.; Kolmakov, Andrei; ...

2016-02-11

Here, noninvasive in situ nanoscale imaging in liquid environments is a current imperative in the analysis of delicate biomedical objects and electrochemical processes at reactive liquid–solid interfaces. Microwaves of a few gigahertz frequencies offer photons with energies of ≈10 μeV, which can affect neither electronic states nor chemical bonds in condensed matter. Here, we describe an implementation of scanning near-field microwave microscopy for imaging in liquids using ultrathin molecular impermeable membranes separating scanning probes from samples enclosed in environmental cells. We imaged a model electroplating reaction as well as individual live cells. Through a side-by-side comparison of the microwave imagingmore » with scanning electron microscopy, we demonstrate the advantage of microwaves for artifact-free imaging.« less

A reactive distillation process for the treatment of LiCl-KCl eutectic waste salt containing rare earth chlorides

NASA Astrophysics Data System (ADS)

Eun, H. C.; Choi, J. H.; Kim, N. Y.; Lee, T. K.; Han, S. Y.; Lee, K. R.; Park, H. S.; Ahn, D. H.

2016-11-01

The pyrochemical process, which recovers useful resources (U/TRU metals) from used nuclear fuel using an electrochemical method, generates LiCl-KCl eutectic waste salt containing radioactive rare earth chlorides (RECl3). It is necessary to develop a simple process for the treatment of LiCl-KCl eutectic waste salt in a hot-cell facility. For this reason, a reactive distillation process using a chemical agent was achieved as a method to separate rare earths from the LiCl-KCl waste salt. Before conducting the reactive distillation, thermodynamic equilibrium behaviors of the reactions between rare earth (Nd, La, Ce, Pr) chlorides and the chemical agent (K2CO3) were predicted using software. The addition of the chemical agent was determined to separate the rare earth chlorides into an oxide form using these equilibrium results. In the reactive distillation test, the rare earth chlorides in LiCl-KCl eutectic salt were decontaminated at a decontamination factor (DF) of more than 5000, and were mainly converted into oxide (Nd2O3, CeO2, La2O3, Pr2O3) or oxychloride (LaOCl, PrOCl) forms. The LiCl-KCl was purified into a form with a very low concentration (<1 ppm) for the rare earth chlorides.

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.

Solar Thermo-coupled Electrochemical Oxidation of Aniline in Wastewater for the Complete Mineralization Beyond an Anodic Passivation Film.

PubMed

Yuan, Dandan; Tian, Lei; Li, Zhida; Jiang, Hong; Yan, Chao; Dong, Jing; Wu, Hongjun; Wang, Baohui

2018-02-15

Herein, we report the solar thermal electrochemical process (STEP) aniline oxidation in wastewater for totally solving the two key obstacles of the huge energy consumption and passivation film in the electrochemical treatment. The process, fully driven by solar energy without input of any other energies, sustainably serves as an efficient thermoelectrochemical oxidation of aniline by the control of the thermochemical and electrochemical coordination. The thermocoupled electrochemical oxidation of aniline achieved a fast rate and high efficiency for the full minimization of aniline to CO 2 with the stability of the electrode and without formation of polyaniline (PAN) passivation film. A clear mechanism of aniline oxidation indicated a switching of the reactive pathway by the STEP process. Due to the coupling of solar thermochemistry and electrochemistry, the electrochemical current remained stable, significantly improving the oxidation efficiency and mineralization rate by apparently decreasing the electrolytic potential when applied with high temperature. The oxidation rate of aniline and chemical oxygen demand (COD) removal rate could be lifted up to 2.03 and 2.47 times magnification compared to conventional electrolysis, respectively. We demonstrate that solar-driven STEP processes are capable of completely mineralizing aniline with high utilization of solar energy. STEP aniline oxidation can be utilized as a green, sustainable water treatment.

Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents.

PubMed

Tessensohn, Malcolm E; Lee, Melvyn; Hirao, Hajime; Webster, Richard D

2015-01-12

Voltammetric experiments with 9,10-anthraquinone and 1,4-benzoquinone performed under controlled moisture conditions indicate that the hydrogen-bond strengths of alcohols in aprotic organic solvents can be differentiated by the electrochemical parameter ΔEp (red) =|Ep (red(1)) -Ep (red(2)) |, which is the potential separation between the two one-electron reduction processes. This electrochemical parameter is inversely related to the strength of the interactions and can be used to differentiate between primary, secondary, tertiary alcohols, and even diols, as it is sensitive to both their steric and electronic properties. The results are highly reproducible across two solvents with substantially different hydrogen-bonding properties (CH3 CN and CH2 Cl2 ) and are supported by density functional theory calculations. This indicates that the numerous solvent-alcohol interactions are less significant than the quinone-alcohol hydrogen-bonding interactions. The utility of ΔEp (red) was illustrated by comparisons between 1) 3,3,3-trifluoro-n-propanol and 1,3-difluoroisopropanol and 2) ethylene glycol and 2,2,2-trifluoroethanol. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

pH-switchable electrochemical sensing platform based on chitosan-reduced graphene oxide/concanavalin a layer for assay of glucose and urea.

PubMed

Song, Yonghai; Liu, Hongyu; Tan, Hongliang; Xu, Fugang; Jia, Jianbo; Zhang, Lixue; Li, Zhuang; Wang, Li

2014-02-18

A facile and effective electrochemical sensing platform for the detection of glucose and urea in one sample without separation was developed using chitosan-reduced graphene oxide (CS-rGO)/concanavalin A (Con A) as a sensing layer. The CS-rGO/Con A with pH-dependent surface net charges exhibited pH-switchable response to negatively charged Fe(CN)6(3-). The principle for glucose and urea detection was essentially based on in situ pH-switchable enzyme-catalyzed reaction in which the oxidation of glucose catalyzed by glucose oxidase or the hydrolyzation of urea catalyzed by urease resulted in a pH change of electrolyte solution to give different electrochemical responses toward Fe(CN)6(3-). It was verified by cyclic voltammograms, differential pulse voltammograms, and electrochemical impedance spectroscopy. The resistance to charge transfer or amperometric current changed proportionally toward glucose concentration from 1.0 to 10.0 mM and urea concentration from 1.0 to 7.0 mM. On the basis of human serum experiments, the sensing platform was proved to be suitable for simultaneous assay of glucose and urea in a practical biosystem. This work not only gives a way to detect glucose and urea in one sample without separation but also provides a potential strategy for the detection of nonelectroactive species based on the enzyme-catalyzed reaction and pH-switchable biosensor.

Novel Nanofiber-based Membrane Separators for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Yanilmaz, Meltem

Lithium-ion batteries have been widely used in electronic devices including mobile phones, laptop computers, and cameras due to their high specific energy, high energy density, long cycling lifetime, and low self-discharge rate. Nowadays, lithium-ion batteries are finding new applications in electric/hybrid vehicles and energy storage for smart grids. To be used in these new applications, novel battery components are needed so that lithiumion batteries with higher cell performance, better safety, and lower cost can be developed. A separator is an important component to obtain safe batteries and its primary function is to prevent electronic contact between electrodes while regulating cell kinetics and ionic flow. Currently, microporous membranes are the most commonly used separator type and they have good mechanical properties and chemical stability. However, their wettability and thermal stabilities are not sufficient for applications that require high operating temperature and high performance. Due to the superior properties such as large specific surface area, small pore size and high porosity, electrospun nanofiber membranes can be good separator candidate for highperformance lithium-ion batteries. In this work, we focus our research on fabricating nanofiber-based membranes to design new high-performance separators with good thermal stability, as well as superior electrochemical performance compared to microporous polyolefin membranes. To combine the good mechanical strength of PP nonwovens with the excellent electrochemical properties of SiO2/polyvinylidene fluoride (PVDF) composite nanofibers, SiO 2/PVDF composite nanofiber-coated PP nonwoven membranes were prepared. It was found that the addition of SiO2 nanoparticles played an important role in improving the overall performance of these nanofiber-coated nonwoven membranes. Although ceramic/polymer composites can be prepared by encapsulating ceramic particles directly into polymer nanofibers, the performance of the resultant composite membranes is restricted because these nanoparticles are not exposed to liquid electrolytes and have limited effect on improving the cell performance. Hence, we introduced new nanoparticle-on-nanofiber hybrid membrane separators by combining electrospraying with electrospinning techniques. Electrochemical properties were enhanced due to the increased surface area caused by the unique hybrid structure of SiO2 nanoparticles and PVDF nanofibers. To design a high-performance separator with enhanced mechanical properties and good thermal stability, electrospun SiO2/nylon 6,6 nanofiber membranes were fabricated. It was found that SiO2/nylon 6,6 nanofiber membranes had superior thermal stability and mechanical strength. Electrospinning has serious drawbacks such as low spinning rate and high production cost. Centrifugal spinning is a fast, cost-effective and safe alternative to the electrospinning. SiO2/polyacrylonitrile (PAN) membranes were produced by using centrifugal spinning. Compared with commercial microporous polyolefin membranes, SiO2/PAN membranes had larger liquid electrolyte uptake, higher electrochemical oxidation limit, and lower interfacial resistance with lithium. SiO2/PAN membrane separators were assembled into lithium/lithium iron phosphate cells and these cells exhibited good cycling and C-rate performance.

Reversible mechano-electrochemical writing of metallic nanostructures with the tip of an atomic force microscope.

PubMed

Obermair, Christian; Kress, Marina; Wagner, Andreas; Schimmel, Thomas

2012-01-01

We recently introduced a method that allows the controlled deposition of nanoscale metallic patterns at defined locations using the tip of an atomic force microscope (AFM) as a "mechano-electrochemical pen", locally activating a passivated substrate surface for site-selective electrochemical deposition. Here, we demonstrate the reversibility of this process and study the long-term stability of the resulting metallic structures. The remarkable stability for more than 1.5 years under ambient air without any observable changes can be attributed to self-passivation. After AFM-activated electrochemical deposition of copper nanostructures on a polycrystalline gold film and subsequent AFM imaging, the copper nanostructures could be dissolved by reversing the electrochemical potential. Subsequent AFM-tip-activated deposition of different copper nanostructures at the same location where the previous structures were deleted, shows that there is no observable memory effect, i.e., no effect of the previous writing process on the subsequent writing process. Thus, the four processes required for reversible information storage, "write", "read", "delete" and "re-write", were successfully demonstrated on the nanometer scale.

Reversible mechano-electrochemical writing of metallic nanostructures with the tip of an atomic force microscope

PubMed Central

Kress, Marina; Wagner, Andreas; Schimmel, Thomas

2012-01-01

Summary We recently introduced a method that allows the controlled deposition of nanoscale metallic patterns at defined locations using the tip of an atomic force microscope (AFM) as a “mechano-electrochemical pen”, locally activating a passivated substrate surface for site-selective electrochemical deposition. Here, we demonstrate the reversibility of this process and study the long-term stability of the resulting metallic structures. The remarkable stability for more than 1.5 years under ambient air without any observable changes can be attributed to self-passivation. After AFM-activated electrochemical deposition of copper nanostructures on a polycrystalline gold film and subsequent AFM imaging, the copper nanostructures could be dissolved by reversing the electrochemical potential. Subsequent AFM-tip-activated deposition of different copper nanostructures at the same location where the previous structures were deleted, shows that there is no observable memory effect, i.e., no effect of the previous writing process on the subsequent writing process. Thus, the four processes required for reversible information storage, “write”, “read”, “delete” and “re-write”, were successfully demonstrated on the nanometer scale. PMID:23365795

Self-doped microphase separated block copolymer electrolyte

DOEpatents

Mayes, Anne M.; Sadoway, Donald R.; Banerjee, Pallab; Soo, Philip; Huang, Biying

2002-01-01

A polymer electrolyte includes a self-doped microphase separated block copolymer including at least one ionically conductive block and at least one second block that is immiscible in the ionically conductive block, an anion immobilized on the polymer electrolyte and a cationic species. The ionically conductive block provides a continuous ionically conductive pathway through the electrolyte. The electrolyte may be used as an electrolyte in an electrochemical cell.

Graphitized-carbon fiber/carbon char fuel

DOEpatents

Cooper, John F [Oakland, CA

2007-08-28

A method for recovery of intact graphitic fibers from fiber/polymer composites is described. The method comprises first pyrolyzing the graphite fiber/polymer composite mixture and then separating the graphite fibers by molten salt electrochemical oxidation.

In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

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

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

2016-11-07

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

Conversion of Carbon Dioxide into Ethanol by Electrochemical Synthesis Method Using Cu-Zn Electrode

NASA Astrophysics Data System (ADS)

Riyanto; Ramadan, S.; Fariduddin, S.; Aminudin, A. R.; Hayatri, A. K.

2018-01-01

Research on conversion of carbon dioxide into ethanol has been done. The conversion process is carried out in a sodium bicarbonate electrolyte solution in an electrochemical synthesis reactor. As cathode was used Cu-Zn, while as anode carbon was utilized. Variations of voltage, concentration of sodium bicarbonate electrolyte solution and time of electrolysis were performed to determine the optimum conditions to convert carbon dioxide into ethanol. Sample of the electrochemical synthesis process was analyzed by gas chromatography. From the result, it is found that the optimum conditions of the electrochemical synthesis process of carbon dioxide conversion into ethanol are voltage, concentration of sodium bicarbonate electrolyte solution and time of electrolysis are 3 volts, 0.4 M and 90 minutes with the ethanol concentration of 10.44%.

Creating an Electronic Reference and Information Database for Computer-aided ECM Design

NASA Astrophysics Data System (ADS)

Nekhoroshev, M. V.; Pronichev, N. D.; Smirnov, G. V.

2018-01-01

The paper presents a review on electrochemical shaping. An algorithm has been developed to implement a computer shaping model applicable to pulse electrochemical machining. For that purpose, the characteristics of pulse current occurring in electrochemical machining of aviation materials have been studied. Based on integrating the experimental results and comprehensive electrochemical machining process data modeling, a subsystem for computer-aided design of electrochemical machining for gas turbine engine blades has been developed; the subsystem was implemented in the Teamcenter PLM system.

Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same

DOEpatents

Xing, Weibing; Buettner-Garrett, Josh

2017-04-18

This disclosure relates generally to cathode materials for electrochemical energy cells, more particularly to metal/air electrochemical energy cell cathode materials containing silver vanadium oxide and methods of making and using the same. The metal/air electrochemical energy cell can be a lithium/air electrochemical energy cell. Moreover the silver vanadium oxide can be a catalyst for one or more of oxidation and reduction processes of the electrochemical energy cell.

Flow injection trace gas analysis method for on-site determination of organoarsenicals

DOEpatents

Aldstadt, J.H. III

1997-06-24

A method is described for real-time determination of the concentration of Lewisite in the ambient atmosphere, the method includes separating and collecting a Lewisite sample from the atmosphere in a collection chamber, converting the collected Lewisite to an arsenite ion solution sample, pumping the arsenite ion containing sample to an electrochemical detector connected to the collection chamber, and electrochemically detecting the converted arsenite ions in the sample, whereby the concentration of arsenite ions detected is proportional to the concentration of Lewisite in the atmosphere. 2 figs.

Electrochemical photovoltaic cells and electrodes

DOEpatents

Skotheim, Terje A.

1984-01-01

Improved electrochemical photovoltaic cells and electrodes for use therein, particularly electrodes employing amorphous silicon or polyacetylene coating are produced by a process which includes filling pinholes or porous openings in the coatings by electrochemical oxidation of selected monomers to deposit insulating polymer in the openings.

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.

The thermodynamics of pyrochemical processes for liquid metal reactor fuel cycles

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

Johnson, I.

1987-01-01

The thermodynamic basis for pyrochemical processes for the recovery and purification of fuel for the liquid metal reactor fuel cycle is described. These processes involve the transport of the uranium and plutonium from one liquid alloy to another through a molten salt. The processes discussed use liquid alloys of cadmium, zinc, and magnesium and molten chloride salts. The oxidation-reduction steps are done either chemically by the use of an auxiliary redox couple or electrochemically by the use of an external electrical supply. The same basic thermodynamics apply to both the salt transport and the electrotransport processes. Large deviations from idealmore » solution behavior of the actinides and lanthanides in the liquid alloys have a major influence on the solubilities and the performance of both the salt transport and electrotransport processes. Separation of plutonium and uranium from each other and decontamination from the more noble fission product elements can be achieved using both transport processes. The thermodynamic analysis is used to make process design computations for different process conditions.« less

Glass composition and process for sealing void spaces in electrochemical devices

DOEpatents

Meinhardt, Kerry D [Richland, WA; Kirby, Brent W [Kennewick, WA

2012-05-01

A glass foaming material and method are disclosed for filling void spaces in electrochemical devices. The glass material includes a reagent that foams at a temperature above the softening point of the glass. Expansion of the glass fills void spaces including by-pass and tolerance channels of electrochemical devices. In addition, cassette to cassette seals can also be formed while channels and other void spaces are filled, reducing the number of processing steps needed.

Electrochromic devices

DOEpatents

Allemand, Pierre M.; Grimes, Randall F.; Ingle, Andrew R.; Cronin, John P.; Kennedy, Steve R.; Agrawal, Anoop; Boulton, Jonathan M.

2001-01-01

An electrochromic device is disclosed having a selective ion transport layer which separates an electrochemically active material from an electrolyte containing a redox active material. The devices are particularly useful as large area architectural and automotive glazings due to there reduced back reaction.

Determination of phenolic constituents of biological interest in red wine by capillary electrophoresis with electrochemical detection.

PubMed

Peng, Youyuan; Chu, Qingcui; Liu, Fanghua; Ye, Jiannong

2004-01-28

A simultaneous determination of trans-resveratrol, (-)-epicatechin, and (+)-catechin in red wine by capillary electrophoresis with electrochemical detection (CE-ED) is reported. The effects of the potential of the working electrode, pH and concentration of running buffer, separation voltage, and injection time on CE-ED were investigated. Under the optimum conditions, the analytes could be separated in a 100 mmol/L borate buffer (pH 9.2) within 20 min. A 300 microm diameter carbon disk electrode has a good response at +0.85 V (vs SCE) for all analytes. The response was linear over 3 orders of magnitude with detection limit (S/N = 3) ranging from 2 x 10(-7) to 5 x 10(-7) g/mL for all analytes. This method has been used for the determination of these analytes in red wine without enrichment, and the assay result was satisfactory.

ELECTROCHEMICAL REMEDIATION TECHNOLOGIES (ECRTS) DEMONSTRATION BULLETIN

EPA Science Inventory

The ElectroChemical Remediation Technologies (ECRTs) process was developed by P2-Soil Remediation, Inc. P-2 Soil Remediation, Inc. formed a partnership with Weiss Associates and ElectroPetroleum, Inc. to apply the technology to contaminated sites. The ECRTs process was evaluated ...

Methods and systems for in-situ electroplating of electrodes

DOEpatents

Zappi, Guillermo Daniel; Zarnoch, Kenneth Paul; Huntley, Christian Andrew; Swalla, Dana Ray

2015-06-02

The present techniques provide electrochemical devices having enhanced electrodes with surfaces that facilitate operation, such as by formation of a porous nickel layer on an operative surface, particularly of the cathode. The porous metal layer increases the surface area of the electrode, which may result in increasing the efficiency of the electrochemical devices. The formation of the porous metal layer is performed in situ, that is, after the assembly of the electrodes into an electrochemical device. The in situ process offers a number of advantages, including the ability to protect the porous metal layer on the electrode surface from damage during assembly of the electrochemical device. The enhanced electrode and the method for its processing may be used in any number of electrochemical devices, and is particularly well suited for electrodes in an electrolyzer useful for splitting water into hydrogen and oxygen.

Occurrence and Removal of Organic Micropollutants in Landfill Leachates Treated by Electrochemical Advanced Oxidation Processes.

PubMed

Oturan, Nihal; van Hullebusch, Eric D; Zhang, Hui; Mazeas, Laurent; Budzinski, Hélène; Le Menach, Karyn; Oturan, Mehmet A

2015-10-20

In recent years, electrochemical advanced oxidation processes have been shown to be an effective alternative for the removal of refractory organic compounds from water. This study is focused on the effective removal of recalcitrant organic matter (micropollutants, humic substances, etc.) present in municipal solid waste landfill leachates. A mixture of eight landfill leachates has been studied by the electro-Fenton process using a Pt or boron-doped diamond (BDD) anode and a carbon felt cathode or by the anodic oxidation process with a BDD anode. These processes exhibit great oxidation ability due to the in situ production of hydroxyl radicals ((•)OH), a highly powerful oxidizing species. Both electrochemical processes were shown to be efficient in the removal of dissolved total organic carbon (TOC) from landfill leachates. Regarding the electro-Fenton process, the replacement of the classical anode Pt by the anode BDD allows better performance in terms of dissolved TOC removal. The occurrence and removal yield of 19 polycyclic aromatic hydrocarbons, 15 volatile organic compounds, 7 alkylphenols, 7 polychlorobiphenyls, 5 organochlorine pesticides, and 2 polybrominated diphenyl ethers in landfill leachate were also investigated. Both electrochemical processes allow one to reach a quasicomplete removal (about 98%) of these organic micropollutants.

Electrochemical Induced Calcium Phosphate Precipitation: Importance of Local pH

PubMed Central

2017-01-01

Phosphorus (P) is an essential nutrient for living organisms and cannot be replaced or substituted. In this paper, we present a simple yet efficient membrane free electrochemical system for P removal and recovery as calcium phosphate (CaP). This method relies on in situ formation of hydroxide ions by electro mediated water reduction at a titanium cathode surface. The in situ raised pH at the cathode provides a local environment where CaP will become highly supersaturated. Therefore, homogeneous and heterogeneous nucleation of CaP occurs near and at the cathode surface. Because of the local high pH, the P removal behavior is not sensitive to bulk solution pH and therefore, efficient P removal was observed in three studied bulk solutions with pH of 4.0 (56.1%), 8.2 (57.4%), and 10.0 (48.4%) after 24 h of reaction time. While P removal efficiencies are not generally affected by bulk solution pH, the chemical-physical properties of CaP solids collected on the cathode are still related to bulk solution pH, as confirmed by structure characterizations. High initial solution pH promotes the formation of more crystalline products with relatively high Ca/P molar ratio. The Ca/P molar ratio increases from 1.30 (pH 4.0) to 1.38 (pH 8.2) and further increases to 1.55 (pH 10.0). The formation of CaP precipitates was a typical crystallization process, with an amorphous phase formed at the initial stage which then transforms to the most stable crystal phase, hydroxyapatite, which is inferred from the increased Ca/P molar ratio from 1.38 (day 1) to the theoretical 1.76 (day 11) and by the formation of needle-like crystals. Finally, we demonstrated the efficiency of this system for real wastewater. This, together with the fact that the electrochemical method can work at low bulk pH, without dosing chemicals and a need for a separation process, highlights the potential application of the electrochemical method for P removal and recovery. PMID:28872838

Processing of Onion-like Carbon for Electrochemical Capacitors

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

Van Aken, Katherine L.; Maleski, Kathleen; Mathis, Tyler S.

Multi-shell fullerenes known as onion-like carbon (OLC) are especially attractive in applications relative to energy storage, such as electrochemical capacitors, due to a near-spherical shape of particles, their nanoscale diameters and high conductivity leading to fast rate performance. Because of this, onion-like carbon can be fabricated into electrodes, used as a conductive additive, and may have potential in composites and additive manufacturing. However due to agglomeration of OLC particles, creating a stable, aqueous dispersion for ink production or formulating composites proves challenging. Also, we explore how attrition milling, acid treatment, and probe sonication can be employed to decrease agglomeration andmore » provide colloidal stability in aqueous media. We also investigate how the electrochemical performance changes with each processing step as well as the treatments in succession. When tested in electrochemical capacitors, the processing increases the capacitance by a factor of three, due to an added pseudocapacitive contribution which is not present in untreated OLC. As a result, the processing of OLC proves to be advantageous for the production of stable, aqueous solutions, which also exhibit improved electrochemical properties suitable for functional inks, conductive additives, and fabrication of composite electrodes.« less

Processing of Onion-like Carbon for Electrochemical Capacitors

DOE PAGES

Van Aken, Katherine L.; Maleski, Kathleen; Mathis, Tyler S.; ...

2017-02-04

Multi-shell fullerenes known as onion-like carbon (OLC) are especially attractive in applications relative to energy storage, such as electrochemical capacitors, due to a near-spherical shape of particles, their nanoscale diameters and high conductivity leading to fast rate performance. Because of this, onion-like carbon can be fabricated into electrodes, used as a conductive additive, and may have potential in composites and additive manufacturing. However due to agglomeration of OLC particles, creating a stable, aqueous dispersion for ink production or formulating composites proves challenging. Also, we explore how attrition milling, acid treatment, and probe sonication can be employed to decrease agglomeration andmore » provide colloidal stability in aqueous media. We also investigate how the electrochemical performance changes with each processing step as well as the treatments in succession. When tested in electrochemical capacitors, the processing increases the capacitance by a factor of three, due to an added pseudocapacitive contribution which is not present in untreated OLC. As a result, the processing of OLC proves to be advantageous for the production of stable, aqueous solutions, which also exhibit improved electrochemical properties suitable for functional inks, conductive additives, and fabrication of composite electrodes.« less

Intense Electrochemical Oxidation on Graphitized Carbon Electrodes in the Presence of Ozone

NASA Astrophysics Data System (ADS)

Klochikhin, V. L.; Potapova, G. F.; Putilov, A. V.

2018-06-01

A new intense oxidation process for water treatment in which oxidation with ozone is coupled to electrochemical processes is described, and the results from its application to water purification are presented along with the discussion of its practical implementation. The use of graphitized carbon materials for this process is explained and tested experimentally. The use of glassy carbon for the anode enables us to achieve very high (up to 25 vol %) concentrations of ozone in the generated ozone-oxygen mixture. The material used for the cathode—graphitized carbon cloth (GCC) reinforced with Ni allows different electrocatalytic processes to proceed on its developed surface, and combines the high sorption capacity of this cathode and potentialcontrolled selectivity of cathodic electrochemical processes.

Electrochemical advanced oxidation processes as decentralized water treatment technologies to remediate domestic washing machine effluents.

PubMed

Dos Santos, Alexsandro Jhones; Costa, Emily Cintia Tossi de Araújo; da Silva, Djalma Ribeiro; Garcia-Segura, Sergi; Martínez-Huitle, Carlos Alberto

2018-03-01

Water scarcity is one of the major concerns worldwide. In order to secure this appreciated natural resource, management and development of water treatment technologies are mandatory. One feasible alternative is the consideration of water recycling/reuse at the household scale. Here, the treatment of actual washing machine effluent by electrochemical advanced oxidation processes was considered. Electrochemical oxidation and electro-Fenton technologies can be applied as decentralized small-scale water treatment devices. Therefore, efficient decolorization and total organic abatement have been followed. The results demonstrate the promising performance of solar photoelectro-Fenton process, where complete color and organic removal was attained after 240 min of treatment under optimum conditions by applying a current density of 66.6 mA cm -2 . Thus, electrochemical technologies emerge as promising water-sustainable approaches.

Mathematical modeling and hydrodynamics of Electrochemical deburring process

NASA Astrophysics Data System (ADS)

Prabhu, Satisha; Abhishek Kumar, K., Dr

2018-04-01

The electrochemical deburring (ECD) is a variation of electrochemical machining is considered as one of the efficient methods for deburring of intersecting features and internal parts. Since manual deburring costs are comparatively high one can potentially use this method in both batch production and flow production. The other advantage of this process is that time of deburring as is on the order of seconds as compared to other methods. In this paper, the mathematical modeling of Electrochemical deburring is analysed from its deburring time and base metal removal point of view. Simultaneously material removal rate is affected by electrolyte temperature and bubble formation. The mathematical model and hydrodynamics of the process throw limelight upon optimum velocity calculations which can be theoretically determined. The analysis can be the powerful tool for prediction of the above-mentioned parameters by experimentation.

A novel broadband impedance method for detection of cell-derived microparticles

PubMed Central

Lvovich, Vadim; Srikanthan, Sowmya; Silverstein, Roy L.

2010-01-01

A novel label-free method is presented to detect and quantify cell-derived microparticles (MPs) by the electrochemical potential-modulated electrochemical impedance spectroscopy (EIS). MPs are present in elevated concentrations during pathological conditions and play a major role in the establishment and pathogenesis of many diseases. Considering this, accurate detection and quantification of MPs is very important in clinical diagnostics and therapeutics. A combination of bulk solution electrokinetic sorting and interfacial impedance responses allows achieving detection limits as low as several MPs per µL. By fitting resulting EIS spectra with an equivalent electrical circuit, the bulk solution electrokinetic and interfacial impedance responses were characterized. In the bulk solution two major relaxations were prominent - β-relaxation in low MHz region due to the MP capacitive membrane bridging, and α-relaxation at ∼ 10 kHz due to counter ions diffusion. At low frequencies (10-0.1 Hz) at electrochemical potentials exceeding −100 mV, a facile interfacial Faradaic process of oxidation in MPs coupled with diffusion and non Faradaic double layer charging dominate, probably due to oxidation of phospholipids and/or proteins on the MP surface and MP lysis. Buffer influence on the MP detection demonstrated that that a relatively low conductivity Tyrode’s buffer background solution is preferential for the MP electrokinetic separation and characterization. This study also demonstrated that standard laboratory methods such as flow cytometry underestimate MP concentrations, especially those with smaller average sizes, by as much as a factor of 2 to 40. PMID:20729061

A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries.

PubMed

Zhang, Xihua; Xie, Yongbing; Cao, Hongbin; Nawaz, Faheem; Zhang, Yi

2014-09-01

To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminum foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15vol.% TFA solution, L/S ratio of 8.0 mL g(-1), reacting at 40°C for 180 min along with appropriate agitation. LiNi1/3Co1/3Mn1/3O2 is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi1/3Co1/3Mn1/3O2 powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi1/3Co1/3Mn1/3O2 are 201 mAh g(-)(1) and 155.4 mAh g(-1) (2.8-4.5 V, 0.1C), respectively. The discharge capacity remains at 129 mAh g(-1) even after 30 cycles with a capacity retention ratio of 83.01%. Copyright © 2014 Elsevier Ltd. All rights reserved.

A novel process for recycling and resynthesizing LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} from the cathode scraps intended for lithium-ion batteries

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

Zhang, Xihua; Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190; Beijing Engineering Research Center of Process Pollution Control, Beijing 100190

Highlights: • A simple process to recycle cathode scraps intended for lithium-ion batteries. • Complete separation of the cathode material from the aluminum foil is achieved. • The recovered aluminum foil is highly pure. • LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} is directly resynthesized from the separated cathode material. - Abstract: To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminummore » foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15 vol.% TFA solution, L/S ratio of 8.0 mL g{sup −1}, reacting at 40 °C for 180 min along with appropriate agitation. LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} are 201 mAh g{sup −1} and 155.4 mAh g{sup −1} (2.8–4.5 V, 0.1 C), respectively. The discharge capacity remains at 129 mAh g{sup −1} even after 30 cycles with a capacity retention ratio of 83.01%.« less

Polymer membranes as separators for supercapacitors

NASA Astrophysics Data System (ADS)

Szubzda, Bronisław; Szmaja, Aleksandra; Ozimek, Mariusz; Mazurkiewicz, Sławomir

2014-12-01

The purpose of the studies described was to examine the influence of low-energy plasma modification of polyamide and polypropylene polymer nonwoven fabrics on the usable properties of supercapacitors when using these fabrics as the separator material. To achieve this goal the following investigations were carried out: testing the time required for electrolyte saturation of separators and the conductivity of the electrolyte contained in the separator, as well as electrochemical examinations of supercapacitor models in which the modified fabric separators were used. The tests conducted fully confirm the usability of this modification for cleaning the surface and improving the wettability of separators by the electrolyte, which in turn results in a significant decrease of the internal resistance of the supercapacitor, thus increasing the usable power of the device.

Hydrogen Generator

NASA Technical Reports Server (NTRS)

1978-01-01

Another spinoff from spacecraft fuel cell technology is the portable hydrogen generator shown. Developed by General Electric Company, it is an aid to safer operation of systems that use hydrogen-for example, gas chromatographs, used in laboratory analysis of gases. or flame ionization detectors used as $ollution monitors. The generator eliminates the need for high-pressure hydrogen storage bottles, which can be a safety hazard, in laboratories, hospitals and industrial plants. The unit supplies high-purity hydrogen by means of an electrochemical process which separates the hydrogen and oxygen in distilled water. The oxygen is vented away and the hydrogen gas is stored within the unit for use as needed. GE's Aircraft Equipment Division is producing about 1,000 of the generators annually.

Concentration specific and tunable photoresponse of bismuth vanadate functionalized hexagonal ZnO nanocrystals based photoanodes for photoelectrochemical application

NASA Astrophysics Data System (ADS)

Singh, Sonal; Ruhela, Aakansha; Rani, Sanju; Khanuja, Manika; Sharma, Rishabh

2018-02-01

In the present work, dual layer BiVO4/ZnO photoanode is instigated for photo-electrochemical (PEC) water splitting applications. Two different photocatalytic layers ZnO and BiVO4, reduces charge carrier recombination and charge transfer resistance at photoanode/electrolyte junction. The concentration-specific, tunable and without 'spike and overshoot' features, photocurrent density response is originated by varying BiVO4 concentration in the BiVO4/ZnO photoanode. The crystal structure of ZnO (hexagonal wurtzite structure) and BiVO4 (monoclinic scheelite structure) is confirmed by X-ray diffraction studies. The band gap of BiVO4/ZnO was estimated to be ca. 2.42 eV through Kubler-Munk function F(R∞) using diffuse reflectance spectroscopy. Electrochemical behavior of samples was analyzed with photocurrent measurements, electrochemical impedance, Mott-Schottky plots, bulk separation efficiency and surface transfer efficiency. The maximum photocurrent density of BiVO4/ZnO photoanode was found to be 2.3 times higher than pristine ZnO sample.0.038 M BiVO4/ZnO exhibited the highest separation efficiency of 72% and surface transfer efficiency of 64.7% at +1.23 V vs. RHE. Mott-Schottky study revealed the maximum charge carrier density in the same sample.

Electrochemical study of aluminum corrosion in boiling high purity water

NASA Technical Reports Server (NTRS)

Draley, J. E.; Legault, R. A.

1969-01-01

Electrochemical study of aluminum corrosion in boiling high-purity water includes an equation relating current and electrochemical potential derived on the basis of a physical model of the corrosion process. The work involved an examination of the cathodic polarization behavior of 1100 aluminum during aqueous oxidation.

Electrochemical oxidation of ciprofloxacin in two different processes: the electron transfer process on the anode surface and the indirect oxidation process in bulk solutions.

PubMed

Shen, Bo; Wen, Xianghua; Korshin, Gregory V

2018-05-14

Herein, the rotating disk electrode technique was used for the first time to investigate the effects of mass-transfer limitations and pH on the electrochemical oxidation of CPX, to determine the kinetics of CPX oxidation and to explore intrinsic mechanisms during the electron transfer process. Firstly, cyclic voltammetry revealed that an obvious irreversible CPX oxidation peak was observed within the potential window from 0.70 to 1.30 V at all pHs. Based on the Levich equation, the electrochemical oxidation of CPX in the electron transfer process was found to be controlled by both diffusion and kinetic processes when pH = 2, 5, 7 and 9; the diffusion coefficient of CPX at pH = 2 was calculated to be 1.5 × 10-7 cm2 s-1. Kinetic analysis indicated that the reaction on the electrode surface was adsorption-controlled compared to a diffusion process; the surface concentration of electroactive species was estimated to be 1.15 × 10-9 mol cm-2, the standard rate constant of the surface reaction was calculated to be 1.37 s-1, and CPX oxidation was validated to be a two-electron transfer process. Finally, a possible CPX oxidation pathway during the electron transfer process was proposed. The electrochemical degradation of CPX on a Ti-based anode was also conducted subsequently to investigate the electrochemical oxidation of CPX in the indirect oxidation process in bulk solutions. The effects of pH and current density were determined and compared to related literature results. The oxidation of CPX at different pHs is believed to be the result of a counterbalance between favorable and unfavorable factors, namely electromigration and side reactions of oxygen evolution, respectively. The effects of current density indicated a diffusion- and reaction-controlled process at low currents followed by a reaction-controlled process at high currents. The results presented in this study provide better understanding of the electrochemical oxidation of CPX and would enable the development of new treatment methods based on electrochemistry.

The synthesis and properties of linear A-π-D-π-A type organic small molecule containing diketopyrrolopyrrole terminal units.

PubMed

Zhang, Shanshan; Niu, Qingfen; Sun, Tao; Li, Yang; Li, Tianduo; Liu, Haixia

2017-08-05

A novel linear A-π-D-π-A-type organic small molecule Ph2(PDPP) 2 consisting diketopyrrolopyrrole (DPP) as acceptor unit, biphenylene as donor unit and acetylene unit as π-linkage has been successfully designed and synthesized. Its corresponding thermal, photophysical and electrochemical properties as well as the photoinduced charge-separation process were investigated. Ph2(PDPP) 2 exhibits high thermal stability and it can be soluble in common organic solvents such as chloroform and tetrahydrofuran. The photophysical properties show that DPP 2 Ph 2 harvests sunlight over the entire visible spectrum range in the thin-film state (300-800nm). DPP 2 Ph 2 has lower band gaps and appropriate energy levels to satisfy the requirement of solution-processable organic solar cells. The efficient photoinduced charge separation process was clearly observed between DPP 2 Ph 2 with PC 61 BM and the K sv value was found to be as high as 2.13×10 4 M -1 . Therefore, these excellent properties demonstrate that the designed A-π-D-π-A-type small molecule Ph2(PDPP) 2 is the prospective candidate as donor material for organic photovoltaic material. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

The effect of strain hardening on resistance to electrochemical corrosion of wires for orthopaedics

NASA Astrophysics Data System (ADS)

Przondziono, J.; Walke, W.; Hadasik, E.; Szymszal, J.

2012-05-01

The purpose of this research is to evaluate electrochemical corrosion resistance of wire with modified surface, made of stainless steel of Cr-Ni-Mo type, widely used in implants for orthopaedics, depending on hardening created in the process of drawing. Tests have been carried out in the environment imitating human osseous tissue. Pitting corrosion was determined on the ground of registered anodic polarisation curves by means of potentiodynamic method with application of electrochemical testing system VoltaLab® PGP 201. Wire corrosion tests were carried out in Tyrode solution on samples that were electrochemically polished as well as electrochemically polished and finally chemically passivated. Initial material for tests was wire rod made of X2CrNiMo17-12-2 steel with diameter of 5.5 mm in supersaturated condition. Wire rod was drawn up to diameter of 1.35 mm. This work shows the course of flow curve of wire made of this grade of steel and mathematical form of yield stress function. The study also presents exemplary curves showing the dependence of polarisation resistance in strain function in the drawing process of electrochemically passivated and electrochemically polished and then chemically passivated wire.

Reuse of Textile Dyeing Effluents Treated with Coupled Nanofiltration and Electrochemical Processes

PubMed Central

Buscio, Valentina; García-Jiménez, María; Vilaseca, Mercè; López-Grimau, Victor; Crespi, Martí; Gutiérrez-Bouzán, Carmen

2016-01-01

The reactive dye Cibacron Yellow S-3R was selected to evaluate the feasibility of combining nanofiltration membranes with electrochemical processes to treat textile wastewater. Synthetic dyeing effluents were treated by means of two nanofiltration membranes, Hydracore10 and Hydracore50. Up to 98% of dye removal was achieved. The influence of salt concentration and pH on membrane treatment was studied. The best dye removal yield was achieved at pH 3 in the presence of 60 g/L of NaCl. After the membrane filtration, the concentrate containing high dye concentration was treated by means of an electrochemical process at three different current densities: 33, 83, and 166 mA/cm2. Results showed a lineal relationship between treatment time and applied current density. Both permeates and electrochemically-decoloured effluents were reused in new dyeing processes (100% of permeate and 70% of decoloured concentrates). Dyed fabrics were evaluated with respect to original dyeing. Colour differences were found to be into the acceptance range. PMID:28773614

SERS- and Electrochemically Active 3D Plasmonic Liquid Marbles for Molecular-Level Spectroelectrochemical Investigation of Microliter Reactions.

PubMed

Koh, Charlynn Sher Lin; Lee, Hiang Kwee; Phan-Quang, Gia Chuong; Han, Xuemei; Lee, Mian Rong; Yang, Zhe; Ling, Xing Yi

2017-07-17

Liquid marbles are emergent microreactors owing to their isolated environment and the flexibility of materials used. Plasmonic liquid marbles (PLMs) are demonstrated as the smallest spectroelectrochemical microliter-scale reactor for concurrent spectro- and electrochemical analyses. The three-dimensional Ag shell of PLMs are exploited as a bifunctional surface-enhanced Raman scattering (SERS) platform and working electrode for redox process modulation. The combination of SERS and electrochemistry (EC) capabilities enables in situ molecular read-out of transient electrochemical species, and elucidate the potential-dependent and multi-step reaction dynamics. The 3D configuration of our PLM-based EC-SERS system exhibits 2-fold and 10-fold superior electrochemical and SERS performance than conventional 2D platforms. The rich molecular-level electrochemical insights and excellent EC-SERS capabilities offered by our 3D spectroelectrochemical system are pertinent in charge transfer processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

PubMed

He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

2016-06-08

Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability.

Cell separator for use in bipolar-stack energy storage devices

DOEpatents

Mayer, Steven T.; Feikert, John H.; Kachmitter, James L.; Pekala, Richard W.

1995-01-01

An improved multi-cell electrochemical energy storage device, such as a battery, fuel cell, or double layer capacitor using a cell separator which allows cells to be stacked and interconnected with low electrical resistance and high reliability while maximizing packaging efficiency. By adding repeating cells, higher voltages can be obtained. The cell separator is formed by applying an organic adhesive on opposing surfaces of adjacent carbon electrodes or surfaces of aerogel electrodes of a pair of adjacent cells prior to or after pyrolysis thereof to form carbon aerogel electrodes. The cell separator is electronically conductive, but ionically isolating, preventing an electrolytic conduction path between adjacent cells in the stack.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development of Self-Powered Wireless-Ready High Temperature Electrochemical Sensors for In-Situ Corrosion Monitoring for Boiler Tubes in Next Generation Coal-based Power Systems

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

Liu, Xingbo

The key innovation of this project is the synergy of the high temperature sensor technology based on the science of electrochemical measurement and state-of-the-art wireless communication technology. A novel self-powered wireless high temperature electrochemical sensor system has been developed for coal-fired boilers used for power generation. An initial prototype of the in-situ sensor demonstrated the capability of the wireless communication system in the laboratory and in a pilot plant (Industrial USC Boiler Setting) environment to acquire electrochemical potential and current signals during the corrosion process. Uniform and localized under-coal ash deposit corrosion behavior of Inconel 740 superalloy has been studiedmore » at different simulated coal ash hot corrosion environments using the developed sensor. Two typical potential noise patterns were found to correlate with the oxidation and sulfidation stages in the hot coal ash corrosion process. Two characteristic current noise patterns indicate the extent of the corrosion. There was a good correlation between the responses of electrochemical test data and the results from corroded surface analysis. Wireless electrochemical potential and current noise signals from a simulated coal ash hot corrosion process were concurrently transmitted and recorded. The results from the performance evaluation of the sensor confirm a high accuracy in the thermodynamic and kinetic response represented by the electrochemical noise and impedance test data.« less

Dynamic and galvanic stability of stretchable supercapacitors.

PubMed

Li, Xin; Gu, Taoli; Wei, Bingqing

2012-12-12

Stretchable electronics are emerging as a new technological advancement, since they can be reversibly stretched while maintaining functionality. To power stretchable electronics, rechargeable and stretchable energy storage devices become a necessity. Here, we demonstrate a facile and scalable fabrication of full stretchable supercapacitor, using buckled single-walled carbon nanotube macrofilms as the electrodes, an electrospun membrane of elastomeric polyurethane as the separator, and an organic electrolyte. We examine the electrochemical performance of the fully stretchable supercapacitors under dynamic stretching/releasing modes in different stretching strain rates, which reveal the true performance of the stretchable cells, compared to the conventional method of testing the cells under a statically stretched state. In addition, the self-discharge of the supercapacitor and the electrochemical behavior under bending mode are also examined. The stretchable supercapacitors show excellent cyclic stability under electrochemical charge/discharge during in situ dynamic stretching/releasing.

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.

Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

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

Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.

Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and massmore » of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag + is reduced to Ag 0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the kinetically and thermodynamically preferred reduction processes at various states of discharge is critical to elucidating the mechanism. Specific advanced in-situ and ex-situ characterization techniques are conducive to gaining insight regarding the electrochemical behavior of these multifunctional materials over multiple length scales. At the material level, optical microscopy, scanning electron microscopy, and local conductivity measurement via a nanoprobe can track the discharge mechanism of an isolated single particle. At the mesoscale electrode level, in-situ data from synchrotron based energy dispersive X-ray diffraction (EDXRD) within fully intact steel batteries can be used to spatially map the distribution of silver metal generated through reduction displacement as a function of discharge depth and discharge rate. As illustrated here, appropriate design of materials with multiple electrochemically active metal centers and properties tuned through strategically conceptualized materials synthesis may provide a path toward the next generation of high energy content electroactive materials and systems. In conclusion, full understanding of the multiple electrochemical mechanisms can be achieved only by utilizing advanced characterization tools over multiple length scales.« less

Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

DOE PAGES

Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.; ...

2016-08-26

Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and massmore » of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag + is reduced to Ag 0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the kinetically and thermodynamically preferred reduction processes at various states of discharge is critical to elucidating the mechanism. Specific advanced in-situ and ex-situ characterization techniques are conducive to gaining insight regarding the electrochemical behavior of these multifunctional materials over multiple length scales. At the material level, optical microscopy, scanning electron microscopy, and local conductivity measurement via a nanoprobe can track the discharge mechanism of an isolated single particle. At the mesoscale electrode level, in-situ data from synchrotron based energy dispersive X-ray diffraction (EDXRD) within fully intact steel batteries can be used to spatially map the distribution of silver metal generated through reduction displacement as a function of discharge depth and discharge rate. As illustrated here, appropriate design of materials with multiple electrochemically active metal centers and properties tuned through strategically conceptualized materials synthesis may provide a path toward the next generation of high energy content electroactive materials and systems. In conclusion, full understanding of the multiple electrochemical mechanisms can be achieved only by utilizing advanced characterization tools over multiple length scales.« less

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

NASA Astrophysics Data System (ADS)

Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

2013-04-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes.

PubMed

Kumar, Amit; Arruda, Thomas M; Tselev, Alexander; Ivanov, Ilia N; Lawton, Jamie S; Zawodzinski, Thomas A; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V

2013-01-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

PubMed Central

Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

2013-01-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes. PMID:23563856

Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes

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

Arges, Christopher G.; Kambe, Yu; Dolejsi, Moshe

Block copolymer electrolytes (BCEs) represent an attractive choice as solid-state ionic conductors for electrochemical technologies used in energy storage and conversion, water treatment, sensors, and data storage and processing. Unlocking the maximum ionic conductivity of BCEs requires an intimate understanding as to how the microphase separated structure influences transport properties. However, elucidating such knowledge remains elusive due to the challenging task of precisely engineering BCEs with a defined structure in bulk materials. In this work, we examined BCEs in a thin film format because it was amenable to attaining BCEs with a desired nanostructure. Specifically, we systematically investigated anion-conducting BCEsmore » with different degrees of connectivity of the ionic domains. For the first time, we demonstrate that increasing terminal defects in the ionic domain from 1 terminal defect per mu m(2) to 20 terminal defects per mu m(2) ( a relatively small amount of defects) decreased ionic conductivity by 67% compared to the maximum value attained. Conversely, maximizing ionic domain connectivity increased the ionic conductivity by two-fold over a non-ordered BCE film. These experiments highlight that microphase separation alone was insufficient for ameliorating ionic conductivity in BCEs. Rather, microphase separation coupled with complete ionic domain connectivity realized BCEs with significantly enhanced ionic conductivity.« less

Electrochemical Removal of Metal Cations from Wastewater Monitored by Differential Pulse Polarography

ERIC Educational Resources Information Center

Bruce, Delphine; Kuhn, Alexander; Sojic, Neso

2004-01-01

Electrodeposition eliminates wastewater pollutants such as electrochemically active metal cations, with different pulse polarography (DPP) scrutinizing the kinetics of the treatment process. These mechanisms produce qualitative and quantitative data about the removal process, while students appreciate the use of electrochemistry in resolving…

Multifunctional System for Observing, Measuring and Analyzing Stimulation-Evoked Neurochemical Signaling

PubMed Central

Kimble, Christopher J.; Boesche, Joshua B.; Eaker, Diane R.; Kressin, Kenneth R.; Trevathan, James K.; Paek, Seungleal; Asp, Anders J.; McIntosh, Malcolm B.; Lujan, J. Luis

2017-01-01

The ability to measure neurotransmitter activity using implanted electrochemical sensors offers researchers a potent technique for analyzing neural activity across specific neural circuitry. We have developed a wirelessly controlled device, WINCS Harmoni, to observe and measure neurotransmitter dynamics at up to four separate sensors, with high temporal and spatial resolution. WINCS Harmoni also incorporates a versatile neurostimulator that can be synchronized with electrochemical recording. The WINCS Harmoni platform is thus optimally suited for probing the neurochemical effects of neurostimulation, and may in turn enable the development of personalized therapies for multiple brain disorders. PMID:29202131

Electrochemical gating-induced reversible and drastic resistance switching in VO2 nanowires

PubMed Central

Sasaki, Tsubasa; Ueda, Hiroki; Kanki, Teruo; Tanaka, Hidekazu

2015-01-01

Reversible and drastic modulation of the transport properties in vanadium dioxide (VO2) nanowires by electric field-induced hydrogenation at room temperature was demonstrated using the nanogaps separated by humid air in field-effect transistors with planer-type gates (PG-FET). These PG-FETs allowed us to investigate behavior of revealed hydrogen intercalation and diffusion aspects with time and spatial evolutions in nanowires. These results show that air nanogaps can operate as an electrochemical reaction field, even in a gaseous atmosphere, and offer new directions to explore emerging functions for electronic and energy devices in oxides. PMID:26584679

Electrochemical cell assembled in discharged state

DOEpatents

Yao, Neng-Ping; Walsh, William J.

1976-01-01

A secondary, electrochemical cell is assembled in a completely discharged state within a sealed containment. As assembled, the cell includes a positive electrode separated from a negative electrode by a molten salt electrolyte. The positive electrode is contained within a porous structure, permitting passage of molten electrolyte, and includes one or more layers of a metallic mesh, e.g. iron, impregnated with an intimate mixture of lithium sulfide and the electrolyte. The negative electrode is a porous plaque of aluminum metal. Prior to using the cell, an electrical charge forms lithium-aluminum alloy within the negative electrode and metal sulfide within the positive electrode.

The Redox Flow System for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Odonnell, P.; Gahn, R. F.; Pfeiffer, W.

1976-01-01

The interfacing of a Solar Photovoltaic System and a Redox Flow System for storage was workable. The Redox Flow System, which utilizes the oxidation-reduction capability of two redox couples, in this case iron and titanium, for its storage capacity, gave a relatively constant output regardless of solar activity so that a load could be run continually day and night utilizing the sun's energy. One portion of the system was connected to a bank of solar cells to electrochemically charge the solutions, while a separate part of the system was used to electrochemically discharge the stored energy.

Splitting algorithm for numerical simulation of Li-ion battery electrochemical processes

NASA Astrophysics Data System (ADS)

Iliev, Oleg; Nikiforova, Marina A.; Semenov, Yuri V.; Zakharov, Petr E.

2017-11-01

In this paper we present a splitting algorithm for a numerical simulation of Li-ion battery electrochemical processes. Liion battery consists of three domains: anode, cathode and electrolyte. Mathematical model of electrochemical processes is described on a microscopic scale, and contains nonlinear equations for concentration and potential in each domain. On the interface of electrodes and electrolyte there are the Lithium ions intercalation and deintercalation processes, which are described by Butler-Volmer nonlinear equation. To approximate in spatial coordinates we use finite element methods with discontinues Galerkin elements. To simplify numerical simulations we develop the splitting algorithm, which split the original problem into three independent subproblems. We investigate the numerical convergence of the algorithm on 2D model problem.

Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms

NASA Astrophysics Data System (ADS)

Morozovska, A. N.; Eliseev, E. A.; Balke, N.; Kalinin, S. V.

2010-09-01

Electrochemical insertion-deintercalation reactions are typically associated with significant change in molar volume of the host compound. This strong coupling between ionic currents and strains underpins image formation mechanisms in electrochemical strain microscopy (ESM), and allows exploring the tip-induced electrochemical processes locally. Here we analyze the signal formation mechanism in ESM, and develop the analytical description of operation in frequency and time domains. The ESM spectroscopic modes are compared to classical electrochemical methods including potentiostatic and galvanostatic intermittent titration, and electrochemical impedance spectroscopy. This analysis illustrates the feasibility of spatially resolved studies of Li-ion dynamics on the sub-10-nm level using electromechanical detection.

Kinetic mechanism for modeling of electrochemical reactions.

PubMed

Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil

2012-04-01

We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.

Simulation of electrochemical behavior in Lithium ion battery during discharge process.

PubMed

Chen, Yong; Huo, Weiwei; Lin, Muyi; Zhao, Li

2018-01-01

An electrochemical Lithium ion battery model was built taking into account the electrochemical reactions. The polarization was divided into parts which were related to the solid phase and the electrolyte mass transport of species, and the electrochemical reactions. The influence factors on battery polarization were studied, including the active material particle radius and the electrolyte salt concentration. The results showed that diffusion polarization exist in the positive and negative electrodes, and diffusion polarization increase with the conducting of the discharge process. The physicochemical parameters of the Lithium ion battery had the huge effect on cell voltage via polarization. The simulation data show that the polarization voltage has close relationship with active material particle size, discharging rate and ambient temperature.

Humic acids as pseudocapacitive electrolyte additive for electrochemical double layer capacitors

NASA Astrophysics Data System (ADS)

Wasiński, Krzysztof; Walkowiak, Mariusz; Lota, Grzegorz

2014-06-01

Novel electrolyte additive for electrochemical capacitors has been reported. It has been demonstrated for the first time that addition of humic acids (HA) to KOH-based electrolyte significantly increases capacitance of symmetrical capacitors with electrodes made of activated carbon. Specific capacitances determined by means of galvanostatic charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy consistently showed increases for HA concentrations ranging from 2% w/w up to saturated solution with maximum positive effect observed for 5% w/w of the additive. The capacitance increase has been attributed to complex faradaic processes involving oxygen-containing groups of HA molecules. Due to abundant resources, low cost and easy processability the reported solution can find application in electrochemical capacitor technologies.

Simulation of electrochemical behavior in Lithium ion battery during discharge process

PubMed Central

Chen, Yong; Lin, Muyi; Zhao, Li

2018-01-01

An electrochemical Lithium ion battery model was built taking into account the electrochemical reactions. The polarization was divided into parts which were related to the solid phase and the electrolyte mass transport of species, and the electrochemical reactions. The influence factors on battery polarization were studied, including the active material particle radius and the electrolyte salt concentration. The results showed that diffusion polarization exist in the positive and negative electrodes, and diffusion polarization increase with the conducting of the discharge process. The physicochemical parameters of the Lithium ion battery had the huge effect on cell voltage via polarization. The simulation data show that the polarization voltage has close relationship with active material particle size, discharging rate and ambient temperature. PMID:29293535

Life, performance and safety of Grace rechargeable lithium-titanium disulfide cells

NASA Astrophysics Data System (ADS)

Zuckerbrod, D.; Giovannoni, R. T.; Grossman, K. R.

The development of rechargeable Li-TiS2 cells is discussed. This proprietary process produces thin, flexible TiS2 cathodes with a life in excess of 500 cycles. TiS2 utilization of 93 percent is typically achieved at a C/5 discharge rate. A life of 200 cycles has been achieved for AA-size cells at a C/5 discharge rate and 60 cycles at the C rate. The practical energy density is 115 Wh/kg. Safety testing is underway. Vibration and high altitude did not cause venting. Crushing did not result in ignition or temperature rise. Forced overcharge and overdischarge did not result in skin temperatures above 40 C. The peak skin temperature during the short-circuit test was 120 C. Safety analyses point to the need for careful control of electrolyte volume and the benefits of a fusible separator. Grace is developing such a separator, which would shut down the electrochemical cell reaction at a temperature of 130 C.

Electrochemical preparation of poly(methylene blue)/graphene nanocomposite thin films

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

Erçarıkcı, Elif; Dağcı, Kader; Topçu, Ezgi

2014-07-01

Highlights: • Poly(MB)/graphene thin films are prepared by a simple electrochemical approach. • Graphene layers in the film show a broad band in visible region of absorbance spectra. • Morphology of composite films indicates both disordered and ordered regions. • XRD reveals that nanocomposite films include rGO layers after electropolymerization process. • Chemically prepared graphene is better than electrochemically prepared graphene for electrooxidation of nitrite. - Abstract: Poly(methylene blue)/graphene nanocomposite thin films were prepared by electropolymerization of methylene blue in the presence of graphene which have been synthesized by two different methods of a chemical oxidation process and an electrochemicalmore » approach. Synthesized nanocomposite thin films were characterized by using cyclic voltammetry, UV–vis. absorption spectroscopy, powder X-ray diffraction, and scanning tunneling microscopy techniques. Electrocatalytical properties of prepared poly(methylene blue)/graphene nanocomposite films were compared toward electrochemical oxidation of nitrite. Under optimized conditions, electrocatalytical effect of nanocomposite films of chemically prepared graphene through electrochemical oxidation of nitrite was better than that of electrochemically prepared graphene.« less

Nanoporous separators for supercapacitor using activated carbon monolith electrode from oil palm empty fruit bunches

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

Nor, N. S. M., E-mail: madra@ukm.my; Deraman, M., E-mail: madra@ukm.my; Omar, R., E-mail: madra@ukm.my

Activated porous carbon electrode prepared from fibres of oil palm empty fruit bunches was used for preparing the carbon based supercapacitor cells. The symmetrical supercapacitor cells were fabricated using carbon electrodes, stainless steel current collector, H{sub 2}SO{sub 4} electrolyte, and three types of nanoporous separators. Cells A, B and C were fabricated using polypropylene, eggshell membrane, and filter paper, respectively. Electrochemical characterizations data from Electrochemical Impedance Spectroscopy, Cyclic Voltammetry, and Galvanic Charge Discharge techniques showed that specific capacitance, specific power and specific energy for cell A were 122 F g{sup −1}, 177 W kg{sup −1}, 3.42 Wh kg{sup −1}, cellmore » B; 125 F g{sup −1}, 179 W kg{sup −1}, and 3.64 Wh kg{sup −1}, and cell C; 180 F g{sup −1}, 178 W kg{sup −1}, 4.27 Wh kg{sup −1}. All the micrographs from Field Emission Scanning Electron Microscope showed that the different in nanoporous structure of the separators lead to a significant different in influencing the values of specific capacitance, power and energy of supercapacitors, which is associated with the mobility of ion into the pore network. These results indicated that the filter paper was superior than the eggshell membrane and polypropylene nanoporous separators. However, we found that in terms of acidic resistance, polypropylene was the best nanoporous separator for acidic medium.« less

DEVELOPMENT OF A SCALABLE, LOW-COST, ULTRANANOCRYSTALLINE DIAMOND ELECTROCHEMICAL PROCESS FOR THE DESTRUCTION OF CONTAMINANTS OF EMERGING CONCERN (CECS) - PHASE II

EPA Science Inventory

This Small Business Innovation Research (SBIR) Phase II project will employ the large scale; highly reliable boron-doped ultrananocrystalline diamond (BD-UNCD®) electrodes developed during Phase I project to build and test Electrochemical Anodic Oxidation process (EAOP)...

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).

Lateral transport of solutes in microfluidic channels using electrochemically generated gradients in redox-active surfactants.

PubMed

Liu, Xiaoyang; Abbott, Nicholas L

2011-04-15

We report principles for a continuous flow process that can separate solutes based on a driving force for selective transport that is generated by a lateral concentration gradient of a redox-active surfactant across a microfluidic channel. Microfluidic channels fabricated with gold electrodes lining each vertical wall were used to electrochemically generate concentration gradients of the redox-active surfactant 11-ferrocenylundecyl-trimethylammonium bromide (FTMA) in a direction perpendicular to the flow. The interactions of three solutes (a hydrophobic dye, 1-phenylazo-2-naphthylamine (yellow AB), an amphiphilic molecule, 2-(4,4-difluoro-5,7-dimethyl-4-bora-3a,4a-diaza-s-indacene-3-pentanoyl)-1-hexadecanoyl-sn-glycero-3-phosphocholine (BODIPY C(5)-HPC), and an organic salt, 1-methylpyridinium-3-sulfonate (MPS)) with the lateral gradients in surfactant/micelle concentration were shown to drive the formation of solute-specific concentration gradients. Two distinct physical mechanisms were identified to lead to the solute concentration gradients: solubilization of solutes by micelles and differential adsorption of the solutes onto the walls of the microchannels in the presence of the surfactant concentration gradient. These two mechanisms were used to demonstrate delipidation of a mixture of BODIPY C(5)-HPC (lipid) and MPS and purification of BODIPY C(5)-HPC from a mixture of BODIPY C(5)-HPC and yellow AB. Overall, the results of this study demonstrate that lateral concentration gradients of redox-active surfactants formed within microfluidic channels can be used to transport solutes across the microfluidic channels in a solute-dependent manner. The approach employs electrical potentials (<1 V) that are sufficiently small to avoid electrolysis of water, can be performed in solutions having high ionic strength (>0.1M), and offers the basis of continuous processes for the purification or separation of solutes in microscale systems. © 2011 American Chemical Society

Carbon Nanotube Based Devices for Intracellular Analysis

NASA Astrophysics Data System (ADS)

Singhal, Riju Mohan

Scientific investigations on individual cells have gained increasing attention in recent years as efforts are being made to understand cellular functioning in complex processes, such as cell division during embryonic development, and owing to realization of heterogeneity amongst a population of a single cell type (for instance, certain individual cancer cells being immune to chemotherapy). Therefore devices enabling electrochemical detection, spectroscopy, optical observations, and separation techniques, along with cell piercing and fluid transfer capabilities at the intra-cellular level, are required. Glass pipettes have conventionally been used for single cell interrogation, however their poor mechanical properties and an intrusive conical geometry have led to limited precision and frequent cell damage or death, justifying research efforts to develop novel, non-intrusive cell probes. Carbon nanotubes (CNTs) are known for their superior physical properties and tunable chemical structure. They possess a high aspect ratio and offer minimally invasive thin carbon walls and tubular geometry. Moreover, possibility of chemical functionalization of CNTs enables multi-functional probes. In this dissertation, novel nanofluidic instruments that have nanostructured carbon tips will be presented along with techniques that utilize the exceptional physical properties of carbon nanotubes, to take miniature biomedical instrumentation to the next level. New methods for fabricating the probes were rigorously developed and their operation was extensively studied. The devices were mechanically robust and were used to inject liquids to a single cell, detect electrochemical signals and enable surface enhanced Raman spectroscopy (SERS) while inducing minimal harm to the cell. Particular attention was focused on the CVD process-which was used to deposit carbon, fluid flow through the nanotubes, and separation of chemical species (atto-liter chromatography) at the nanometer scale that would potentially lead to the highly sought after "selective component extraction" and analysis from a single cell. These multi-functional devices therefore provide a picture of the physiological state of a living cell and function as endoscopes for single cell analysis.

Improved Electrochemical Performance of Carbon-Coated LiFeBO 3 Nanoparticles for Lithium-Ion Batteries

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

Li, Zhaoping; Wang, Yiping; Hu, Querui

2015-09-01

Carbon-coated LiFeBO 3 nanoparticles have been successfully prepared by surfactant-assisted ball milling and a size selection process based on centrifugal separation. We observed monodispersed LiFeBO 3 nanoparticles with dimensions of 10–20 nm by transmission electron microscope. The introduced surfactant acts as the dispersant as well as the carbon source for LiFeBO 3 nanoparticles. Greatly improved discharge capacities of 190.4 mA h g –1 at 0.1 C and 106.6 mA h g –1 at 1 C rate have been achieved in the LiFeBO 3 nanoparticles when cycling the cells between 1.0 V and 4.8 V. Meanwhile, the as-prepared micro-size LiFeBO 3more » electrodes show lower discharge capacities of 142 mA h g –1 and 93.3 mA h g –1 at 0.1 C and 1 C rates. Moreover, the post-treated LiFeBO 3 nanostructure has drastically enhanced the electrochemical performance due to the short diffusion length and ameliorated electrical contract between LiFeBO 3 nano particles.« less

Electrochemical CO2 Reduction via Gas-Phase Catholyte

NASA Astrophysics Data System (ADS)

Carter, Brittany E.; Nesbitt, Nathan T.; D'Imperio, Luke A.; Naughton, Jeffrey R.; Courtney, Dave T.; Shepard, Steve; Burns, Michael J.; Vermaas, David A.; Smith, Wilson A.; Naughton, Michael J.

Reducing CO2 to CO through electrolysis, for the eventual conversion to hydrocarbons, provides a path towards utility-scale seasonal storage of renewable energy. Electrochemical reduction of CO2 has previously been achieved using a two chamber system. The chambers are typically separated by a semipermeable Nafion membrane, with an oxygen evolution catalyst anode on one side, a gold cathode on the other, and a solution containing CO2 on both sides. If instead, CO2 gas was in the second chamber, the reaction should yield more CO formed from CO2 at a given overpotential; this would result from the increased concentration of CO2 at the cathode surface and more facile mass transport of the CO and CO2. With liquid in one chamber and gas in the other, electrolysis is performed by integrating the cathode onto the semipermeable Nafion membrane. This membrane electrode assembly is fabricated via nanoimprint lithography (NIL), simultaneously achieving high active surface area and permeability. Challenges to the Nafion NIL process, and the performance of the system in CO2 reduction, will be presented. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

How much does size really matter? Exploring the limits of graphene as Li ion battery anode material

NASA Astrophysics Data System (ADS)

Sun, H.; Varzi, A.; Pellegrini, V.; Dinh, D. A.; Raccichini, R.; Del Rio-Castillo, A. E.; Prato, M.; Colombo, M.; Cingolani, R.; Scrosati, B.; Passerini, S.; Bonaccorso, F.

2017-02-01

We unravel the role of flake dimensionality on the lithiation/de-lithiation processes and electrochemical performance of anodes based on few-(FLG) and multi-layer graphene (MLG) flakes prepared by liquid phase exfoliation (LPE) of pristine graphite. The flakes are sorted by lateral size (from 380 to 75 nm) and thickness from 20 (MLG) to 2 nm (FLG) exploiting a sedimentation-based separation in centrifugal field and, finally, deposited onto Cu disks for the realization of four binder-free anodes. The electrochemical results show that decreasing lateral size and thickness leads to an increase of the initial specific capacity from ≈590 to ≈1270mAhg-1. However, an increasing irreversible capacity is also associated to the reduction of flakes' size. We find, in addition, that the preferential Li ions storage by adsorption rather than intercalation in small lateral size (<100 nm) FLG flakes has a detrimental effect on the average de-lithiation voltage, resulting on low voltage efficiency of these anodes. We believe that the results reported in this work, provide the guidelines for the practical exploitation of graphene-based electrodes.

A novel bio-electrochemical system with sand/activated carbon separator, Al anode and bio-anode integrated micro-electrolysis/electro-flocculation cost effectively treated high load wastewater with energy recovery.

PubMed

Gao, Changfei; Liu, Lifen; Yang, Fenglin

2018-02-01

A novel bio-electrochemical system (BES) was developed by integrating micro-electrolysis/electro-flocculation from attaching a sacrificing Al anode to the bio-anode, it effectively treated high load wastewater with energy recovery (maximum power density of 365.1 mW/m 3 and a maximum cell voltage of 0.97 V), and achieving high removals of COD (>99.4%), NH 4 + -N (>98.7%) and TP (>98.6%). The anode chamber contains microbes, activated carbon (AC)/graphite granules and Al anode. It was separated from the cathode chamber containing bifunctional catalytic and filtration membrane cathode (loaded with Fe/Mn/C/F/O catalyst) by a multi-medium chamber (MMC) filled with manganese sand and activated carbon granules, which replaced expensive PEM and reduced cost. An air contact oxidation bed for aeration was still adopted before liquid entering the cathode chamber. micro-electrolysis/electro-flocculation helps in achieving high removal efficiencies and contributes to membrane fouling migration. The increase of activated carbon in the separator MMC increased power generation and reduced system electric resistance. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis and Modeling of Boundary Layer Separation Method (BLSM).

PubMed

Pethő, Dóra; Horváth, Géza; Liszi, János; Tóth, Imre; Paor, Dávid

2010-09-01

Nowadays rules of environmental protection strictly regulate pollution material emission into environment. To keep the environmental protection laws recycling is one of the useful methods of waste material treatment. We have developed a new method for the treatment of industrial waste water and named it boundary layer separation method (BLSM). We apply the phenomena that ions can be enriched in the boundary layer of the electrically charged electrode surface compared to the bulk liquid phase. The main point of the method is that the boundary layer at correctly chosen movement velocity can be taken out of the waste water without being damaged, and the ion-enriched boundary layer can be recycled. Electrosorption is a surface phenomenon. It can be used with high efficiency in case of large electrochemically active surface of electrodes. During our research work two high surface area nickel electrodes have been prepared. The value of electrochemically active surface area of electrodes has been estimated. The existence of diffusion part of the double layer has been experimentally approved. The electrical double layer capacity has been determined. Ion transport by boundary layer separation has been introduced. Finally we have tried to estimate the relative significance of physical adsorption and electrosorption.

Preparation and electrochemical characterization of ionic-conducting lithium lanthanum titanate oxide/polyacrylonitrile submicron composite fiber-based lithium-ion battery separators

NASA Astrophysics Data System (ADS)

Liang, Yinzheng; Ji, Liwen; Guo, Bingkun; Lin, Zhan; Yao, Yingfang; Li, Ying; Alcoutlabi, Mataz; Qiu, Yiping; Zhang, Xiangwu

Lithium lanthanum titanate oxide (LLTO)/polyacrylonitrile (PAN) submicron composite fiber-based membranes were prepared by electrospinning dispersions of LLTO ceramic particles in PAN solutions. These ionic-conducting LLTO/PAN composite fiber-based membranes can be directly used as lithium-ion battery separators due to their unique porous structure. Ionic conductivities were evaluated after soaking the electrospun LLTO/PAN composite fiber-based membranes in a liquid electrolyte, 1 M lithium hexafluorophosphate (LiPF 6) in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (1:1 vol). It was found that, among membranes with various LLTO contents, 15 wt.% LLTO/PAN composite fiber-based membranes provided the highest ionic conductivity, 1.95 × 10 -3 S cm -1. Compared with pure PAN fiber membranes, LLTO/PAN composite fiber-based membranes had greater liquid electrolyte uptake, higher electrochemical stability window, and lower interfacial resistance with lithium. In addition, lithium//1 M LiPF 6/EC/EMC//lithium iron phosphate cells containing LLTO/PAN composite fiber-based membranes as the separator exhibited high discharge specific capacity of 162 mAh g -1 and good cycling performance at 0.2 C rate at room temperature.

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.

Battery Separator Characterization and Evaluation Procedures for NASA's Advanced Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennet, William R.; Wong, Eunice K.; Lewton, MaryBeth R.; Harris, Megan K.

2010-01-01

To address the future performance and safety requirements for the electrical energy storage technologies that will enhance and enable future NASA manned aerospace missions, advanced rechargeable, lithium-ion battery technology development is being pursued within the scope of the NASA Exploration Technology Development Program s (ETDP's) Energy Storage Project. A critical cell-level component of a lithium-ion battery which significantly impacts both overall electrochemical performance and safety is the porous separator that is sandwiched between the two active cell electrodes. To support the selection of the optimal cell separator material(s) for the advanced battery technology and chemistries under development, laboratory characterization and screening procedures were established to assess and compare separator material-level attributes and associated separator performance characteristics.

PALLADIUM-FACILITATED ELECTROLYTIC DECHLORINATION OF 2-CHLOROBIPHENYL USING A GRANULAR-GRAPHITE ELECTRODE.

EPA Science Inventory

Palladium-assisted electrocatalytic dechlorination of 2-chlorobiphenyl (2-Cl BP) in aqueous solutions was conducted in a membrane-separated electrochemical reactor with granular-graphite packed electrodes. The dechlorination took place at a granular-graphite cathode while Pd was ...

Ion Selective Ceramics for Waste Separations. Input for Annual Accomplishments Report

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

Spoerke, Erik David

This report discusses“Ion-Selective Ceramics for Waste Separations” which aims to develop an electrochemical approach to remove fission product waste (e.g., Cs+ ) from the LiCl-KCl molten salts used in the pyroprocessing of spent nuclear fuel.

Novel Fission-Product Separation based on Room-Temperature Ionic Liquids

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

Rogers, Robin D.

2004-12-31

U.S. DOE's underground storage tanks at Hanford, SRS, and INEEL contain liquid wastes with high concentrations of radioactive cesium-137 and strontium-90. Because the primary chemical components of alkaline supernatants are sodium nitrate and sodium hydroxide, the majority of this could be disposed of as low level waste if radioactive cesium-137 and strontium- 90 could be selectively removed. The underlying goal of this project was to investigate the application of ionic liquids as novel solvents for new solvent extraction processes for separation of cesium-137 and strontium-90 from tank wastes. Ionic liquids are a distinct sub-set of liquids, comprising only of cationsmore » and anions they are proving to be increasingly interesting fluids for application in systems from electrochemistry to energetic materials, and are also rapidly establishing their promise as viable media for synthesis and separations operations. Properties including low melting points, electrochemical conductivity, wide liquid ranges, lack of vapor-pressure, and chemical tunability have encouraged researchers to explore the uses of ILs in place of volatile organic solvents. The most promising current developments arise from control of the unique combinations of chemical and physical properties characteristic of ionic liquids.« less

Electrochemical magnetoimmunosensing approach for the sensitive detection of H9N2 avian influenza virus particles.

PubMed

Zhou, Chuan-Hua; Shu, Yun; Hong, Zheng-Yuan; Pang, Dai-Wen; Zhang, Zhi-Ling

2013-09-01

A novel electrochemical magnetoimmunosensor for fast and ultrasensitive detection of H9N2 avian influenza virus particles (H9N2 AIV) was designed based on the combination of high-efficiency immunomagnetic separation, enzyme catalytic amplification, and the biotin-streptavidin system. The reusable, homemade magneto Au electrode (M-AuE) was designed and used for the direct sensing. Immunocomplex-coated magnetic beads (IMBs) were easily accumulated on the surface of the M-AuE to obtain the catalytically reduced electrochemical signal of H2 O2 after the immunoreaction. The transducer was regenerated through a simple washing procedure, which made it possible to detect all the samples on a single electrode with higher reproducibility. The magnetic-bead-based electrochemical immunosensor showed better analytical performance than the planar-electrode-based immunosensor with the same sandwich construction. Amounts as low as 10 pg mL(-1) H9N2 AIV could be detected even in samples of chicken dung. This electrochemical magnetoimmunosensor not only provides a simple platform for the detection of the virus with high sensitivity, selectivity, and reproducibility but also shows great potential in the early diagnosis of diseases. Copyright © 2013 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.

Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

NASA Technical Reports Server (NTRS)

Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

1992-01-01

The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology

PubMed Central

Körbahti, Bahadır K.; Demirbüken, Pelin

2017-01-01

Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD) was investigated in a batch electrochemical reactor in the presence of Na2SO4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100–500 g/L), current density (2–10 mA/cm2), Na2SO4 concentration (0–20 g/L), and reaction temperature (25–45°C) was analyzed on electrochemical oxidation using response surface methodology (RSM). The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm2 current density, 12 g/L Na2SO4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction. PMID:29082225

An insight into the adsorption and electrochemical processes occurring during the analysis of copper and lead in wines, using an electrochemical quartz crystal nanobalance.

PubMed

Yamasaki, Alzira; Oliveira, João A B P; Duarte, Armando C; Gomes, M Teresa S R

2012-08-30

Copper and lead in wine were quantified by anodic stripping voltammetry (ASV), performed onto the gold electrode of a piezoelectric quartz crystal. Both current or mass changes could be used as analytical signals, without a statistical difference in the results (α=0.05). However, the plot of mass vs. potential provided an in depth understanding of the electrochemical processes and allowed studying adsorption phenomena. Copper interaction with fructose is an example of a process which was not possible to ignore by observing the mass change on the gold electrode of the piezoelectric quartz crystal. Copyright © 2012 Elsevier B.V. All rights reserved.

Galvanic high energy cells with molten salt electrolytes

NASA Astrophysics Data System (ADS)

Borger, W.; Kappus, W.; Kunze, D.; Laig-Hoerstebrock, H.; Panesar, H.; Sterr, G.

1981-02-01

Engineering scale LiAl/LiCl Kcl/FeS electrochemical storage cells were developed for electric vehicle propulsion and peak current compensation. More than 300 deep cycles and 50 Whr/kg in 100 Ahr cells and up to 100 deep cycles and more than 80 Whr/kg in 200 Ahr cells were demonstrated. Separator development for LiAl/FeS cells was focused on ceramic powders. The aluminum nitride powder separator is promising for LiAl/FeS cells. The further development of these cells includes the enhancement of energy density and lifetime as well as ceramic powder separators.

A Comprehensive Pitting Study of High Velocity Oxygen Fuel Inconel 625 Coating by Using Electrochemical Testing Techniques

NASA Astrophysics Data System (ADS)

Niaz, Akbar; Khan, Sajid Ullah

2016-01-01

In the present work, Inconel 625 was coated on a mild steel substrate using a high velocity oxygen fuel coating process. The pitting propensity of the coating was tested by using open circuit potential versus time, potentiodynamic polarization, electrochemical potentiokinetic reactivation, and scanning electrochemical microscopy. The pitting propensity of the coating was compared with bulk Inconel 625 alloy. The results confirmed that there were regions of different electrochemical activities on the coating which have caused pitting corrosion.

Electrochemical Investigation of the Corrosion of Different Microstructural Phases of X65 Pipeline Steel under Saturated Carbon Dioxide Conditions

PubMed Central

Yang, Yuanfeng; Joshi, Gaurav R.; Akid, Robert

2015-01-01

The aim of this research was to investigate the influence of metallurgy on the corrosion behaviour of separate weld zone (WZ) and parent plate (PP) regions of X65 pipeline steel in a solution of deionised water saturated with CO2, at two different temperatures (55 °C and 80 °C) and at initial pH~4.0. In addition, a non-electrochemical immersion experiment was also performed at 80 °C in CO2, on a sample portion of X65 pipeline containing part of a weld section, together with adjacent heat affected zones (HAZ) and parent material. Electrochemical impedance spectroscopy (EIS) was used to evaluate the corrosion behaviour of the separate weld and parent plate samples. This study seeks to understand the significance of the different microstructures within the different zones of the welded X65 pipe in CO2 environments on corrosion performance; with particular attention given to the formation of surface scales; and their composition/significance. The results obtained from grazing incidence X-ray diffraction (GIXRD) measurements suggest that, post immersion, the parent plate substrate is scale free, with only features arising from ferrite (α-Fe) and cementite (Fe3C) apparent. In contrast, at 80 °C, GIXRD from the weld zone substrate, and weld zone/heat affected zone of the non-electrochemical sample indicates the presence of siderite (FeCO3) and chukanovite (Fe2CO3(OH)2) phases. Scanning Electron Microscopy (SEM) on this surface confirmed the presence of characteristic discrete cube-shaped crystallites of siderite together with plate-like clusters of chukanovite.

Co-flow planar SOFC fuel cell stack

DOEpatents

Chung, Brandon W.; Pham, Ai Quoc; Glass, Robert S.

2004-11-30

A co-flow planar solid oxide fuel cell stack with an integral, internal manifold and a casing/holder to separately seal the cell. This construction improves sealing and gas flow, and provides for easy manifolding of cell stacks. In addition, the stack construction has the potential for an improved durability and operation with an additional increase in cell efficiency. The co-flow arrangement can be effectively utilized in other electrochemical systems requiring gas-proof separation of gases.

Acoustofluidic bacteria separation

NASA Astrophysics Data System (ADS)

Li, Sixing; Ma, Fen; Bachman, Hunter; Cameron, Craig E.; Zeng, Xiangqun; Huang, Tony Jun

2017-01-01

Bacterial separation from human blood samples can help with the identification of pathogenic bacteria for sepsis diagnosis. In this work, we report an acoustofluidic device for label-free bacterial separation from human blood samples. In particular, we exploit the acoustic radiation force generated from a tilted-angle standing surface acoustic wave (taSSAW) field to separate Escherichia coli from human blood cells based on their size difference. Flow cytometry analysis of the E. coli separated from red blood cells shows a purity of more than 96%. Moreover, the label-free electrochemical detection of the separated E. coli displays reduced non-specific signals due to the removal of blood cells. Our acoustofluidic bacterial separation platform has advantages such as label-free separation, high biocompatibility, flexibility, low cost, miniaturization, automation, and ease of in-line integration. The platform can be incorporated with an on-chip sensor to realize a point-of-care sepsis diagnostic device.

Mechanical Deformation of a Lithium-Metal Anode Due to a Very Stiff Separator

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

Ferrese, A; Newman, J

2014-05-21

This work builds on the two-dimensional model presented by Ferrese et al. [J. Electrochem. Soc., 159, A1615 (2012)1, which captures the movement of lithium metal at the negative electrode during cycling in a Li-metal/LiCoO2 cell. In this paper, the separator is modeled as a dendrite-inhibiting polymer separator with an elastic modulus of 16 GPa. The separator resists the movement of lithium through the generation of stresses in the cell. These stresses affect the negative electrode through two mechanisms altering the thermodynamics of the negative electrode and deforming the negative electrode mechanically. From this analysis, we find that the dendrite-inhibiting separatormore » causes plastic and elastic deformation of the lithium at the negative electrode which flattens the electrode considerably when compared to the liquid-electrolyte case. This flattening of the negative electrode causes only very slight differences in the local state of charge in the positive electrode. When comparing the magnitude of the effects flattening the negative electrode, we find that the plastic deformation plays a much larger role than either the pressure-modified reaction kinetics or elastic deformation. This is due to the low yield strength of the lithium metal, which limits the stresses such that they have only a small effect on the reaction kinetics. (C) 2014 The Electrochemical Society. All rights reserved.« less

Analysis of polyphenols in white wine by CZE with amperometric detection using carbon nanotube-modified electrodes.

PubMed

Moreno, Mónica; Arribas, Alberto Sánchez; Bermejo, Esperanza; Zapardiel, Antonio; Chicharro, Manuel

2011-04-01

A method for the simultaneous detection of five polyphenols (caffeic, chlorogenic, ferulic and gallic acids and (+)-catechin) by CZE with electrochemical detection was developed. Separation of these polyphenols was performed in a 100 mM borate buffer (pH 9.2) within 15 min. Under optimized separation conditions, the performance of glassy carbon (GC) electrodes modified with multiwalled carbon nanotube layer obtained from different dispersions was examined. GC electrode modified with a dispersion of multi-walled carbon nanotubes (CNT) in polyethylenimine has proven to be the most suitable CNT-based electrode for its application as amperometric detector for the CZE separation of the studied compounds. The excellent electrochemical properties of this electrode allowed the detection of the selected polyphenols at +200 mV and improved the efficiency and the resolution of their CZE separation. Limits of detection below 3.1 μM were obtained with linear ranges covering the 10⁻⁵ to 10⁻⁴  M range. The proposed method has been successfully applied for the detection (ferulic, caffeic and gallic acids and (+)-catechin) and the quantification (gallic acid and (+)-catechin) of polyphenols in two different white wines without any preconcentration step. A remarkable signal stability was observed on the electrode performance despite the presence of potential fouling substances in wine. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of LiMn 2O 4 cathodes by electrochemical strain microscopy

DOE PAGES

Alikin, D. O.; Ievlev, A. V.; Luchkin, S. Yu.; ...

2016-03-15

Electrochemical strain microscopy (ESM) is a scanning probe microscopy(SPM) method in which the local electrodiffusion is probed via application of AC voltage to the SPM tip and registration of resulting electrochemical strain. In this study, we implemented ESM to measure local strain in bulk LiMn 2O 4 cathodes of a commercial Li-battery in different states of charge to investigate distribution of Li-ion mobility and concentration. Ramped AC ESM imaging and voltage spectroscopy were used to find the most reliable regime of measurements allowing separating and diminishing different contributions to ESM. This is not a trivial task due to complex geometrymore » of the sample and various obstacles resulting in less predictable contributions of different origins into ESM response: electrostatic tip–surface interactions, charge injection, electrostriction, and flexoelectricity. Finally, understanding and control of these contributions is an important step towards quantitative interpretation of ESM data.« less

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.

Active membrane having uniform physico-chemically functionalized ion channels

DOEpatents

Gerald, II, Rex E; Ruscic, Katarina J; Sears, Devin N; Smith, Luis J; Klingler, Robert J; Rathke, Jerome W

2012-09-24

The present invention relates to a physicochemically-active porous membrane for electrochemical cells that purports dual functions: an electronic insulator (separator) and a unidirectional ion-transporter (electrolyte). The electrochemical cell membrane is activated for the transport of ions by contiguous ion coordination sites on the interior two-dimensional surfaces of the trans-membrane unidirectional pores. One dimension of the pore surface has a macroscopic length (1 nm-1000 .mu.m) and is directed parallel to the direction of an electric field, which is produced between the cathode and the anode electrodes of an electrochemical cell. The membrane material is designed to have physicochemical interaction with ions. Control of the extent of the interactions between the ions and the interior pore walls of the membrane and other materials, chemicals, or structures contained within the pores provides adjustability of the ionic conductivity of the membrane.

Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

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

Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.

Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparativemore » studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.« less

Reducing carbon dioxide to products

DOEpatents

Cole, Emily Barton; Sivasankar, Narayanappa; Parajuli, Rishi; Keets, Kate A

2014-09-30

A method reducing carbon dioxide to one or more products may include steps (A) to (C). Step (A) may bubble said carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode may reduce said carbon dioxide into said products. Step (B) may adjust one or more of (a) a cathode material, (b) a surface morphology of said cathode, (c) said electrolyte, (d) a manner in which said carbon dioxide is bubbled, (e), a pH level of said solution, and (f) an electrical potential of said divided electrochemical cell, to vary at least one of (i) which of said products is produced and (ii) a faradaic yield of said products. Step (C) may separate said products from said solution.

Method and apparatus for capacitive deionization and electrochemical purification and regeneration of electrodes

DOEpatents

Tran, Tri D.; Farmer, Joseph C.; Murguia, Laura

2001-01-01

An electrically regeneratable electrochemical cell (30) for capacitive deionization and electrochemical purification and regeneration of electrodes includes two end plates (31, 32), one at each end of the cell (30). A new regeneration method is applied to the cell (30) which includes slowing or stopping the purification cycle, electrically desorbing contaminants and removing the desorbed contaminants. The cell (30) further includes a plurality of generally identical double-sided intermediate electrodes (37-43) that are equidistally separated from each other, between the two end electrodes (35, 36). As the electrolyte enters the cell, it flows through a continuous open serpentine channel (65-71) defined by the electrodes, substantially parallel to the surfaces of the electrodes. By polarizing the cell (30), ions are removed from the electrolyte and are held in the electric double layers formed at the carbon aerogel surfaces of the electrodes. The cell (30) is regenerated electrically to desorb such previously removed ions.

Electrochemically driven mechanical energy harvesting.

PubMed

Kim, Sangtae; Choi, Soon Ju; Zhao, Kejie; Yang, Hui; Gobbi, Giorgia; Zhang, Sulin; Li, Ju

2016-01-06

Efficient mechanical energy harvesters enable various wearable devices and auxiliary energy supply. Here we report a novel class of mechanical energy harvesters via stress-voltage coupling in electrochemically alloyed electrodes. The device consists of two identical Li-alloyed Si as electrodes, separated by electrolyte-soaked polymer membranes. Bending-induced asymmetric stresses generate chemical potential difference, driving lithium ion flux from the compressed to the tensed electrode to generate electrical current. Removing the bending reverses ion flux and electrical current. Our thermodynamic analysis reveals that the ideal energy-harvesting efficiency of this device is dictated by the Poisson's ratio of the electrodes. For the thin-film-based energy harvester used in this study, the device has achieved a generating capacity of 15%. The device demonstrates a practical use of stress-composition-voltage coupling in electrochemically active alloys to harvest low-grade mechanical energies from various low-frequency motions, such as everyday human activities.

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1990-01-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

DOE PAGES

Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.; ...

2016-06-02

Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparativemore » studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.« less

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Electrochemically driven mechanical energy harvesting

PubMed Central

Kim, Sangtae; Choi, Soon Ju; Zhao, Kejie; Yang, Hui; Gobbi, Giorgia; Zhang, Sulin; Li, Ju

2016-01-01

Efficient mechanical energy harvesters enable various wearable devices and auxiliary energy supply. Here we report a novel class of mechanical energy harvesters via stress–voltage coupling in electrochemically alloyed electrodes. The device consists of two identical Li-alloyed Si as electrodes, separated by electrolyte-soaked polymer membranes. Bending-induced asymmetric stresses generate chemical potential difference, driving lithium ion flux from the compressed to the tensed electrode to generate electrical current. Removing the bending reverses ion flux and electrical current. Our thermodynamic analysis reveals that the ideal energy-harvesting efficiency of this device is dictated by the Poisson's ratio of the electrodes. For the thin-film-based energy harvester used in this study, the device has achieved a generating capacity of 15%. The device demonstrates a practical use of stress-composition–voltage coupling in electrochemically active alloys to harvest low-grade mechanical energies from various low-frequency motions, such as everyday human activities. PMID:26733282

Combined electrochemical, heat generation, and thermal model for large prismatic lithium-ion batteries in real-time applications

NASA Astrophysics Data System (ADS)

Farag, Mohammed; Sweity, Haitham; Fleckenstein, Matthias; Habibi, Saeid

2017-08-01

Real-time prediction of the battery's core temperature and terminal voltage is very crucial for an accurate battery management system. In this paper, a combined electrochemical, heat generation, and thermal model is developed for large prismatic cells. The proposed model consists of three sub-models, an electrochemical model, heat generation model, and thermal model which are coupled together in an iterative fashion through physicochemical temperature dependent parameters. The proposed parameterization cycles identify the sub-models' parameters separately by exciting the battery under isothermal and non-isothermal operating conditions. The proposed combined model structure shows accurate terminal voltage and core temperature prediction at various operating conditions while maintaining a simple mathematical structure, making it ideal for real-time BMS applications. Finally, the model is validated against both isothermal and non-isothermal drive cycles, covering a broad range of C-rates, and temperature ranges [-25 °C to 45 °C].

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.

Cyclically optimized electrochemical processes

NASA Astrophysics Data System (ADS)

Ruedisueli, Robert Louis

It has been frequently observed in experiment and industry practice that electrochemical processes (deposition, dissolution, fuel cells) operated in an intermittent or cyclic (AC) mode show improvements in efficiency and/or quality and yield over their steady (DC) mode of operation. Whether rationally invoked by design or empirically tuned-in, the optimal operating frequency and duty cycle is dependent upon the dominant relaxation time constant for the process in question. The electrochemical relaxation time constant is a function of: double-layer and reaction intermediary pseudo-capacitances, ion (charge) transport via electrical migration (mobility), and diffusion across a concentration gradient to electrode surface reaction sites where charge transfer and species incorporation or elimination occurs. The rate determining step dominates the time constant for the reaction or process. Electrochemical impedance spectroscopy (EIS) and piezoelectric crystal electrode (PCE) response analysis have proven to be useful tools in the study and identification of reaction mechanisms. This work explains and demonstrates with the electro-deposition of copper the application of EIS and PCE measurement and analysis to the selection of an optimum cyclic operating schedule, an optimum driving frequency for efficient, sustained cyclic (pulsed) operation.

Electrochemical Hydrogen Peroxide Generator

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

2010-01-01

Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials needed are water and oxygen or air. 2. The product is pure and can therefore be used in disinfection applications directly or after proper dilution with water. 3. Oxygen generated in the anode compartment is used in the electrochemical reduction process; in addition, external oxygen is used to establish a high flow rate in the cathode compartment to remove the desired product efficiently. Exiting oxygen can be recycled after separation of liquid hydrogen peroxide product, if so desired. 4. The process can be designed for peroxide generation under microgravity conditions. 5. High concentrations of the order of 6-7 wt% can be generated by this method. This method at the time of this reporting is superior to what other researchers have reported. 6. The cell design allows for stacking of cells to increase the hydrogen peroxide production. 7. The catalyst mix containing a diquaternary ammonium compound enabled not only higher concentration of hydrogen peroxide but also higher current efficiency, improved energy efficiency, and catalyst stability. 8. The activity of the catalyst is maintained even after repeated periods of system shutdown. 9. The catalyst system can be extended for fuel-cell cathodes with suitable modifications.

Method for forming a cell separator for use in bipolar-stack energy storage devices

DOEpatents

Mayer, Steven T.; Feikert, John H.; Kaschmitter, James L.; Pekala, Richard W.

1994-01-01

An improved multi-cell electrochemical energy storage device, such as a battery, fuel cell, or double layer capacitor using a cell separator which allows cells to be stacked and interconnected with low electrical resistance and high reliability while maximizing packaging efficiency. By adding repeating cells, higher voltages can be obtained. The cell separator is formed by applying an organic adhesive on opposing surfaces of adjacent carbon electrodes or surfaces of aerogel electrodes of a pair of adjacent cells prior to or after pyrolysis thereof to form carbon aerogel electrodes. The cell separator is electronically conductive, but ionically isolating, preventing an electrolytic conduction path between adjacent cells in the stack.

Cell separator for use in bipolar-stack energy storage devices

DOEpatents

Mayer, S.T.; Feikert, J.H.; Kachmitter, J.L.; Pekala, R.W.

1995-02-28

An improved multi-cell electrochemical energy storage device is described, such as a battery, fuel cell, or double layer capacitor using a cell separator which allows cells to be stacked and interconnected with low electrical resistance and high reliability while maximizing packaging efficiency. By adding repeating cells, higher voltages can be obtained. The cell separator is formed by applying an organic adhesive on opposing surfaces of adjacent carbon electrodes or surfaces of aerogel electrodes of a pair of adjacent cells prior to or after pyrolysis thereof to form carbon aerogel electrodes. The cell separator is electronically conductive, but ionically isolating, preventing an electrolytic conduction path between adjacent cells in the stack. 2 figs.

Method for forming a cell separator for use in bipolar-stack energy storage devices

DOEpatents

Mayer, S.T.; Feikert, J.H.; Kaschmitter, J.L.; Pekala, R.W.

1994-08-09

An improved multi-cell electrochemical energy storage device, such as a battery, fuel cell, or double layer capacitor using a cell separator which allows cells to be stacked and interconnected with low electrical resistance and high reliability while maximizing packaging efficiency. By adding repeating cells, higher voltages can be obtained. The cell separator is formed by applying an organic adhesive on opposing surfaces of adjacent carbon electrodes or surfaces of aerogel electrodes of a pair of adjacent cells prior to or after pyrolysis thereof to form carbon aerogel electrodes. The cell separator is electronically conductive, but ionically isolating, preventing an electrolytic conduction path between adjacent cells in the stack. 2 figs.

Submicron patterned metal hole etching

DOEpatents

McCarthy, Anthony M.; Contolini, Robert J.; Liberman, Vladimir; Morse, Jeffrey

2000-01-01

A wet chemical process for etching submicron patterned holes in thin metal layers using electrochemical etching with the aid of a wetting agent. In this process, the processed wafer to be etched is immersed in a wetting agent, such as methanol, for a few seconds prior to inserting the processed wafer into an electrochemical etching setup, with the wafer maintained horizontal during transfer to maintain a film of methanol covering the patterned areas. The electrochemical etching setup includes a tube which seals the edges of the wafer preventing loss of the methanol. An electrolyte composed of 4:1 water: sulfuric is poured into the tube and the electrolyte replaces the wetting agent in the patterned holes. A working electrode is attached to a metal layer of the wafer, with reference and counter electrodes inserted in the electrolyte with all electrodes connected to a potentiostat. A single pulse on the counter electrode, such as a 100 ms pulse at +10.2 volts, is used to excite the electrochemical circuit and perform the etch. The process produces uniform etching of the patterned holes in the metal layers, such as chromium and molybdenum of the wafer without adversely effecting the patterned mask.

Toward quantitative electrochemical measurements on the nanoscale by scanning probe microscopy: environmental and current spreading effects.

PubMed

Arruda, Thomas M; Kumar, Amit; Jesse, Stephen; Veith, Gabriel M; Tselev, Alexander; Baddorf, Arthur P; Balke, Nina; Kalinin, Sergei V

2013-09-24

The application of electric bias across tip-surface junctions in scanning probe microscopy can readily induce surface and bulk electrochemical processes that can be further detected though changes in surface topography, Faradaic or conductive currents, or electromechanical strain responses. However, the basic factors controlling tip-induced electrochemical processes, including the relationship between applied tip bias and the thermodynamics of local processes, remains largely unexplored. Using the model Li-ion reduction reaction on the surface in Li-ion conducting glass ceramic, we explore the factors controlling Li-metal formation and find surprisingly strong effects of atmosphere and back electrode composition on the process. We find that reaction processes are highly dependent on the nature of the counter electrode and environmental conditions. Using a nondepleting Li counter electrode, Li particles could grow significantly larger and faster than a depleting counter electrode. Significant Li ion depletion leads to the inability for further Li reduction. Time studies suggest that Li diffusion replenishes the vacant sites after ∼12 h. These studies suggest the feasibility of SPM-based quantitative electrochemical studies under proper environmental controls, extending the concepts of ultramicroelectrodes to the single-digit nanometer scale.

Facile route to covalently-jointed graphene/polyaniline composite and it's enhanced electrochemical performances for supercapacitors

NASA Astrophysics Data System (ADS)

Qiu, Hanxun; Han, Xuebin; Qiu, Feilong; Yang, Junhe

2016-07-01

A polyaniline/graphene composite with covalently-bond is synthesized by a novel approach. In this way, graphene oxide is functionalized firstly by introducing amine groups onto the surface with the reduction of graphene oxide in the process and then served as the anchor sites for the growth of polyaniline (PANI) via in-situ polymerization. The composite material is characterized by electron microscopy, the resonant Raman spectra, X-ray diffraction, transform infrared spectroscopy and X-ray photoelectron spectroscopy. The electrochemical properties of the composite are measured by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charging/discharging. With the functionalization process, the graphene/polyaniline composite electrode exhibits remarkably enhanced electrochemical performance with specific capacitance of 489 F g-1 at 0.5 A g-1, which is superior to those of its individual components. The outstanding electrochemical performance of the hybrid can be attributed to its covalently synergistic effect between graphene and polyaniline, suggesting promising potentials for supercapacitors.

Conductive diamond sono-electrochemical disinfection (CDSED) for municipal wastewater reclamation.

PubMed

Llanos, Javier; Cotillas, Salvador; Cañizares, Pablo; Rodrigo, Manuel A

2015-01-01

In the present work, the disinfection of actual effluents from a municipal wastewater treatment plant (WWTP) by a conductive diamond sono-electrochemical process was assessed. First, efficiency of single electrodisinfection process with diamond anodes (without the contribution of ultrasounds) was studied, finding that the total disinfection can be attained at current charges applied below 0.02kAhm(-3). It was also found that the main disinfection mechanism is the attack of Escherichia coli (E. coli) by the disinfectants produced in the electrochemical cell and that the production of chlorates is avoided when working at current densities not higher than 1.27Am(-2). Next, a marked synergistic effect was found when coupling ultrasound (US) irradiation to the electrochemical system (sono-electrochemical disinfection). This increase in the disinfection rate was found to be related to the suppression of the agglomeration of E. coli cells and the enhancement in the production of disinfectant species. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization of electrochemically deposited polypyrrole using magnetoelastic material transduction elements

NASA Technical Reports Server (NTRS)

Ersoz, Arzu; Ball, J. Christopher; Grimes, Craig A.; Bachas, Leonidas G.

2002-01-01

Magnetoelastic alloy films have been used as a working electrode in an electrochemical cell. This material allows magnetic interrogation of electrochemical deposition. This technique was used to monitor the electrochemical deposition of polypyrrole by multisweep (CV) and potentiostatic methods. Since the determination of the mass-sensitive magnetoelastic film's resonance frequency is based on magnetic transduction, an inherent advantage of this method is that it requires no electrical connections other than the working lead of the potentiostat. Increases in pyrrole deposition correlated with a decrease in the peak resonance frequency of the magnetoelastic alloy. This technique provides a novel approach by which one can monitor electrochemical processes.

Space Electrochemical Research and Technology

NASA Technical Reports Server (NTRS)

1991-01-01

The proceedings of NASA's third Space Electrochemical Research and Technology (SERT) conference are presented. The objective of the conference was to assess the present status and general thrust of research and development in those areas of electrochemical technology required to enable NASA missions in the next century. The conference provided a forum for the exchange of ideas and opinions of those actively involved in the field, in order to define new opportunities for the application of electrochemical processes in future NASA missions. Papers were presented in three technical areas: the electrochemical interface, the next generation in aerospace batteries and fuel cells, and electrochemistry for nonenergy storage applications.

Panoramic View of Electrochemical Pseudocapacitor and Organic Solar Cell Research in Molecularly Engineered Energy Materials (MEEM)

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

Aguirre, Jordan C.; Ferreira, Amy; Ding, Hong

2014-07-09

Our program on capacitive energy storage is a comprehensive one that combines experimental and computational components to achieve a fundamental understanding of charge storage processes in redox-based materials, specifically transition metal oxides. Some of the highlights of this program are the identification of intercalation pseudocapacitance in Nb2O5, which enables high energy density to be achieved at high rates, and the development of a new route for synthesizing mesoporous films in which preformed nanocrystal building blocks are used in combination with polymer templating. The resulting material architectures have large surface areas and enable electrolyte access to the redox active pore walls,more » while the interconnected mesoporous film provides good electronic conductivity. Select first-principles density-functional theory studies of prototypical pseudocapacitor materials are reviewed, providing insight into the key physical and chemical features involved in charge transfer and ion diffusion. Rigorous multiscale physical models and numerical tools have been developed and used to reproduce electrochemical properties of carbon-based electrochemical capacitors with the ultimate objective of facilitating the optimization of electrode design. For the organic photovoltaic (OPV) program, our focus has been ongoing beyond the trial-and-error Edisonian approaches that have been responsible for the increase in power conversion efficiency of blend-cast (BC) bulk heterojunction blends of polymers and fullerenes. Our first approach has been to use molecular self-assembly to create the ideal nanometer-scale architecture using thermodynamics rather than relying on the kinetics of spontaneous phase segregation. We have created fullerenes that self-assemble into one-dimensional stacks and have shown that use of these self-assembled fullerenes lead to dramatically enhanced OPV performance relative to fullerenes that do not assemble. We also have created self-assembling conjugated polymers that form gels based on electrically continuous cross-linked micelles in solution, opening the possibility for water-processable “green” production of OPVs based on these materials. Our second approach has been to avoid kinetic control over phase separation by using a sequential processing (SqP) technique to deposit the polymer and fullerene materials in separate deposition steps. The polymer layer is deposited first, using solvents and deposition conditions that optimize the polymer crystallinity for swelling and hole mobility. The fullerene layer is then deposited in a second step from a solvent that swells the polymer but does not dissolve it, allowing the fullerene to penetrate into the polymer underlayer to the desired degree. Careful comparison of composition- and thickness-matched BC and SqP devices shows that SqP not only produces more efficient devices but also leads to devices that behave more consistently.« less

Electrochemical cell having cylindrical electrode elements

DOEpatents

Nelson, Paul A.; Shimotake, Hiroshi

1982-01-01

A secondary, high temperature electrochemical cell especially adapted for lithium alloy negative electrodes, transition metal chalcogenide positive electrodes and alkali metal halide or alkaline earth metal halide electrolyte is disclosed. The cell is held within an elongated cylindrical container in which one of the active materials is filled around the outside surfaces of a plurality of perforate tubular current collectors along the length of the container. Each of the current collector tubes contain a concentric tubular layer of electrically insulative ceramic as an interelectrode separator. The active material of opposite polarity in elongated pin shape is positioned longitudinally within the separator layer. A second electrically conductive tube with perforate walls can be swagged or otherwise bonded to the outer surface of the pin as a current collector and the electrically insulative ceramic layer can be coated or otherwise layered onto the outer surface of this second current collector. Alternatively, the central pin electrode can include an axial core as a current collector.

Thermal analysis, optimization and design of a Martian oxygen production plant

NASA Technical Reports Server (NTRS)

Iyer, Venkatesh A.; Sridhar, K. R.

1991-01-01

The objective is to optimally design the thermal components of a system that uses carbon dioxide (CO2) from the Martian atmosphere to produce oxygen (O2) for spacecraft propulsion and/or life-support. Carbon dioxide is thermally decomposed into carbon monoxide (CO) and O2 followed by the electrochemical separation of O2. The design of the overall system and its various individual components depends on, among other things, the fraction of the stoichiometric yield of O2 that can be realized in the system and the temperature of operation of the electrochemical separation membrane. The analysis indicates that a substantial reduction could be obtained in the mass and power requirements of the system if the unreacted CO2 were to be recycled. The concepts of an optimum temperature of the zirconia cell and impracticality of plant operation at low cell efficiencies are also discussed. The design of the thermal equipment is such that the mass and power requirements of the individual components and of the overall system are optimized.

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.

Localized Charges Control Exciton Energetics and Energy Dissipation in Doped Carbon Nanotubes.

PubMed

Eckstein, Klaus H; Hartleb, Holger; Achsnich, Melanie M; Schöppler, Friedrich; Hertel, Tobias

2017-10-24

Doping by chemical or physical means is key for the development of future semiconductor technologies. Ideally, charge carriers should be able to move freely in a homogeneous environment. Here, we report on evidence suggesting that excess carriers in electrochemically p-doped semiconducting single-wall carbon nanotubes (s-SWNTs) become localized, most likely due to poorly screened Coulomb interactions with counterions in the Helmholtz layer. A quantitative analysis of blue-shift, broadening, and asymmetry of the first exciton absorption band also reveals that doping leads to hard segmentation of s-SWNTs with intrinsic undoped segments being separated by randomly distributed charge puddles approximately 4 nm in width. Light absorption in these doped segments is associated with the formation of trions, spatially separated from neutral excitons. Acceleration of exciton decay in doped samples is governed by diffusive exciton transport to, and nonradiative decay at charge puddles within 3.2 ps in moderately doped s-SWNTs. The results suggest that conventional band-filling in s-SWNTs breaks down due to inhomogeneous electrochemical doping.

Wireless programmable electrochemical drug delivery micropump with fully integrated electrochemical dosing sensors.

PubMed

Sheybani, Roya; Cobo, Angelica; Meng, Ellis

2015-08-01

We present a fully integrated implantable electrolysis-based micropump with incorporated EI dosing sensors. Wireless powering and data telemetry (through amplitude and frequency modulation) were utilized to achieve variable flow control and a bi-directional data link with the sensors. Wireless infusion rate control (0.14-1.04 μL/min) and dose sensing (bolus resolution of 0.55-2 μL) were each calibrated separately with the final circuit architecture and then simultaneous wireless flow control and dose sensing were demonstrated. Recombination detection using the dosing system, as well as, effects of coil separation distance and misalignment in wireless power and data transfer were studied. A custom-made normally closed spring-loaded ball check valve was designed and incorporated at the reservoir outlet to prevent backflow of fluids as a result of the reverse pressure gradient caused by recombination of electrolysis gases. Successful delivery, infusion rate control, and dose sensing were achieved in simulated brain tissue.

Supercritical fluid attachment of palladium nanoparticles on aligned carbon nanotubes.

PubMed

Ye, Xiang-Rong; Lin, Yuehe; Wai, Chien M; Talbot, Jan B; Jin, Sungho

2005-06-01

Nanocomposite materials consisting of Pd nanoparticles deposited on aligned multi-walled carbon nanotubes have been fabricated through hydrogen reduction of palladium-beta-diketone precursor in supercritical carbon dioxide. The supercritical fluid processing allowed deposition of high-density Pd nanoparticles (approximately 5-10 nm) on both as-grown (unfunctionalized) and functionalized (using HNO3 oxidation) nanotubes. However, the wet processing for functionalization results in pre-agglomerated, bundle-shaped nanotubes, thus significantly reducing the effective surface area for Pd particle deposition, although the bundling provides more secure, lock-in-place positioning of nanotubes and Pd catalyst particles. The nanotube bundling is substantially mitigated by Pd nanoparticle deposition on the unfunctionalized and geometrically separated nanotubes, which provides much higher catalyst surface area. Such nanocomposite materials utilizing geometrically secured and aligned nanotubes can be useful for providing much enhanced catalytic activities to chemical and electrochemical reactions (e.g., fuel cell reactions), and eliminate the need for tedious catalyst recovery process after the reaction is completed.

High Performance Hybrid Energy Storage with Potassium Ferricyanide Redox Electrolyte.

PubMed

Lee, Juhan; Choudhury, Soumyadip; Weingarth, Daniel; Kim, Daekyu; Presser, Volker

2016-09-14

We demonstrate stable hybrid electrochemical energy storage performance of a redox-active electrolyte, namely potassium ferricyanide in aqueous media in a supercapacitor-like setup. Challenging issues associated with such a system are a large leakage current and high self-discharge, both stemming from ion redox shuttling through the separator. The latter is effectively eliminated when using an ion exchange membrane instead of a porous separator. Other critical factors toward the optimization of a redox-active electrolyte system, especially electrolyte concentration and volume of electrolyte, have been studied by electrochemical methods. Finally, excellent long-term stability is demonstrated up to 10 000 charge/discharge cycles at 1.2 and 1.8 V, with a broad maximum stability window of up to 1.8 V cell voltage as determined via cyclic voltammetry. An energy capacity of 28.3 Wh/kg or 11.4 Wh/L has been obtained from such cells, taking the nonlinearity of the charge-discharge profile into account. The power performance of our cell has been determined to be 7.1 kW/kg (ca. 2.9 kW/L or 1.2 kW/m(2)). These ratings are higher compared to the same cell operated in aqueous sodium sulfate. This hybrid electrochemical energy storage system is believed to find a strong foothold in future advanced energy storage applications.

New superconductor LixFe1+δSe (x ≤ 0.07, Tc up to 44 K) by an electrochemical route

NASA Astrophysics Data System (ADS)

Alekseeva, Anastasia M.; Drozhzhin, Oleg A.; Dosaev, Kirill A.; Antipov, Evgeny V.; Zakharov, Konstantin V.; Volkova, Olga S.; Chareev, Dmitriy A.; Vasiliev, Alexander N.; Koz, Cevriye; Schwarz, Ulrich; Rosner, Helge; Grin, Yuri

2016-05-01

The superconducting transition temperature (Tc) of tetragonal Fe1+δSe was enhanced from 8.5 K to 44 K by chemical structure modification. While insertion of large alkaline cations like K or solvated lithium and iron cations in the interlayer space, the [Fe2Se2] interlayer separation increases significantly from 5.5 Å in native Fe1+δSe to >7 Å in KxFe1-ySe and to >9 Å in Li1-xFex(OH)Fe1-ySe, we report on an electrochemical route to modify the superconducting properties of Fe1+δSe. In contrast to conventional chemical (solution) techniques, the electrochemical approach allows to insert non-solvated Li+ into the Fe1+δSe structure which preserves the native arrangement of [Fe2Se2] layers and their small separation. The amount of intercalated lithium is extremely small (about 0.07 Li+ per f.u.), however, its incorporation results in the enhancement of Tc up to ˜44 K. The quantum-mechanical calculations show that Li occupies the octahedrally coordinated position, while the [Fe2Se2] layers remain basically unmodified. The obtained enhancement of the electronic density of states at the Fermi level clearly exceeds the effect expected on basis of rigid band behavior.

Electrical conductivity measurements of bacterial nanowires from Pseudomonas aeruginosa

NASA Astrophysics Data System (ADS)

Maruthupandy, Muthusamy; Anand, Muthusamy; Maduraiveeran, Govindhan; Sait Hameedha Beevi, Akbar; Jeeva Priya, Radhakrishnan

2015-12-01

The extracellular appendages of bacteria (flagella) that transfer electrons to electrodes are called bacterial nanowires. This study focuses on the isolation and separation of nanowires that are attached via Pseudomonas aeruginosa bacterial culture. The size and roughness of separated nanowires were measured using transmission electron microscopy (TEM) and atomic force microscopy (AFM), respectively. The obtained bacterial nanowires indicated a clear image of bacterial nanowires measuring 16 nm in diameter. The formation of bacterial nanowires was confirmed by microscopic studies (AFM and TEM) and the conductivity nature of bacterial nanowire was investigated by electrochemical techniques. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), which are nondestructive voltammetry techniques, suggest that bacterial nanowires could be the source of electrons—which may be used in various applications, for example, microbial fuel cells, biosensors, organic solar cells, and bioelectronic devices. Routine analysis of electron transfer between bacterial nanowires and the electrode was performed, providing insight into the extracellular electron transfer (EET) to the electrode. CV revealed the catalytic electron transferability of bacterial nanowires and electrodes and showed excellent redox activities. CV and EIS studies showed that bacterial nanowires can charge the surface by producing and storing sufficient electrons, behave as a capacitor, and have features consistent with EET. Finally, electrochemical studies confirmed the development of bacterial nanowires with EET. This study suggests that bacterial nanowires can be used to fabricate biomolecular sensors and nanoelectronic devices.

Composite Cathodes for Dual-Rate Li-Ion Batteries

NASA Technical Reports Server (NTRS)

Whitacre, Jay; West, William; Bugga, Ratnakumar

2008-01-01

Composite-material cathodes that enable Li-ion electrochemical cells and batteries to function at both high energy densities and high discharge rates are undergoing development. Until now, using commercially available cathode materials, it has been possible to construct cells that have either capability for high-rate discharge or capability to store energy at average or high density, but not both capabilities. However, both capabilities are needed in robotic, standby-power, and other applications that involve duty cycles that include long-duration, low-power portions and short-duration, high-power portions. The electrochemically active ingredients of the present developmental composite cathode materials are: carbon-coated LiFePO4, which has a specific charge capacity of about 160 mA h/g and has been used as a high-discharge-rate cathode material and Li[Li(0.17)Mn(0.58)Ni(0.25)]O2, which has a specific charge capacity of about 240 mA h/g and has been used as a high-energy-density cathode material. In preparation for fabricating the composite material cathode described, these electrochemically active ingredients are incorporated into two sub-composites: a mixture comprising 10 weight percent of poly(vinylidine fluoride); 10 weight percent of carbon and 80 weight percent of carbon coated LiFePO4; and, a mixture comprising 10 weight percent of PVDF, and 80 weight percent of Li[Li(0.17)Mn(0.58)Ni(0.25)]O2. In the fabrication process, these mixtures are spray-deposited onto an aluminum current collector. Electrochemical tests performed thus far have shown that better charge/discharge performance is obtained when either 1) each mixture is sprayed on a separate area of the current collector or (2) the mixtures are deposited sequentially (in contradistinction to simultaneously) on the same current-collector area so that the resulting composite cathode material consists of two different sub-composite layers.

The role of ultra-thin SiO2 layers in metal-insulator-semiconductor (MIS) photoelectrochemical devices (Presentation Recording)

NASA Astrophysics Data System (ADS)

Esposito, Daniel V.

2015-08-01

Solid-state junctions based on a metal-insulator-semiconductor (MIS) architecture are of great interest for a number of optoelectronic applications such as photovoltaics, photoelectrochemical cells, and photodetection. One major advantage of the MIS junction compared to the closely related metal-semiconductor junction, or Schottky junction, is that the thin insulating layer (1-3 nm thick) that separates the metal and semiconductor can significantly reduce the density of undesirable interfacial mid-gap states. The reduction in mid-gap states helps "un-pin" the junction, allowing for significantly higher built-in-voltages to be achieved. A second major advantage of the MIS junction is that the thin insulating layer can also protect the underlying semiconductor from corrosion in an electrochemical environment, making the MIS architecture well-suited for application in (photo)electrochemical applications. In this presentation, discontinuous Si-based MIS junctions immersed in electrolyte are explored for use as i.) photoelectrodes for solar-water splitting in photoelectrochemical cells (PECs) and ii.) position-sensitive photodetectors. The development and optimization of MIS photoelectrodes for both of these applications relies heavily on understanding how processing of the thin SiO2 layer impacts the properties of nano- and micro-scale MIS junctions, as well as the interactions of the insulating layer with the electrolyte. In this work, we systematically explore the effects of insulator thickness, synthesis method, and chemical treatment on the photoelectrochemical and electrochemical properties of these MIS devices. It is shown that electrolyte-induced inversion plays a critical role in determining the charge carrier dynamics within the MIS photoelectrodes for both applications.

A novel broadband impedance method for detection of cell-derived microparticles.

PubMed

Lvovich, Vadim; Srikanthan, Sowmya; Silverstein, Roy L

2010-10-15

A novel label-free method is presented to detect and quantify cell-derived microparticles (MPs) by the electrochemical potential-modulated electrochemical impedance spectroscopy (EIS). MPs are present in elevated concentrations during pathological conditions and play a major role in the establishment and pathogenesis of many diseases. Considering this, accurate detection and quantification of MPs is very important in clinical diagnostics and therapeutics. A combination of bulk solution electrokinetic sorting and interfacial impedance responses allows achieving detection limits as low as several MPs per μL. By fitting resulting EIS spectra with an equivalent electrical circuit, the bulk solution electrokinetic and interfacial impedance responses were characterized. In the bulk solution two major relaxations were prominent-β-relaxation in low MHz region due to the MP capacitive membrane bridging, and α-relaxation at ∼10 kHz due to counter ions diffusion. At low frequencies (10-0.1 Hz) at electrochemical potentials exceeding -100 mV, a facile interfacial Faradaic process of oxidation in MPs coupled with diffusion and non-Faradaic double layer charging dominate, probably due to oxidation of phospholipids and/or proteins on the MP surface and MP lysis. Buffer influence on the MP detection demonstrated that a relatively low conductivity Tyrode's buffer background solution is preferential for the MP electrokinetic separation and characterization. This study also demonstrated that standard laboratory methods such as flow cytometry underestimate MP concentrations, especially those with smaller average sizes, by as much as a factor of 2-40. Copyright © 2010 Elsevier B.V. All rights reserved.

An electrochemical sensing approach for scouting microbial chemolithotrophic metabolisms.

PubMed

Saavedra, Albert; Figueredo, Federico; Cortón, Eduardo; Abrevaya, Ximena C

2018-05-01

The present study was aimed to test an electrochemical sensing approach for the detection of an active chemolithotrophic metabolism (and therefore the presence of chemolithotrophic microorganisms) by using the corrosion of pyrite by Acidithiobacillus ferrooxidans as a model. Different electrochemical techniques were combined with adhesion studies and scanning electron microscopy (SEM). The experiments were performed in presence or absence of A. ferrooxidans and without or with ferrous iron in the culture medium (0 and 0.5 g L -1 , respectively). Electrochemical parameters were in agreement with voltammetric studies and SEM showing that it is possible to distinguish between an abiotically-induced corrosion process (AIC) and a microbiologically-induced corrosion process (MIC). The results show that our approach not only allows the detection of chemolithotrophic activity of A. ferrooxidans but also can characterize the corrosion process. This may have different kind of applications, from those related to biomining to life searching missions in other planetary bodies. Copyright © 2018 Elsevier B.V. All rights reserved.

Dissecting anode swelling in commercial lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Ningxin; Tang, Huaqiong

2012-11-01

An innovative method is applied to investigate anode swelling during electrochemical processes in commercial lithium-ion batteries. Cathode surface is partially covered with a piece of paste to block the transportation of lithium ion from active material during charging/discharging, and the corresponding part on the anode film shows no formation of Li-graphite compounds during different electrochemical processes, which is confirmed by XRD analysis. The increases of anode thickness within and outside lithiated zone are measured, and defined as electrochemical swelling and physical swelling respectively. The microscopic lattice expansion of graphite due to lithiation process correlates to mesoscopic electrochemical swelling synchronically, while physical swelling tends to decrease steadily with time. The relationship among the microscopic stress due to lithium-ion intercalation, the mesoscopic stress resulting in anode swelling, and the macroscopic rippling of pouch cell after a large number of cycle test, is analyzed and correlated in terms of stress evolution across different scales, and suggestions for solving anode swelling are provided.

Electrochemical characterization of monoclinic and orthorhombic Li3CrF6 as positive electrodes in lithium-ion batteries synthesized by a sol-gel process with environmentally benign chemicals

NASA Astrophysics Data System (ADS)

Lieser, Georg; Winkler, Volker; Geßwein, Holger; de Biasi, Lea; Glatthaar, Sven; Hoffmann, M. J.; Ehrenberg, Helmut; Binder, Joachim R.

2015-10-01

Lithium transition metal fluorides (Li3MF6; M = Fe, V) with cryolite structure are investigated as positive electrode materials for lithium-ion batteries. A novel sol-gel process with trifluoroacetic acid as fluorine source was used to synthesize monoclinic and orthorhombic Li3CrF6. A ball milling process with Li3CrF6, binder, and conductive agent was applied to form a Li3CrF6 composite, which was electrochemically characterized against lithium metal for the first time. The electrochemical properties of two different modifications are quite similar, with a reversible specific capacity of 111 mAhg-1 for monoclinic Li3CrF6 and 106 mAhg-1 for orthorhombic Li3CrF6 (1 eq. Li ≙ 143 mAhg-1). The electrochemically active redox couple CrIII/CrII was confirmed by X-ray photoelectron spectroscopy.

Pulsed Electrochemical Mass Spectrometry for Operando Tracking of Interfacial Processes in Small-Time-Constant Electrochemical Devices such as Supercapacitors.

PubMed

Batisse, Nicolas; Raymundo-Piñero, Encarnación

2017-11-29

A more detailed understanding of the electrode/electrolyte interface degradation during the charging cycle in supercapacitors is of great interest for exploring the voltage stability range and therefore the extractable energy. The evaluation of the gas evolution during the charging, discharging, and aging processes is a powerful tool toward determining the stability and energy capacity of supercapacitors. Here, we attempt to fit the gas analysis resolution to the time response of a low-gas-generation power device by adopting a modified pulsed electrochemical mass spectrometry (PEMS) method. The pertinence of the method is shown using a symmetric carbon/carbon supercapacitor operating in different aqueous electrolytes. The differences observed in the gas levels and compositions as a function of the cell voltage correlate to the evolution of the physicochemical characteristics of the carbon electrodes and to the electrochemical performance, giving a complete picture of the processes taking place at the electrode/electrolyte interface.

An Easy-to-Machine Electrochemical Flow Microreactor: Efficient Synthesis of Isoindolinone and Flow Functionalization.

PubMed

Folgueiras-Amador, Ana A; Philipps, Kai; Guilbaud, Sébastien; Poelakker, Jarno; Wirth, Thomas

2017-11-27

Flow electrochemistry is an efficient methodology to generate radical intermediates. An electrochemical flow microreactor has been designed and manufactured to improve the efficiency of electrochemical flow reactions. With this device only little or no supporting electrolytes are needed, making processes less costly and enabling easier purification. This is demonstrated by the facile synthesis of amidyl radicals used in intramolecular hydroaminations to produce isoindolinones. The combination with inline mass spectrometry facilitates a much easier combination of chemical steps in a single flow process. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Single bead-based electrochemical biosensor.

PubMed

Liu, Changchun; Schrlau, Michael G; Bau, Haim H

2009-12-15

A simple, robust, single bead-based electrochemical biosensor was fabricated and characterized. The sensor's working electrode consists of an electrochemically etched platinum wire, with a nominal diameter of 25 microm, hermetically heat-fusion sealed in a pulled glass capillary (micropipette). The sealing process does not require any epoxy or glue. A commercially available, densely functionalized agarose bead was mounted on the tip of the etched platinum wire. The use of a pre-functionalized bead eliminates the tedious and complicated surface functionalization process that is often the bottleneck in the development of electrochemical biosensors. We report on the use of a biotin agarose bead-based, micropipette, electrochemical (Bio-BMP) biosensor to monitor H(2)O(2) concentration and the use of a streptavidin bead-based, micropipette, electrochemical (SA-BMP) biosensor to detect DNA amplicons. The Bio-BMP biosensor's response increased linearly as the H(2)O(2) concentration increased in the range from 1 x 10(-6) to 1.2 x10(-4)M with a detection limit of 5 x 10(-7)M. The SA-BMP was able to detect the amplicons of 1pg DNA template of B. Cereus bacteria, thus providing better detection sensitivity than conventional gel-based electropherograms.

Electrochemical analyses of redox-active iron minerals: a review of nonmediated and mediated approaches.

PubMed

Sander, Michael; Hofstetter, Thomas B; Gorski, Christopher A

2015-05-19

Redox-active minerals are ubiquitous in the environment and are involved in numerous electron transfer reactions that significantly affect biogeochemical processes and cycles as well as pollutant dynamics. As a consequence, research in different scientific disciplines is devoted to elucidating the redox properties and reactivities of minerals. This review focuses on the characterization of mineral redox properties using electrochemical approaches from an applied (bio)geochemical and environmental analytical chemistry perspective. Establishing redox equilibria between the minerals and working electrodes is a major challenge in electrochemical measurements, which we discuss in an overview of traditional electrochemical techniques. These issues can be overcome with mediated electrochemical analyses in which dissolved redox mediators are used to increase the rate of electron transfer and to facilitate redox equilibration between working electrodes and minerals in both amperometric and potentiometric measurements. Using experimental data on an iron-bearing clay mineral, we illustrate how mediated electrochemical analyses can be employed to derive important thermodynamic and kinetic data on electron transfer to and from structural iron. We summarize anticipated methodological advancements that will further contribute to advance an improved understanding of electron transfer to and from minerals in environmentally relevant redox processes.

Electrochemical characterization and electrode kinetics for antimony electrodeposition from its oxychloride solution in the presence of tartaric acid

NASA Astrophysics Data System (ADS)

Majidzade, Vusala Asim; Guliyev, Parvin Heydar; Aliyev, Akif Shikhan; Elrouby, Mahmoud; Tagiyev, Dilgam Babir

2017-05-01

This work is devoted to investigate the process of the electrochemical deposition of antimony from antimony oxychloride solution in the presence of tartaric acid in aqueous media. The kinetics and the mechanism of the electrodeposition process at the electrode surface are studied and proposed by the aid of cyclic, linear sweep voltammetric and chronoamperometric characterization methods. It is found that, the process is affected by the presence of tartaric acid and some factors during the electro-reduction process. The results also show that, the temperature, the potential sweep rate and the concentration of antimony have a great influence on the achievement of the electrodeposition process. Some important parameters are calculated such as, the activation energy of the electrochemical reaction, the diffusion coefficient and the number of saturated nucleation sites. The electrodeposited film is examined using X-ray diffraction, scanning electron microscopy and Energy Dispersive Spectroscopy.

Cold pressure welding of aluminium-steel blanks: Manufacturing process and electrochemical surface preparation

NASA Astrophysics Data System (ADS)

Schmidt, Hans Christian; Homberg, Werner; Orive, Alejandro Gonzalez; Grundmeier, Guido; Hordych, Illia; Maier, Hans Jürgen

2018-05-01

In this study the manufacture of aluminium-steel blanks by cold pressure welding and their preparation for a welding process through electrochemical surface treatment are investigated and discussed. The cold pressure welding process was done with an incremental rolling tool that allows for the partial pressure welding of two blanks along a prepared path. The influence of the surface preparation by electrochemical deposition of bond promoting organosilane-based agents and roughening on a nano-scale is investigated and compared to conventional surface treatments. Coating the surfaces with a thin organosilane-based film incorporating specific functional groups should promote additional bonding between the mating oxide layers; its influence on the total weld strength is studied. Pressure welding requires suitable process strategies, and the current advances in the proposed incremental rolling process for the combination of mild steel and aluminium are presented.

A Combustion Products Analyzer for contingency use during thermodegradation events on spacecraft

NASA Technical Reports Server (NTRS)

Limero, Thomas; James, John T.; Beck, Steven; Cromer, Raymond

1991-01-01

This paper will describe the Combustion Products Analyzer (CPA), which is being developed under the direction of the Toxicology Laboratory at Johnson Space Center to provide necessary data on air quality in the Shuttle following a thermodegradation incident. Using separate electrochemical sensors, the CPA monitors four gases (hydrogen fluoride/carbonyl fluoride, hydrogen chloride, hydrogen cyanide, and carbon monoxide), which were selected as the most hazardous compounds likely to be released during thermodegradation of synthetic materials. Electrochemical sensors have been available for several years; the CPA sensors, which are unique because of their small size and zero-gravity compatibility, will be described in detail.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOEpatents

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher; Lane, George Hamilton; Morgan, Dane; Nevin, Josh; Ceder, Gerbrand; Persson, Kristin Aslaug; Eaglesham, David

2015-10-27

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqeuous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negative electrode active material is described.

In situ electrochemical and photo-electrochemical generation of the fenton reagent: a potentially important new water treatment technology.

PubMed

Peralta-Hernández, J M; Meas-Vong, Yunny; Rodríguez, Francisco J; Chapman, Thomas W; Maldonado, Manuel I; Godínez, Luis A

2006-05-01

In this work, the design and construction of an annular tube reactor for the electrochemical and photo-electrochemical in situ generation of H2O2 are described. By cathodic reduction of dissolved oxygen and the coupled oxidation of water at a UV-illuminated nanocrystalline-TiO2 semiconductor anode, it was found that the electrochemically generated H2O2 can be employed to readily oxidize the model compound Direct Yellow-52 in dilute acidic solution at high rates in the presence of small quantities of dissolved iron(II). Although, the model organic compound is chemically stable under UV radiation, its electrochemical oxidation rate increases substantially when the semiconductor anode is illuminated as compared to the same processes carried out in the dark.

Solution Processed PEDOT Analogues in Electrochemical Supercapacitors.

PubMed

Österholm, Anna M; Ponder, James F; Kerszulis, Justin A; Reynolds, John R

2016-06-01

We have designed fully soluble ProDOTx-EDOTy copolymers that are electrochemically equivalent to electropolymerized PEDOT without using any surfactants or dispersants. We show that these copolymers can be incorporated as active layers in solution processed thin film supercapacitors to demonstrate capacitance, stability, and voltage similar to the values of those that use electrodeposited PEDOT as the active material with the added advantage of the possibility for large scale, high-throughput processing. These Type I supercapacitors provide exceptional cell voltages (up to 1.6 V), highly symmetrical charge/discharge behavior, promising long-term stability exceeding 50 000 charge/discharge cycles, as well as energy (4-18 Wh/kg) and power densities (0.8-3.3 kW/kg) that are comparable to those of electrochemically synthesized analogues.

Electrochemical removal of tannins from aqueous solutions

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

Buso, A.; Balbo, L.; Giomo, M.

2000-02-01

The application of electrochemical methods to remove tannins from wastewater was investigated. Gallotannic acid was used as the reference substance. Electrochemical experiments were performed using platinum electrodes. Macroscale potentiostatic or galvanostatic electrolyses were carried out with sodium sulfate or sodium chloride as supporting electrolytes, to analyze direct and indirect oxidation processes. Operating variables such as pH and chloride concentration were considered to determine their influence on the efficiency and energy consumption of the process. The simulation of a pilot plant was carried out with a mathematical model, the parameters of which were determined by fitting of experimental profiles. The resultsmore » of a preliminary investigation on the oxidation-coagulation process using sacrificial electrodes are also reported.« less

Mutual promotion of electrochemical-localized surface plasmon resonance on nanochip for sensitive sialic acid detection.

PubMed

Li, Shuang; Liu, Jinglong; Lu, Yanli; Zhu, Long; Li, Candong; Hu, Lijiang; Li, Jun; Jiang, Jing; Low, Szeshin; Liu, Qingjun

2018-06-01

Localized surface plasmon resonance (LSPR) induced charge separation were concentrated on the metal nanoparticles surface, which made it sensitive to the surface refractive index changes during optical sensing. Similarly, electrochemical detection was based on the electron transformation on the electrode surface. Herein, we fabricated a nanochip by decorating a nanocone-array substrate with gold nanoparticles and silver nanoparticles for dynamic electro-optical spectroscopy. Mercaptophenyl boronic acid (MPBA) was immobilized firmly on the nanochip by the metal-S bond for sensitive sialic acid sensing. Owing to the high stability of gold nanoparticles and the high sensitivity of silver nanoparticles, the nanochip showed good performance in LSPR detection with rich and high responses. Besides, the nanochip also showed sensitive electrical signals during electrochemical detection due to the excitation of the energetic charges from the nanoparticles surface to the reaction system. The dynamic electro-optical spectroscopy was based on a unique combination of LSPR and linear sweep voltammetry (LSV). On the one hand, electrochemical signals activated the electrons on the nanochip to promote the propagation and resonance of surface plasmon. On the other hand, LSPR concentrated the electrons on the nanochip surface, which made the electrons easily driven to enhance the current in electrochemical detection. Results showed that mutual promotion of electrochemical-LSPR on nanochip covered a linear dynamic range from 0.05 mM to 5 mM on selective sialic acid detection with a low detection limit of 17 μM. The synchronous amplification of the electro-optical response during electrochemical-LSPR, opened up a new perspective for efficient and sensitive biochemical detection. Copyright © 2018 Elsevier B.V. All rights reserved.

High Energy Density Capacitors

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

None

2010-07-01

BEEST Project: Recapping is developing a capacitor that could rival the energy storage potential and price of today’s best EV batteries. When power is needed, the capacitor rapidly releases its stored energy, similar to lightning being discharged from a cloud. Capacitors are an ideal substitute for batteries if their energy storage capacity can be improved. Recapping is addressing storage capacity by experimenting with the material that separates the positive and negative electrodes of its capacitors. These separators could significantly improve the energy density of electrochemical devices.

Microfabricated capillary electrophoresis chip and method for simultaneously detecting multiple redox labels

DOEpatents

Mathies, Richard A.; Singhal, Pankaj; Xie, Jin; Glazer, Alexander N.

2002-01-01

This invention relates to a microfabricated capillary electrophoresis chip for detecting multiple redox-active labels simultaneously using a matrix coding scheme and to a method of selectively labeling analytes for simultaneous electrochemical detection of multiple label-analyte conjugates after electrophoretic or chromatographic separation.

Stereoisomers Separation

NASA Astrophysics Data System (ADS)

Wieczorek, Piotr

The use of capillary electrophoresis for enantiomer separation and optical purity determination is presented. The contents start with basic information about the nature of stereoizomers and the mechanism of enantioseparation using capillary electrophoresis techniques. The molecules to be separated show identical chemical structure and electrochemical behavior. Therefore, the chiral recognition of enantiomers is possible only by bonding to chiral selector and the separation based on very small differences in complexation energies of diastereomer complexes formed. This method is useful for this purpose due to the fact that different compounds can be used as chiral selectors. The mostly used chiral selectors like cyclodextrins, crown ethers, chiral surfactants, macrocyclic antibiotics, transition metal complexes, natural, and synthetic polymers and their application for this purpose is also discussed. Finally, examples of practical applications of electromigration techniques for enantiomers separation and determination are presented.

Large silver-cadmium technology program

NASA Technical Reports Server (NTRS)

Charlip, S.; Lerner, S.

1971-01-01

The effects of varying cell design on operation factors on the electrochemical performance of sealed, silver-cadmium cells were determined. A factorial experiment was conducted for all test cells constructed with organic separators. Three operating factors were evaluated: temperature, depth of discharge, and charge rate. The six construction factors considered were separator, absorber, electrolyte quantity, cadmium electrode type, cadmium-to-silver ratio, and auxiliary electrode. Test cells of 4 ampere-hour capacity were fabricated and cycled. The best performing cells, on a 94 minute orbit, at 40% depth of discharge, were those containing silver-treated fibrous sausage casings as the separator, and Teflon-ated, pressed cadmium electrodes. Cycling data of cells with inorganic separators (Astroset) are given. Best performance was shown by cells with nonwoven nylon absorbers. Rigid inorganic separators provided the best barrier to silver migration.

Controlled assembly and single electron charging of monolayer protected Au144 clusters: an electrochemistry and scanning tunneling spectroscopy study

NASA Astrophysics Data System (ADS)

Bodappa, Nataraju; Fluch, Ulrike; Fu, Yongchun; Mayor, Marcel; Moreno-García, Pavel; Siegenthaler, Hans; Wandlowski, Thomas

2014-11-01

Single gold particles may serve as room temperature single electron memory units because of their size dependent electronic level spacing. Here, we present a proof-of-concept study by electrochemically controlled scanning probe experiments performed on tailor-made Au particles of narrow dispersity. In particular, the charge transport characteristics through chemically synthesized hexane-1-thiol and 4-pyridylbenzene-1-thiol mixed monolayer protected Au144 clusters (MPCs) by differential pulse voltammetry (DPV) and electrochemical scanning tunneling spectroscopy (EC-STS) are reported. The pyridyl groups exposed by the Au-MPCs enable their immobilization on Pt(111) substrates. By varying the humidity during their deposition, samples coated by stacks of compact monolayers of Au-MPCs or decorated with individual, laterally separated Au-MPCs are obtained. DPV experiments with stacked monolayers of Au144-MPCs and EC-STS experiments with laterally separated individual Au144-MPCs are performed both in aqueous and ionic liquid electrolytes. Lower capacitance values were observed for individual clusters compared to ensemble clusters. This trend remains the same irrespective of the composition of the electrolyte surrounding the Au144-MPC. However, the resolution of the energy level spacing of the single clusters is strongly affected by the proximity of neighboring particles.Single gold particles may serve as room temperature single electron memory units because of their size dependent electronic level spacing. Here, we present a proof-of-concept study by electrochemically controlled scanning probe experiments performed on tailor-made Au particles of narrow dispersity. In particular, the charge transport characteristics through chemically synthesized hexane-1-thiol and 4-pyridylbenzene-1-thiol mixed monolayer protected Au144 clusters (MPCs) by differential pulse voltammetry (DPV) and electrochemical scanning tunneling spectroscopy (EC-STS) are reported. The pyridyl groups exposed by the Au-MPCs enable their immobilization on Pt(111) substrates. By varying the humidity during their deposition, samples coated by stacks of compact monolayers of Au-MPCs or decorated with individual, laterally separated Au-MPCs are obtained. DPV experiments with stacked monolayers of Au144-MPCs and EC-STS experiments with laterally separated individual Au144-MPCs are performed both in aqueous and ionic liquid electrolytes. Lower capacitance values were observed for individual clusters compared to ensemble clusters. This trend remains the same irrespective of the composition of the electrolyte surrounding the Au144-MPC. However, the resolution of the energy level spacing of the single clusters is strongly affected by the proximity of neighboring particles. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03793f

Low-Cost alpha Alane for Hydrogen Storage

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

Fabian, Tibor; Petrie, Mark; Crouch-Baker, Steven

This project was directed towards the further development of the Savannah River National Laboratory (SRNL) lab-scale electrochemical synthesis of the hydrogen storage material alpha-alane and Ardica Technologies-SRI International (SRI) chemical downstream processes that are necessary to meet DoE cost metrics and transition alpha-alane synthesis to an industrial scale. Ardica has demonstrated the use of alpha-alane in a fuel-cell system for the U.S. Army WFC20 20W soldier power system that has successfully passed initial field trials with individual soldiers. While alpha-alane has been clearly identified as a desirable hydrogen storage material, cost-effective means for its production and regeneration on a scalemore » of use applicable to the industry have yet to be established. We focused on three, principal development areas: 1. The construction of a comprehensive engineering techno-economic model to establish the production costs of alpha-alane by both electrochemical and chemical routes at scale. 2. The identification of critical, cost-saving design elements of the electrochemical cell and the quantification of the product yields of the primary electrochemical process. A moving particle-bed reactor design was constructed and operated. 3. The experimental quantification of the product yields of candidate downstream chemical processes necessary to produce alpha-alane to complete the most cost-effective overall manufacturing process. Our techno-economic model shows that under key assumptions most 2015 and 2020 DOE hydrogen storage system cost targets for low and medium power can be achieved using the electrochemical alane synthesis process. To meet the most aggressive 2020 storage system cost target, $1/g, our model indicates that 420 metric tons per year (MT/y) production of alpha-alane is required. Laboratory-scale experimental work demonstrated that the yields of two of the three critical component steps within the overall “electrochemical process” were sufficiently high to meet this production target. In the case of the yield of the third step, the crystallization of alpha-alane from the primary alane-related product of the electrochemical reaction, further development is required.« less

Integration of thermocouple microelectrode in the scanning electrochemical microscope at variable temperatures: simultaneous temperature and electrochemical imaging and its kinetic studies.

PubMed

Pan, He; Zhang, Hailing; Lai, Junhui; Gu, Xiaoxin; Sun, Jianjun; Tang, Jing; Jin, Tao

2017-03-24

We describe herein a method for the simultaneous measurement of temperature and electrochemical signal with a new type of thermocouple microelectrode. The thermocouple microelectrode can be used not only as a thermometer but also as a scanning electrochemical microscope (SECM) tip in the reaction between tip-generated bromine and a heated Cu sample. The influence of temperature on the SECM imaging process and the related kinetic parameters have been studied, such as kinetic constant and activation energy.

Integration of thermocouple microelectrode in the scanning electrochemical microscope at variable temperatures: simultaneous temperature and electrochemical imaging and its kinetic studies

PubMed Central

Pan, He; Zhang, Hailing; Lai, Junhui; Gu, Xiaoxin; Sun, Jianjun; Tang, Jing; Jin, Tao

2017-01-01

We describe herein a method for the simultaneous measurement of temperature and electrochemical signal with a new type of thermocouple microelectrode. The thermocouple microelectrode can be used not only as a thermometer but also as a scanning electrochemical microscope (SECM) tip in the reaction between tip-generated bromine and a heated Cu sample. The influence of temperature on the SECM imaging process and the related kinetic parameters have been studied, such as kinetic constant and activation energy. PMID:28338002