Ion-selective detection by plasticized poly(vinyl chloride) membrane in glass nanopipette with alternating voltage modulation.

PubMed

Deng, Xiao Long; Takami, Tomohide; Son, Jong Wan; Kang, Eun Ji; Kawai, Tomoji; Park, Bae Ho

2013-08-01

An alternating current (AC) voltage modulation was applied to ion-selective observations with plasticized poly(vinyl chloride) membranes in glass nanopipettes. The liquid confronting the membranes in the nanopipettes, the conditioning process, and AC voltage modulation play important roles in the ion-selective detection. In the AC detection system developed by us, where distilled water was used as the liquid within the nanopipettes, potassium ions were selectively detected in the sample solution of sodium and potassium ions because sodium ions were captured at the membrane containing bis(12-crown-4) ionophores, before the saturation of the ionophores. The membrane lost the selectivity after the saturation. On using sodium chloride as the liquid within the nanopipette, the membrane selectively detected potassium and sodium ions before and after the saturation of ionophores, respectively. The ion-selective detection of our system can be explained by the ion extraction-diffusion-dissolution mechanism through the bis(12-crown-4) ionophores with AC voltage modulation.

Kinetic Modulation of Pulsed Chrono-potentiometric Polymeric Membrane Ion Sensors by Polyelectrolyte Multilayers

PubMed Central

Xu, Yida; Xu, Chao; Shvarev, Alexey; Becker, Thomas; De Marco, Roland

2010-01-01

Polymeric membrane ion selective electrodes are normally interrogated by zero current potentiometry, and their selectivity is understood to be primarily dependent on an extraction/ion-exchange equilibrium between the aqueous sample and polymeric membrane. If concentration gradients in the contacting diffusion layers are insubstantial, the membrane response is thought to be rather independent of kinetic processes such as surface blocking effects. In this work, the surface of calcium-selective polymeric ion-selective electrodes is coated with polyelectrolyte multilayers as evidenced by zeta potential measurements, atomic force microscopy and electrochemical impedance spectroscopy. Indeed, such multilayers have no effect on their potentiometric response if the membranes are formulated in a traditional manner, containing a lipophilic ion-exchanger and a calcium-selective ionophore. However, drastic changes in the potential response are observed if the membranes are operated in a recently introduced kinetic mode using pulsed chronopotentiometry. The results suggest that the assembled nanostructured multilayers drastically alter the kinetics of ion transport to the sensing membrane, making use of the effect that polyelectrolyte multilayers have different permeabilities toward ions with different valences. The results have implications to the design of chemically selective ion sensors since surface localized kinetic limitations can now be used as an additional dimension to tune the operational ion selectivity. PMID:17711298

A new ion selective electrode for cesium (I) based on calix[4]arene-crown-6 compounds.

PubMed

Ramanjaneyulu, P S; Kumar, Abha Naveen; Sayi, Y S; Ramakumar, K L; Nayak, S K; Chattopadhyay, S

2012-02-29

A polyvinylchloride (PVC) based liquid membrane ion selective electrode (ISE) for cesium has been developed. 25,27-Dihydroxycalix[4]arene-crown-6 (L1), 5,11,17,23-tetra-tert-butyl-25,27-dimethoxycalix[4]arene-crown-6 (L2) and 25,27-bis(1-octyloxy)calix[4]arene-crown-6 (L3) were investigated for their use as ionophores. The cation exchange resin DOWEX-50W was used to maintain low activity Cs+ in inner filling solution to improve the performance. The best response for cesium was observed with L3 along with optimized membrane constituents and composition. Excellent Nernstian response (56.6 mV/decade of Cs(I)) over the concentration range 10(-7) to 10(-2)M of Cs(I) was obtained with a fast response time of less than 10s. Detection limit for Cs(I) using the present ISE is 8.48×10(-8) M Cs(I). Separate solution method (SSM) was applied to ascertain the selectivity for Cs(I) over alkali, alkaline earth and transition metal ions. The response of ISE for Cs(I) was fairly constant over the pH range of 4-11. The lifetime of the electrode is 10 months which is the highest life for any membrane based Cs-ISE so far developed. The concentration of cesium ion in two simulated high level active waste streams was determined and results agreed well with those obtained independently employing AAS. Copyright © 2011 Elsevier B.V. All rights reserved.

Development of a ceramic membrane from a lithian spinel, Li1+xMyMn2-yO4 (M=trivalent or tetravalent cations) for a Li ion-selective electrode

NASA Astrophysics Data System (ADS)

Yoon, H.; Venugopal, N.; Rim, T.; Yang, B.; Chung, K.; Ko, T.

2010-12-01

Recently a few lithium containing ceramics are reported as promising cathodes for application in lithium batteries. Among them, a spinel-type lithium manganate (LM) exhibits an exceptionally high ion selectivity at room temperature. Thus, LM could have a great potential as an ion selective membrane material for screening interfering ions from lithium ion for the determination of lithium ion in salt solution. In this study, we developed an ion-selective electrode based on LM as a membrane material and investigated its lithium ion selectivity by varying the content of M in composition. A sol-gel process was successfully applied for preparing LM films without resorting to calcination at a high temperature. The LM thin film-type membranes exhibit a high selectivity for Li ion over other cations, a wide operation detection range of 10-5 ~ 10-2 M, and a fast response time less than 60 s. Furthermore, our result demonstrates a linear potentiometric response over a wide range of lithium concentration, which is compared to that of a lithium ion-selective electrode based on an ionophore. Acknowledgements: This research was supported by a grant from the Development of Technology for Extraction of Resources Dissolved in Sea Water Program funded by Ministry of Land Transport and Maritime Affairs in Korean Government (2010).

Direct evidence of ionic fluxes across ion-selective membranes: a scanning electrochemical microscopic and potentiometric study.

PubMed

Gyurcsányi, R E; Pergel, E; Nagy, R; Kapui, I; Lan, B T; Tóth, K; Bitter, I; Lindner, E

2001-05-01

Scanning electrochemical microscopy (SECM) supplemented with potentiometric measurements was used to follow the time-dependent buildup of a steady-state diffusion layer at the aqueous-phase boundary of lead ion-selective electrodes (ISEs). Differential pulse voltammetry is adapted to SECM for probing the local concentration profiles at the sample side of solvent polymeric membranes. Major factors affecting the membrane transport-related surface concentrations were identified from SECM data and the potentiometric transients obtained under different experimental conditions (inner filling solution composition, membrane thickness, surface pretreatment). The amperometrically determined surface concentrations correlated well with the lower detection limits of the lead ion-selective electrodes.

Ion distribution and selectivity of ionic liquids in microporous electrodes.

PubMed

Neal, Justin N; Wesolowski, David J; Henderson, Douglas; Wu, Jianzhong

2017-05-07

The energy density of an electric double layer capacitor, also known as supercapacitor, depends on ion distributions in the micropores of its electrodes. Herein we study ion selectivity and partitioning of symmetric, asymmetric, and mixed ionic liquids among different pores using the classical density functional theory. We find that a charged micropore in contact with mixed ions of the same valence is always selective to the smaller ions, and the ion selectivity, which is strongest when the pore size is comparable to the ion diameters, drastically falls as the pore size increases. The partitioning behavior in ionic liquids is fundamentally different from those corresponding to ion distributions in aqueous systems whereby the ion selectivity is dominated by the surface energy and entropic effects insensitive to the degree of confinement.

Solid-contact pH-selective electrode using multi-walled carbon nanotubes.

PubMed

Crespo, Gastón A; Gugsa, Derese; Macho, Santiago; Rius, F Xavier

2009-12-01

Multi-walled carbon nanotubes (MWCNT) are shown to be efficient transducers of the ionic-to-electronic current. This enables the development of a new solid-contact pH-selective electrode that is based on the deposition of a 35-microm thick layer of MWCNT between the acrylic ion-selective membrane and the glassy carbon rod used as the electrical conductor. The ion-selective membrane was prepared by incorporating tridodecylamine as the ionophore, potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as the lipophilic additive in a polymerized methylmethacrylate and an n-butyl acrylate matrix. The potentiometric response shows Nernstian behaviour and a linear dynamic range between 2.89 and 9.90 pH values. The response time for this electrode was less than 10 s throughout the whole working range. The electrode shows a high selectivity towards interfering ions. Electrochemical impedance spectroscopy and chronopotentiometry techniques were used to characterise the electrochemical behaviour and the stability of the carbon-nanotube-based ion-selective electrodes.

Picomolar detection limits with current-polarized Pb2+ ion-selective membranes.

PubMed

Pergel, E; Gyurcsányi, R E; Tóth, K; Lindner, E

2001-09-01

Minor ion fluxes across ion-selective membranes bias submicromolar activity measurements with conventional ion-selective electrodes. When ion fluxes are balanced, the lower limit of detection is expected to be dramatically improved. As proof of principle, the flux of lead ions across an ETH 5435 ionophore-based lead-selective membrane was gradually compensated by applying a few nanoamperes of galvanostatic current. When the opposite ion fluxes were matched, and the undesirable leaching of primary ions was eliminated, Nernstian response down to 3 x 10(-12) M was achieved.

Asymmetric battery having a semi-solid cathode and high energy density anode

DOEpatents

Tan, Taison; Chiang, Yet-Ming; Ota, Naoki; Wilder, Throop; Duduta, Mihai

2017-11-28

Embodiments described herein relate generally to devices, systems and methods of producing high energy density batteries having a semi-solid cathode that is thicker than the anode. An electrochemical cell can include a positive electrode current collector, a negative electrode current collector and an ion-permeable membrane disposed between the positive electrode current collector and the negative electrode current collector. The ion-permeable membrane is spaced a first distance from the positive electrode current collector and at least partially defines a positive electroactive zone. The ion-permeable membrane is spaced a second distance from the negative electrode current collector and at least partially defines a negative electroactive zone. The second distance is less than the first distance. A semi-solid cathode that includes a suspension of an active material and a conductive material in a non-aqueous liquid electrolyte is disposed in the positive electroactive zone, and an anode is disposed in the negative electroactive zone.

Asymmetric battery having a semi-solid cathode and high energy density anode

DOEpatents

Tan, Taison; Chiang, Yet-Ming; Ota, Naoki; Wilder, Throop; Duduta, Mihai

2016-09-06

Embodiments described herein relate generally to devices, systems and methods of producing high energy density batteries having a semi-solid cathode that is thicker than the anode. An electrochemical cell can include a positive electrode current collector, a negative electrode current collector and an ion-permeable membrane disposed between the positive electrode current collector and the negative electrode current collector. The ion-permeable membrane is spaced a first distance from the positive electrode current collector and at least partially defines a positive electroactive zone. The ion-permeable membrane is spaced a second distance from the negative electrode current collector and at least partially defines a negative electroactive zone. The second distance is less than the first distance. A semi-solid cathode that includes a suspension of an active material and a conductive material in a non-aqueous liquid electrolyte is disposed in the positive electroactive zone, and an anode is disposed in the negative electroactive zone.

Miniaturizable Ion-Selective Arrays Based on Highly Stable Polymer Membranes for Biomedical Applications

PubMed Central

Mir, Mònica; Lugo, Roberto; Tahirbegi, Islam Bogachan; Samitier, Josep

2014-01-01

Poly(vinylchloride) (PVC) is the most common polymer matrix used in the fabrication of ion-selective electrodes (ISEs). However, the surfaces of PVC-based sensors have been reported to show membrane instability. In an attempt to overcome this limitation, here we developed two alternative methods for the preparation of highly stable and robust ion-selective sensors. These platforms are based on the selective electropolymerization of poly(3,4-ethylenedioxythiophene) (PEDOT), where the sulfur atoms contained in the polymer covalently interact with the gold electrode, also permitting controlled selective attachment on a miniaturized electrode in an array format. This platform sensor was improved with the crosslinking of the membrane compounds with poly(ethyleneglycol) diglycidyl ether (PEG), thus also increasing the biocompatibility of the sensor. The resulting ISE membranes showed faster signal stabilization of the sensor response compared with that of the PVC matrix and also better reproducibility and stability, thus making these platforms highly suitable candidates for the manufacture of robust implantable sensors. PMID:24999717

Direct Observation of Ion Distributions near Electrodes in Ionic Polymer Actuators Containing Ionic Liquids

PubMed Central

Liu, Yang; Lu, Caiyan; Twigg, Stephen; Ghaffari, Mehdi; Lin, Junhong; Winograd, Nicholas; Zhang, Q. M.

2013-01-01

The recent boom of energy storage and conversion devices, exploiting ionic liquids (ILs) to enhance the performance, requires an in-depth understanding of this new class of electrolytes in device operation conditions. One central question critical to device performance is how the mobile ions accumulate near charged electrodes. Here, we present the excess ion depth profiles of ILs in ionomer membrane actuators (Aquivion/1-butyl-2,3-dimethylimidazolium chloride (BMMI-Cl), 27 μm thick), characterized directly by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) at liquid nitrogen temperature. Experimental results reveal that for the IL studied, cations and anions are accumulated at both electrodes. The large difference in the total volume occupied by the excess ions between the two electrodes cause the observed large bending actuation of the actuator. Hence we demonstrate that ToF-SIMS experiment provides great insights on the physics nature of ionic devices. PMID:23512124

Influence of Inner Transducer Properties on EMF Response and Stability of Solid-Contact Anion Selective Membrane Electrodes Based on Metalloporphyrin Ionophores

PubMed Central

Górski, Łukasz; Matusevich, Alexey; Pietrzak, Mariusz; Wang, Lin; Meyerhoff, Mark E.; Malinowska, Elżbieta

2010-01-01

The performance of solid-contact/coated wire type electrodes with plasticized PVC membranes containing metalloporphyrins as anion selective ionophores is reported. The membranes are deposited on transducers based on graphite pastes and graphite rods. The hydrophobicity of the underlying conductive transducer surface is found to be a key factor that influences the formation of an aqueous layer beneath the polymer film. Elimination of this ill-defined water layer greatly improves the electrochemical properties of the ion-sensors, such as EMF stability and life-time. Only highly lipophilic electrode substrates, namely graphite paste with mineral oil, were shown to prevent the formation of aqueous layer underneath the ion-sensing membrane. The possibility of employing Co(III)-tetraphenylporphyrin both as NO2− selective ionophore and as electron/ion conducting species to ensure ion-to-electron translation was also discussed based on the results of preliminary experiments. PMID:20357903

Single-ion polymer electrolyte membranes enable lithium-ion batteries with a broad operating temperature range.

PubMed

Cai, Weiwei; Zhang, Yunfeng; Li, Jing; Sun, Yubao; Cheng, Hansong

2014-04-01

Conductive processes involving lithium ions are analyzed in detail from a mechanistic perspective, and demonstrate that single ion polymeric electrolyte (SIPE) membranes can be used in lithium-ion batteries with a wide operating temperature range (25-80 °C) through systematic optimization of electrodes and electrode/electrolyte interfaces, in sharp contrast to other batteries equipped with SIPE membranes that display appreciable operability only at elevated temperatures (>60 °C). The performance is comparable to that of batteries using liquid electrolyte of inorganic salt, and the batteries exhibit excellent cycle life and rate performance. This significant widening of battery operation temperatures coupled with the inherent flexibility and robustness of the SIPE membranes makes it possible to develop thin and flexible Li-ion batteries for a broad range of applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly selective direct determination of chlorate ions by using a newly developed potentiometric electrode based on modified smectite.

PubMed

Topcu, Cihan

2016-12-01

A novel polyvinyl chloride membrane chlorate (ClO 3 - ) selective electrode based on modified smectite was developed for the direct determination of chlorate ions and the potentiometric performance characteristics of its were examined. The best selectivity and sensitivity for chlorate ions were obtained for the electrode membrane containing ionophore/polyvinylchloride/o-nitrophenyloctylether in composition of 12/28/60 (w/w%). The proposed electrode showed a Nernstian response toward chlorate ions at pH=7 in the concentration range of 1×10 -7 -1×10 -1 M and the limit of detection was calculated as 9×10 -8 M from the constructed response plot. The linear slope of the electrode was -61±1mVdecade -1 for chlorate activity in the mentioned linear working range. The selectivity coefficients were calculated according to both the matched potential method and the separate solution method. The calculated selectivity coefficients showed that the electrode performed excellent selectivity for chlorate ions. The potentiometric response of electrode toward chlorate ions was found to be highly reproducible. The electrode potential was stable between pH=4-10 and it had a dynamic response time of <5s. The potentiometric behavior of the electrode in partial non-aqueous medium was also investigated and the obtained results (up to 5% (v/v) alcohol) were satisfactory. The proposed electrode was used during 15 weeks without any significant change in its potential response. Additionally, the electrode was very useful in water analysis studies such as dam water, river water, tap water, and swimming pool water where the direct determination of chlorate ions was required. Copyright © 2016 Elsevier B.V. All rights reserved.

Integration of reconfigurable potentiometric electrochemical sensors into a digital microfluidic platform.

PubMed

Farzbod, Ali; Moon, Hyejin

2018-05-30

This paper presents the demonstration of on-chip fabrication of a potassium-selective sensor array enabled by electrowetting on dielectric digital microfluidics for the first time. This demonstration proves the concept that electrochemical sensors can be seamlessly integrated with sample preparation units in a digital microfluidic platform. More significantly, the successful on-chip fabrication of a sensor array indicates that sensors become reconfigurable and have longer lifetime in a digital microfluidic platform. The on-chip fabrication of ion-selective electrodes includes electroplating Ag followed by forming AgCl layer by chemical oxidation and depositing a thin layer of desired polymer-based ion selective membrane on one of the sensor electrodes. In this study, potassium ionophores work as potassium ion channels and make the membrane selective to potassium ions. This selectiveness results in the voltage difference across the membrane layer, which is correlated with potassium ion concentration. The calibration curve of the fabricated potassium-selective electrode demonstrates the slope of 58 mV/dec for potassium concentration in KCl sample solutions and shows good agreement with the ideal Nernstian response. The proposed sensor platform is an outstanding candidate for a portable home-use for continuous monitoring of ions thanks to its advantages such as easy automation of sample preparation and detection processes, elongated sensor lifetime, minimal membrane and sample consumption, and user-definable/reconfigurable sensor array. Copyright © 2018 Elsevier B.V. All rights reserved.

Method and apparatus for removing ions from soil

DOEpatents

Bibler, J.P.

1993-03-02

A method and apparatus are presented for selectively removing species of ions from an area of soil. Permeable membranes 14 and 18 impregnated with an ion exchange resin that is specific to one or more species of chemical ions are inserted into ground 12 in close proximity to, and on opposing sides of, a soil area of interest 22. An electric potential is applied across electrodes 26 and 28 to cause the migration of ions out of soil area 22 toward the membranes 14 and 18. Preferably, the resin exchanges ions of sodium or hydrogen for ions of mercury that it captures from soil area 22. Once membranes 14 and 18 become substantially saturated with mercury ions, the potential applied across electrodes 26 and 28 is discontinued and membranes 14 and 18 are preferably removed from soil 12 for storage or recovery of the ions. The membranes are also preferably impregnated with a buffer to inhibit the effect of the hydrolysis of water by current from the electrodes.

Method and apparatus for removing ions from soil

DOEpatents

Bibler, Jane P.

1993-01-01

A method and apparatus for selectively removing species of ions from an area of soil. Permeable membranes 14 and 18 impregnated with an ion exchange resin that is specific to one or more species of chemical ions are inserted into ground 12 in close proximity to, and on opposing sides of, a soil area of interest 22. An electric potential is applied across electrodes 26 and 28 to cause the migration of ions out of soil area 22 toward the membranes 14 and 18. Preferably, the resin exchanges ions of sodium or hydrogen for ions of mercury that it captures from soil area 22. Once membranes 14 and 18 become substantially saturated with mercury ions, the potential applied across electrodes 26 and 28 is discontinued and membranes 14 and 18 are preferably removed from soil 12 for storage or recovery of the ions. The membranes are also preferably impregnated with a buffer to inhibit the effect of the hydrolysis of water by current from the electrodes.

Membrane permeation process for dehydration of organic liquid mixtures using sulfonated ion-exchange polyalkene membranes

DOEpatents

Cabasso, Israel; Korngold, Emmanuel

1988-01-01

A membrane permeation process for dehydrating a mixture of organic liquids, such as alcohols or close boiling, heat sensitive mixtures. The process comprises causing a component of the mixture to selectively sorb into one side of sulfonated ion-exchange polyalkene (e.g., polyethylene) membranes and selectively diffuse or flow therethrough, and then desorbing the component into a gas or liquid phase on the other side of the membranes.

Potentiometric measurement of polymer-membrane electrodes based on lanthanum

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

Saefurohman, Asep, E-mail: saefurohman.asep78@Gmail.com; Buchari,, E-mail: saefurohman.asep78@Gmail.com; Noviandri, Indra, E-mail: saefurohman.asep78@Gmail.com

2014-03-24

Quantitative analysis of rare earth elements which are considered as the standard method that has a high accuracy, and detection limits achieved by the order of ppm is inductively coupled plasma atomic emission spectroscopy (ICPAES). But these tools are expensive and valuable analysis of the high cost of implementation. In this study be made and characterized selective electrode for the determination of rare earth ions is potentiometric. Membrane manufacturing techniques studied is based on immersion (liquid impregnated membrane) in PTFE 0.5 pore size. As ionophores to be used tri butyl phosphate (TBP) and bis(2-etylhexyl) hydrogen phosphate. There is no reportmore » previously that TBP used as ionophore in polymeric membrane based lanthanum. Some parameters that affect the performance of membrane electrode such as membrane composition, membrane thickness, and types of membrane materials studied in this research. Manufacturing of Ion Selective Electrodes (ISE) Lanthanum (La) by means of impregnation La membrane in TBP in kerosene solution has been done and showed performance for ISE-La. FTIR spectrum results for PTFE 0.5 pore size which impregnated in TBP and PTFE blank showed difference of spectra in the top 1257 cm{sup −1}, 1031 cm{sup −1} and 794.7 cm{sup −1} for P=O stretching and stretching POC from group −OP =O. The result showed shift wave number for P =O stretching of the cluster (−OP=O) in PTFE-TBP mixture that is at the peak of 1230 cm{sup −1} indicated that no interaction bond between hydroxyl group of molecules with molecular clusters fosforil of TBP or R{sub 3}P = O. The membrane had stable responses in pH range between 1 and 9. Good responses were obtained using 10{sup −3} M La(III) internal solution, which produced relatively high potential. ISE-La showed relatively good performances. The electrode had a response time of 29±4.5 second and could be use for 50 days. The linear range was between 10{sup −5} and 10{sup −1} M.« less

Liquid membrane coated ion-exchange column solids

DOEpatents

Barkey, Dale P.

1988-01-01

This invention relates to a method for improving the performance of liquid membrane separations by coating a liquid membrane onto solid ion-exchange resin beads in a fixed bed. Ion-exchange beads fabricated from an ion-exchange resin are swelled with water and are coated with a liquid membrane material that forms a film over the beads. The beads constitute a fixed bed ion-exchange column. Fluid being treated that contains the desired ion to be trapped by the ion-exchange particle is passed through the column. A carrier molecule, contained in the liquid membrane ion-exchange material, is selective for the desired ion in the fluid. The carrier molecule forms a complex with the desired ion, transporting it through the membrane and thus separating it from the other ions. The solution is fed continuously until breakthrough occurs at which time the ion is recovered, and the bed is regenerated.

Systems and methods for selective hydrogen transport and measurement

DOEpatents

Glatzmaier, Gregory C

2013-10-29

Systems and methods for selectively removing hydrogen gas from a hydrogen-containing fluid volume are disclosed. An exemplary system includes a proton exchange membrane (PEM) selectively permeable to hydrogen by exclusively conducting hydrogen ions. The system also includes metal deposited as layers onto opposite sides or faces of the PEM to form a membrane-electrode assembly (MEA), each layer functioning as an electrode so that the MEA functions as an electrochemical cell in which the ionic conductors are hydrogen ions, and the MEA functioning as a hydrogen selective membrane (HSM) when located at the boundary between a hydrogen-containing fluid volume and a second fluid.

Potentiometric Response Characteristics of Membrane-Based Cs + -Selective Electrodes Containing Ionophore-Functionalized Polymeric Microspheres

DOE PAGES

Peper, Shane; Gonczy, Chad

2011-01-01

Csmore » + -selective solvent polymeric membrane-based ion-selective electrodes (ISEs) were developed by doping ethylene glycol-functionalized cross-linked polystyrene microspheres (P-EG) into a plasticized poly(vinyl chloride) (PVC) matrix containing sodium tetrakis-(3,5-bis(trifluoromethyl)phenyl) borate (TFPB) as the ion exchanger. A systematic study examining the effects of the membrane plasticizers bis(2-ethylhexyl) sebacate (DOS), 2-nitrophenyl octyl ether (NPOE), and 2-fluorophenyl nitrophenyl ether (FPNPE) on the potentiometric response and selectivity of the corresponding electrodes was performed. Under certain conditions, P-EG-based ion-selective electrodes (ISEs) containing TFPB and plasticized with NPOE exhibited a super-Nernstian response between 1 × 10 − 3 and 1 × 10 − 4  M + , a response characteristic not observed in analogous membranes plasticized with either DOS or FPNPE. Additionally, the performance of P-EG-based ISEs was compared to electrodes based on two mobile ionophores, a neutral lipophilic ethylene glycol derivative (ethylene glycol monooctadecyl ether (U-EG)) and a charged metallacarborane ionophore, sodium bis(dicarbollyl)cobaltate(III) (CC). In general, P-EG-based electrodes plasticized with FPNPE yielded the best performance, with a linear range from 10 -1 –10 -5  M + , a conventional lower detection limit of 8.1 × 10 − 6  M + , and a response slope of 57.7 mV/decade. The pH response of P-EG ISEs containing TFPB was evaluated for membranes plasticized with either NPOE or FPNPE. In both cases, the electrodes remained stable throughout the pH range 3–12, with only slight proton interference observed below pH 3.« less

Liquid membrane coated ion-exchange column solids

DOEpatents

Barkey, Dale P.

1989-01-01

This invention relates to a method for improving the performance of liquid embrane separations by coating a liquid membrane onto solid ion-exchange resin beads in a fixed bed. Ion-exchange beads fabricated from an ion-exchange resin are swelled with water and are coated with a liquid membrane material that forms a film over the beads. The beads constitute a fixed bed ion-exchange column. Fluid being treated that contains the desired ion to be trapped by the ion-exchange particle is passed through the column. A carrier molecule, contained in the liquid membrane ion-exchange material, is selected for the desired ion in the fluid. The carrier molecule forms a complex with the desired ion, transporting it through the membrane and thus separating it from the other ions. The solution is fed continuously until breakthrough occurs at which time the ion is recovered, and the bed is regenerated.

Junction Potentials Bias Measurements of Ion Exchange Membrane Permselectivity.

PubMed

Kingsbury, Ryan S; Flotron, Sophie; Zhu, Shan; Call, Douglas F; Coronell, Orlando

2018-04-17

Ion exchange membranes (IEMs) are versatile materials relevant to a variety of water and waste treatment, energy production, and industrial separation processes. The defining characteristic of IEMs is their ability to selectively allow positive or negative ions to permeate, which is referred to as permselectivity. Measured values of permselectivity that equal unity (corresponding to a perfectly selective membrane) or exceed unity (theoretically impossible) have been reported for cation exchange membranes (CEMs). Such nonphysical results call into question our ability to correctly measure this crucial membrane property. Because weighing errors, temperature, and measurement uncertainty have been shown to not explain these anomalous permselectivity results, we hypothesized that a possible explanation are junction potentials that occur at the tips of reference electrodes. In this work, we tested this hypothesis by comparing permselectivity values obtained from bare Ag/AgCl wire electrodes (which have no junction) to values obtained from single-junction reference electrodes containing two different electrolytes. We show that permselectivity values obtained using reference electrodes with junctions were greater than unity for CEMs. In contrast, electrodes without junctions always produced permselectivities lower than unity. Electrodes with junctions also resulted in artificially low permselectivity values for AEMs compared to electrodes without junctions. Thus, we conclude that junctions in reference electrodes introduce two biases into results in the IEM literature: (i) permselectivity values larger than unity for CEMs and (ii) lower permselectivity values for AEMs compared to those for CEMs. These biases can be avoided by using electrodes without a junction.

Construction of a new selective coated disk electrode for Ag (I) based on modified polypyrrole-carbon nanotubes composite with new lariat ether.

PubMed

Abbaspour, A; Tashkhourian, J; Ahmadpour, S; Mirahmadi, E; Sharghi, H; Khalifeh, R; Shahriyari, M R

2014-01-01

A poly (vinyl chloride) (PVC) matrix membrane ion-selective electrode for silver (I) ion is fabricated based on modified polypyrrole - multiwalled carbon nanotubes composite with new lariat ether. This sensor has a Nernstian slope of 59.4±0.5mV/decade over a wide linear concentration range of 1.0×10(-7) to 1.0×10(-1)molL(-1) for silver (I) ion. It has a short response time of about 8.0s and can be used for at least 50days. The detection limit is 9.3×10(-8)molL(-1) for silver (I) ion, and the electrode was applicable in the wide pH range of 1.6 -7.7. The electrode shows good selectivity for silver ion against many cations such as Hg (II), which usually imposes serious interference in the determination of silver ion concentration. The use of multiwalled carbon nanotubes (MWCNTs) in a polymer matrix improves the linear range and sensitivity of the electrode. In addition by coating the solid contact with a layer of the polypyrrole (Ppy) before coating the membrane on it, not only did it reduce the drift in potential, but a shorter response time was also resulted. The proposed electrode was used as an indicator electrode for potentiometric titration of silver ions with chloride anions and in the titration of mixed halides. This electrode was successfully applied for the determination of silver ions in silver sulphadiazine as a burning cream. © 2013.

Determination of Cd2+ in aqueous solution using polyindole-Ce(IV) vanadophosphate conductive nanocomposite ion-selective membrane electrode

NASA Astrophysics Data System (ADS)

Khan, Asif Ali; Quasim Khan, Mohd; Hussain, Rizwan

2017-09-01

In the present study an organic-inorganic nanocomposite ion exchanger Polyindole-Ce(IV) vanadophosphate (PIn-CVP) was synthesized via sol-gel process showing excellent ion exchange capacity (IEC‒1.90 meqg-1). The material was characterized by SEM, TEM, XRD, FTIR, and TGA. A heterogeneous ion exchange membrane of PIn-CVP (IEC‒0.90 meqg-1) was also prepared by solution casting method. PIn-CVP shows high electrical conductivity (5.5  ×  10-2 S cm-1) and it is stable up to 120 °C under ambient conditions. Cd2+ selective membrane electrode was fabricated and its linear working range (3.98  ×  10-7 M to 1.0  ×  10-1 M), response time (25 s), Nerstian slope 25.00 mV dec-1 and working pH range (4-7) were calculated. It was employed as an indicator electrode in the potentiometric titration of Cd2+.

Laboratory Evaluation of Ion-Selective Electrodes for Simultaneous Analysis of Macronutrients in Hydroponic Solution

USDA-ARS?s Scientific Manuscript database

Automated sensing of macronutrients in hydroponic solution would allow more efficient management of nutrients for crop growth in closed hydroponic systems. Ion-selective microelectrode technology requires an ion-selective membrane or a solid metal material that responds selectively to one analyte in...

Electrodialytic extraction of anionic pharmaceutical compounds from a single drop of whole blood using a supported liquid membrane.

PubMed

Imoto, Yurika; Nishiyama, Hiroka; Nakamura, Yukihide; Ohira, Shin-Ichi; Toda, Kei

2018-05-01

A method to introduce target analytes to a chromatograph from a single drop of whole blood was investigated for minimally invasive monitoring of anionic pharmaceuticals. In this work, salicylate and loxoprofen were examined as organic anions. A micro ion extractor (MIE) has been developed for extraction of inorganic trace anions from whole blood, but this device is not suitable for extraction of pharmaceuticals. In the present study, we improved and optimized the MIE device for organic anion extraction. Various supported liquid membranes were evaluated for use as the ion transfer membrane, with each membrane placed between a droplet sample (donor) and an acceptor solution. A supported liquid membrane of porous polypropylene impregnated with 1-butanol was selected. In addition, the methods for electric field creation and electrode contact were examined to improve the characteristics of the MIE device. The current and extraction time were also optimized. With the optimized method, salicylate and loxoprofen were successfully extracted from a single drop of whole blood. Changes in the concentrations of these pharmaceuticals in blood over time were monitored after administration. As only 25μL of whole blood was required for analysis, repeat measurements could be conducted to monitor changes in the concentrations. This MIE will be useful for monitoring pharmaceutical concentrations in blood. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrochemically Switchable Polymeric Membrane Ion-Selective Electrodes.

PubMed

Zdrachek, Elena; Bakker, Eric

2018-06-07

We present here for the first time a solid contact ion-selective electrode suitable for the simultaneous sensing of cations (tetrabutylammonium) and anions (hexafluorophosphate), achieved by electrochemical switching. The membrane is based on a thin plasticized polyurethane membrane deposited on poly(3-octylthiophene) (POT) and contains a cation exchanger and lipophilic electrolyte (ETH 500). The cation exchanger is initially in excess; the ion-selective electrode exhibits an initial potentiometric response to cations. During an oxidative current pulse, POT is converted into POT + , which results in the expulsion of cations from the membrane followed by the extraction of anions from the sample solution to fulfill the electroneutrality condition. This creates a defined excess of lipophilic cation in the membrane, resulting in a potentiometric anion response. A reductive current pulse restores the original cation response by triggering the conversion of POT + back into POT, which is accompanied by the expulsion of anions from the membrane and the extraction of cations from the sample solution. Various current pulse magnitudes and durations are explored, and the best results in terms of response slope values and signal stability were observed with an oxidation current pulse of 140 μA cm -2 applied for 8 s and a reduction current pulse of -71 μA cm -2 applied for 8 s.

Modern Directions for Potentiometric Sensors

PubMed Central

Bakker, Eric; Chumbimuni-Torres, Karin

2009-01-01

This paper gives an overview of the newest developments of polymeric membrane ion-selective electrodes. A short essence of the underlying theory is given, emphasizing how the electromotive force may be used to assess binding constants of the ionophore, and how the selectivity and detection limit are related to the underlying membrane processes. The recent developments in lowering the detection limits of ISEs are described, including recent approaches of developing all solid state ISEs, and breakthroughs in detecting ultra-small quantities of ions at low concentrations. These developments have paved the way to use potentiometric sensors as in ultra-sensitive affinity bioanalysis in conjunction with nanoparticle labels. Recent results establish that potentiometry compares favorably to electrochemical stripping analysis. Other new developments with ion-selective electrodes are also described, including the concept of backside calibration potentiometry, controlled current coulometry, pulsed chronopotentiometry, and localized flash titration with ion-selective membranes to design sensors for the direct detection of total acidity without net sample perturbation. These developments have further opened the field for exciting new possibilities and applications. PMID:19890473

Construction and performance characteristics of polymeric membrane electrode and coated graphite electrode for the selective determination of Fe³⁺ ion.

PubMed

Bandi, Koteswara Rao; Singh, Ashok K; Upadhyay, Anjali

2014-03-01

Novel Fe(3+) ion-selective polymeric membrane electrodes (PMEs) were prepared using three different ionophores N-(4-(dimethylamino)benzylidene)thiazol-2-amine [L1], 5-((3-methylthiophene-2yl) methyleneamino)-1,3,4-thiadiazole-2-thiol [L2] and N-((3-methylthiophene-2yl)methylene)thiazol-2-amine [L3] and their potentiometric characteristics were discussed. Effect of various plasticizers and anion excluders was also studied in detail and improved performance was observed. The best performance was obtained for the membrane electrode having a composition of L2:PVC:o-NPOE:NaTPB as 3:38.5:56:2.5 (w/w; mg). A coated graphite electrode (CGE) was also prepared with the same composition and compared. CGE is found to perform better as it shows a wider working concentration range of 8.3×10(-8)-1.0×10(-1)molL(-1), a lower detection limit of 2.3×10(-8)molL(-1), and a near Nernstian slope of 19.5 ± 0.4 mVdecade(-1) of activity with a response time of 10s. The CGE shows a shelf life of 6 weeks and in view of high selectivity, it can be used to quantify Fe(3+) ion in water, soil, vegetable and medicinal plants. It can also be used as an indicator electrode in potentiometric titration of EDTA with Fe(3+) ion. Copyright © 2013. Published by Elsevier B.V.

Membrane Bioprobe Electrodes

ERIC Educational Resources Information Center

Rechnitz, Garry A.

1975-01-01

Describes the design of ion selective electrodes coupled with immobilized enzymes which operate either continuously or on drop-sized samples. Cites techniques for urea, L-phenylalanine and amygdalin. Micro size electrodes for use in single cells are discussed. (GH)

Direct Sensing of Total Acidity by Chronopotentiometric Flash Titrations at Polymer Membrane Ion-Selective Electrodes

PubMed Central

Gemene, Kebede L.; Bakker, Eric

2008-01-01

Polymer membrane ion-selective electrodes containing lipophilic ionophores are traditionally interrogated by zero current potentiometry, which, ideally, gives information on the sample activity of ionic species. It is shown here that a discrete cathodic current pulse across an H+-selective polymeric membrane doped with the ionophore ETH 5294 may be used for the chronopotentiometric detection of pH in well buffered samples. However, a reduction in the buffer capacity leads to large deviations from the expected Nernstian response slope. This is explained by the local depletion of hydrogen ions at the sample-membrane interface as a result of the galvanostatically imposed ion flux in direction of the membrane. This depletion is found to be a function of the total acidity of the sample and can be directly monitored chronopotentiometrically in a flash titration experiment. The subsequent application of a baseline potential pulse reverses the extraction process of the current pulse, allowing one to interrogate the sample with minimal perturbation. In one protocol, total acidity is found to be proportional to the magnitude of applied current at the flash titration endpoint. More conveniently, the square root of the flash titration endpoint time observed at a fixed applied current is a linear function of the total acid concentration. This suggests that it is possible to perform rapid localized pH titrations at ion-selective electrodes without the need for volumetric titrimetry. The technique is explored here for acetic acid, MES and citric acid with promising results. Polymeric membrane electrodes on the basis of poly(vinyl chloride) plasticized with o-nitrophenyloctylether in a 1:2 mass ratio may be used for the detection of acids of up to ca. 1 mM concentration, with flash titration times on the order of a few seconds. Possible limitations of the technique are discussed, including variations of the acid diffusion coefficients and influence of electrical migration. PMID:18370399

Potentiometric sensors with carbon black supporting platinum nanoparticles.

PubMed

Paczosa-Bator, Beata; Cabaj, Leszek; Piech, Robert; Skupień, Krzysztof

2013-11-05

For the first time, a single-piece, all-solid-state ion-selective electrode was fabricated with carbon black supporting platinum nanoparticles (PtNPs-CB) and a polymeric membrane. The PtNPs-CB, as an intermediate layer, was drop-casted directly on the solid substrate, and then an ionophore-doped solvent polymeric membrane was added in order to form a sensor. The performance of the newly developed electrodes was evaluated on the basis of potassium and nitrate ions. The stability of the electrical potential for the electrodes was examined by performing current-reversal chronopotentiometry, and the influence of the interfacial water film was assessed by the potentiometric aqueous-layer test. Fabricated potassium- and nitrate-selective electrodes displayed a Nernstian slope and several outstanding properties such as high long-term potential stability, potential repeatability, and reproducibility.

Samarium (III) Selective Membrane Sensor Based on Tin (IV) Boratophosphate

PubMed Central

Mittal, Susheel K.; Sharma, Harish Kumar; Kumar, Ashok S. K.

2004-01-01

A number of Sm (III) selective membranes of varying compositions using tin (IV) boratophosphate as electroactive material were prepared. Polyvinyl chloride, polystyrene and epoxy resin were used as binding materials. Membrane having composition of 40% exchanger and 60% epoxy resin exhibited best performance. This membrane worked well over a wide concentration range of 1×10-5M to 1×10-1 M of samarium ions with a Super-Nernstian slope of 40 mV/decade. It has a fast response time of less than 10 seconds and can be used for at least six months without any considerable divergence in potentials. The proposed sensor revealed good selectivities with respect to alkali, alkaline earth, some transition and rare earth metal ions and can be used in the pH range of 4.0-10.0. It was used as an indicator electrode in the potentiometric titration of Sm (III) ions against EDTA. Effect of internal solution was studied and the electrode was successfully used in non-aqueous media, too.

Charge Dynamics and Bending Actuation in Aquivion Membrane Swelled with Ionic Liquids.

PubMed

Lin, Junhong; Liu, Yang; Zhang, Q M

2011-01-21

The actuation strain and speed of ionic electroactive polymer (EAP) actuators are mainly determined by the charge transport through the actuators and excess ion storage near the electrodes. We employ a recently developed theory on ion transport and storage to investigate the charge dynamics of short-side-chain Aquivion® (Hyflon®) membranes with different uptakes of ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf). The results reveal the existence of a critical uptake of ionic liquids above which the membrane exhibit a high ionic conductivity (σ>5×10(-2) mS/cm). Especially, we investigate the charge dynamics under voltages which are in the range for practical device operation (~1 volts and higher). The results show that the ionic conductivity, ionic mobility, and mobile ion concentration do not change with the applied voltage below 1 volt (and for σ below 4 volts). The results also show that bending actuation of the Aquivion membrane with 40 wt% EMI-Tf is much larger than that of Nafion, indicating that the shorter flexible side chains improve the electromechanical coupling between the excess ions and the membrane backbones, while not affect the actuation speed.

Charge Dynamics and Bending Actuation in Aquivion Membrane Swelled with Ionic Liquids

PubMed Central

Lin, Junhong; Liu, Yang; Zhang, Q. M.

2011-01-01

The actuation strain and speed of ionic electroactive polymer (EAP) actuators are mainly determined by the charge transport through the actuators and excess ion storage near the electrodes. We employ a recently developed theory on ion transport and storage to investigate the charge dynamics of short-side-chain Aquivion® (Hyflon®) membranes with different uptakes of ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf). The results reveal the existence of a critical uptake of ionic liquids above which the membrane exhibit a high ionic conductivity (σ>5×10−2 mS/cm). Especially, we investigate the charge dynamics under voltages which are in the range for practical device operation (~1 volts and higher). The results show that the ionic conductivity, ionic mobility, and mobile ion concentration do not change with the applied voltage below 1 volt (and for σ below 4 volts). The results also show that bending actuation of the Aquivion membrane with 40 wt% EMI-Tf is much larger than that of Nafion, indicating that the shorter flexible side chains improve the electromechanical coupling between the excess ions and the membrane backbones, while not affect the actuation speed. PMID:21339839

Integrated photoelectrochemical cell and system having a liquid electrolyte

DOEpatents

Deng, Xunming; Xu, Liwei

2010-07-06

An integrated photoelectrochemical (PEC) cell generates hydrogen and oxygen from water while being illuminated with radiation. The PEC cell employs a liquid electrolyte, a multi-junction photovoltaic electrode, and a thin ion-exchange membrane. A PEC system and a method of making such PEC cell and PEC system are also disclosed.

Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes

PubMed Central

2018-01-01

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

Faradaically selective membrane for liquid metal displacement batteries

NASA Astrophysics Data System (ADS)

Yin, Huayi; Chung, Brice; Chen, Fei; Ouchi, Takanari; Zhao, Ji; Tanaka, Nobuyuki; Sadoway, Donald R.

2018-02-01

In the realm of stationary energy storage, a plurality of candidate chemistries continues to vie for acceptance, among them the Na-NiCl2 displacement battery, which has eluded widespread adoption owing to the fragility of the β″-Al2O3 membrane. Here we report a porous electronically conductive membrane, which achieves chemical selectivity by preferred faradaic reaction instead of by regulated ionic conduction. Fitted with a porous membrane of TiN, a displacement cell comprising a liquid Pb positive electrode, a liquid Li-Pb negative electrode and a molten-salt electrolyte of PbCl2 dissolved in LiCl-KCl eutectic was cycled at a current density of 150 mA cm-2 at a temperature of 410 °C and exhibited a coulombic efficiency of 92% and a round-trip energy efficiency of 71%. As an indication of industrial scalability, we show comparable performance in a cell fitted with a faradaic membrane fashioned out of porous metal.

A copper ion-selective electrode with high selectivity prepared by sol-gel and coated wire techniques.

PubMed

Mazloum Ardakani, M; Salavati-Niasari, M; Khayat Kashani, M; Ghoreishi, S M

2004-03-01

A sol-gel electrode and a coated wire ion-selective poly(vinyl chloride) membrane, based on thiosemicarbazone as a neutral carrier, were successfully developed for the detection of Cu (II) in aqueous solutions. The sol-gel electrode and coated electrode exhibited linear response with Nernstian slopes of 29.2 and 28.1 mV per decade respectively, within the copper ion concentration ranges 1.0 x 10(-5) - 1.0 x 10(-1) M and 6.0 x 10(-6) - 1.0 x 10(-1) M for coated and sol-gel sensors. The coated and sol-gel electrodes show detection limits of 3.0 x 10(-6) and 6.0 x 10(-6) M respectively. The electrodes exhibited good selectivities for a number of alkali, alkaline earth, transition and heavy metal ions. The proposed electrodes have response times ranging from 10-50 s to achieve a 95% steady potential for Cu2+ concentration. The electrodes are suitable for use in aqueous solutions over a wide pH range (4-7.5). Applications of these electrodes for the determination of copper in real samples, and as an indicator electrode for potentiometric titration of Cu2+ ion using EDTA, are reported. The lifetimes of the electrodes were tested over a period of six months to investigate their stability. No significant change in the performance of the sol-gel electrode was observed over this period, but after two months the coated wire copper-selective electrode exhibited a gradual decrease in the slope. The selectivity of the sol-gel electrode was found to be better than that of the coated wire copper-selective electrode. Based on these results, a novel sol-gel copper-selective electrode is proposed for the determination of copper, and applied to real sample assays.

Ion Exchange Polymeric Coatings for Selective Capacitive Deionization

NASA Astrophysics Data System (ADS)

Jain, Amit; Kim, Jun; Li, Qilin; Verduzco, Rafael

Capacitive deionization (CDI) is an energy-efficient technology for adsorbing and removing scalants and foulants from water by utilizing electric potential between porous carbon electrodes. Currently, industrial application of CDI is limited to low salinity waters due to the limited absorption capacities of carbon electrodes. However, CDI can potentially be used as a low-cost approach to selectively remove divalent ions from high salinity water. Divalent ions such as sulfonates and carbonates cause scaling and thus performance deterioration of membrane-based desalination systems. In this work, we investigated ion-exchange polymer coatings for use in a membrane capacitive deionization (MCDI) process for selective removal of divalent ions. Poly-Vinyl Alcohol (PVA) base polymer was crosslinked and charged using sulfo-succinic acid (SSA) to give a cation exchange layer. 50 um thick standalone polymer films had a permeability of 4.25*10-7 cm2/s for 10mM NaCl feed. Experiments on electrodes with as low as 10 υm thick coating of cation exchange polymer are under progress and will be evaluated on the basis of their selective salt removal efficiency and charge efficiency, and in future we will extend this work to sulfonated block copolymers and anion exchange polymers.

Highly selective potentiometric and colorimetric determinations of cobalt (II) ion using thiazole based ligands.

PubMed

Singhal, Divya; Singh, Ashok Kumar; Upadhyay, Anjali

2014-12-01

New PVC-membrane electrodes were prepared by using 2-((thiazol-2-ylimino)methyl)phenol (L1) and 2-((thiazol-2-ylamino)methyl)phenol (L2) and explored as Co(II) selective electrodes. The effect of various plasticizers and anion excluder was studied in detail and improved performance was observed. It was found that the electrode based on L1 shows better response characteristics in comparison to L2. Optimum performance was observed for the membrane electrode having a composition of L1:NaTPB:DBP:PVC≡2:8:78:62 (w/w, mg). The performance of PME based on L1 was compared with that of CGE. The electrodes exhibit Nernstian slope for Co(II) ions with a limit of detection of 6.91×10(-7) mol L(-1) for PME and 7.94×10(-8) mol L(-1) for CGE. The response time for PME and CGE was found to be 15s and 12 s respectively. The potentiometric responses are independent in the pH range 3.0-9.0 for CGE. The CGE could be used for a period of 90 days. The CGE was used as an indicator electrode in potentiometric titration of EDTA with Co(2+) ion. Further the selectivity of the L1 and L2 was also confirmed by the UV-vis and colorimetric studies and found that L1 is more selective for Co(II) ion. Copyright © 2014 Elsevier B.V. All rights reserved.

Ferrocene bound poly(vinyl chloride) as ion to electron transducer in electrochemical ion sensors.

PubMed

Pawlak, Marcin; Grygolowicz-Pawlak, Ewa; Bakker, Eric

2010-08-15

We report here on the synthesis of poly(vinyl chloride) (PVC) covalently modified with ferrocene groups (FcPVC) and the electrochemical behavior of the resulting polymeric membranes in view of designing all solid state voltammetric ion sensors. The Huisgen cycloaddition ("click chemistry") was found to be a simple and efficient method for ferrocene attachment. A degree of PVC modification with ferrocene groups between 1.9 and 6.1 mol % was achieved. The chemical modification of the PVC backbone does not significantly affect the ion-selective properties (selectivity, mobility, and solvent casting ability) of potentiometric sensing membranes applying this polymer. Importantly, the presence of such ferrocene groups may eliminate the need for an additional redox-active layer between the membrane and the inner electric contact in all solid state sensor designs. Electrochemical doping of this system was studied in a symmetrical sandwich configuration: glassy carbon electrode |FcPVC| glassy carbon electrode. Prior electrochemical doping from aqueous solution, resulting in a partial oxidation of the ferrocene groups, was confirmed to be necessary for the sandwich configuration to pass current effectively. The results suggest that only approximately 2.3 mol % of the ferrocene groups are electrochemically accessible, likely due to surface confined electrochemical behavior in the polymer. Indeed, cyclic voltammetry of aqueous hexacyanoferrate (III) remains featureless at cathodic potentials (down to -0.5 V). This indicates that the modified membrane is not responsive to redox-active species in the sample solution, making it possible to apply this polymer as a traditional, single membrane. Yet, the redox capacity of the electrode modified with this type of membrane was more than 520 microC considering a 20 mm(2) active electrode area, which appears to be sufficient for numerous practical ion voltammetric applications. The electrode was observed to operate reproducibly, with 1% standard deviation, when applying pulsed amperometric techniques.

New Signal Readout Principle for Solid-Contact Ion-Selective Electrodes.

PubMed

Vanamo, Ulriika; Hupa, Elisa; Yrjänä, Ville; Bobacka, Johan

2016-04-19

A novel approach to signal transduction concerning solid-contact ion-selective electrodes (SC-ISE) with a conducting polymer (CP) as the solid contact is investigated. The method presented here is based on constant potential coulometry, where the potential of the SC-ISE vs the reference electrode is kept constant using a potentiostat. The change in the potential at the interface between the ion-selective membrane (ISM) and the sample solution, due to the change in the activity of the primary ion, is compensated with a corresponding but opposite change in the potential of the CP solid contact. This enforced change in the potential of the solid contact results in a transient reducing/oxidizing current flow through the SC-ISE. By measuring and integrating the current needed to transfer the CP to a new state of equilibrium, the total cumulated charge that is linearly proportional to the change of the logarithm of the primary ion activity is obtained. In this work, different thicknesses of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrenesulfonate) (PSS) were used as solid contact. Also, coated wire electrodes (CWEs) were included in the study to show the general validity of the new approach. The ISM employed was selective for K(+) ions, and the selectivity of the membrane under implementation of the presented transduction mechanism was confirmed by measurements performed with a constant background concentration of Na(+) ions. A unique feature of this signal readout principle is that it allows amplification of the analytical signal by increasing the capacitance (film thickness) of the solid contact of the SC-ISE.

A Liquid Chromatography Detector for Transition and Rare-Earth Metal Ions Based on a Cupric Ion-Selective Electrode

DTIC Science & Technology

1981-05-01

RARE-EARTH METAL IONS BASED ON A CUPRIC ION-SELECTIVE ELECTRODE By - 4 R. CAMERON DOREY TECHNICAL REPORT FJSRL-TR-81-0005 MAY 1981 Approved for public...FORM . REPORT NUMBER 12. GOVT ACCESSION NO. 3. RECIPIENT’S CATALOG NUMBER FJSRL-TR-81-0005BO CO ENGO 4 . TITLE (and Subtitle) 5. TYPE OF REPORT & PERIOD...common anions, including halide ions, is shown, and the advantages and limitations of the system are discussed. II ’ 4 UNCLASSIFIED SECURITY

A Novel Ion - selective Polymeric Membrane Sensor for Determining Thallium(I) With High Selectivity

NASA Astrophysics Data System (ADS)

Kassim, Anuar; Rezayi, Majid; Ahmadzadeh, Saeid; Rounaghi, Gholamhossein; Mohajeri, Masoomeh; Azah Yusof, Noor; Tee, Tan Wee; Yook Heng, Lee; Halim Abdullah, Abd

2011-02-01

Thallium is a toxic metal that introduced into the environment mainly as a waste from the production of zinc, cadmium, and lead and by combustion of coal. Thallium causes gastrointestinal irritation and nerve damage when people are exposed to it for relatively short period of time. For long term, thallium has the potential to cause the following effects: change in blood chemistry, damage to liver, kidney, intestinal and testicular tissue, and hair loss. In this work a membrane was prepared by use of 4'-nitrobenzo -18-crown-6 (4'NB18C6) as an ion carrier, polyvinylchloride (PVC) as a matrix, and diocthylphetalate (DOP) as a plasticizer for making an ion selective electrode for measurement of Tl+ cation in solutions. The amount of 4'-nitrobenzo-18C6 and polyvinylchloride were optimized in the preparation of the membrane. The response of the electrode was Nernstian within the concentration range 1.0 × 10-8 to 1.0 × 10-1M. This sensor displays a drift in Nernstian response for this cation with increasing the amount of ionophore and decreasing the amount of polyvinylchloride.The results of potentiometric measurements showed that, this electrode also responses to Cu2+ Ni2+ and Pb2+ cations, but the electrode has a wider dynamic range and a lower detection limit to Tl+ cation. The effects of various parameters such as pH, different cations interferences, effect of the amount of ionophore and polyvinylchloride and time on response of the coated ion selective electrode were investigated. Finally the constructed electrode was used in complexometric and precipitation titrations of Tl+ cation with EDTA and KBr, respectively. The response of the fabricated electrode at concentration range from 1.0 × 10-8 to 1.0 × 10-1M is linear with a Nernstian slope of 57.27 mV.

Liquid Silicon Pouch Anode

DTIC Science & Technology

2017-09-06

discharge from cell 10A shown in FIG. 1, as electrons are utilized from negative electrode 28, lithium ions in anolyte 24 travel across membrane 14 to join...Docket No. 300139 11 of 13 [0029] As cell 10B shown in FIG. 2 is charged, lithium ions in catholyte 16 travel across membrane 14. Discharge of these...with a cell 10B’ in a discharged state. Reservoir 32B contracts as anolyte 24 reduces in volume while cell is discharging. Anolyte 24 travels from

Plasticizer Effects in the PVC Membrane of the Dibasic Phosphate Selective Electrode

PubMed Central

Carey, Clifton

2016-01-01

The PVC membrane of an ion-selective electrode (ISE) sensitive to dibasic phosphate ions (HPO4-ISE) has not been optimized for maximum selectivity, sensitivity, and useable ISE lifetime and further work was necessary to improve its performance. Two areas of investigation are reported here: include the parameters for the lipophilicity of the plasticizer compound used and the amount of cyclic polyamine ionophore incorporated in the PVC membrane. Six candidate plasticizers with a range of lipophilicity were evaluated for their effect on the useable lifetime, sensitivity, and selectivity of the ISE against 13 different anions. Selectivity was determined by a modified fixed interferent method, sensitivity was determined without interferents, and the usable lifetime evaluated at the elapsed time where 50% of the HPO4-ISE failed (L50). The results show that choosing a plasticizer that has a lipophilicity similar to the ionophore's results in the best selectivity and sensitivity and the longest L50. PMID:27347487

A coated-wire ion-selective electrode for ionic calcium measurements

NASA Technical Reports Server (NTRS)

Hines, John W.; Arnaud, Sara; Madou, Marc; Joseph, Jose; Jina, Arvind

1991-01-01

A coated-wire ion-selective electrode for measuring ionic calcium was developed, in collaboration with Teknektron Sensor Development Corporation (TSDC). This coated wire electrode sensor makes use of advanced, ion-responsive polyvinyl chloride (PVC) membrane technology, whereby the electroactive agent is incorporated into a polymeric film. The technology greatly simplifies conventional ion-selective electrode measurement technology, and is envisioned to be used for real-time measurement of physiological and environment ionic constituents, initially calcium. A primary target biomedical application is the real-time measurement of urinary and blood calcium changes during extended exposure to microgravity, during prolonged hospital or fracture immobilization, and for osteoporosis research. Potential advanced life support applications include monitoring of calcium and other ions, heavy metals, and related parameters in closed-loop water processing and management systems. This technology provides a much simplified ionic calcium measurement capability, suitable for both automated in-vitro, in-vivo, and in-situ measurement applications, which should be of great interest to the medical, scientific, chemical, and space life sciences communities.

Solid-Contact pH Sensor without CO2 Interference with a Superhydrophobic PEDOT-C14 as Solid Contact: The Ultimate "Water Layer" Test.

PubMed

Guzinski, Marcin; Jarvis, Jennifer M; D'Orazio, Paul; Izadyar, Anahita; Pendley, Bradford D; Lindner, Ernő

2017-08-15

The aim of this study was to find a conducting polymer-based solid contact (SC) for ion-selective electrodes (ISEs) that could become the ultimate, generally applicable SC, which in combination with all kinds of ion-selective membranes (ISMs) would match the performance characteristics of conventional ISEs. We present data collected with electrodes utilizing PEDOT-C 14 , a highly hydrophobic derivative of poly(3,4-ethylenedioxythiophene), PEDOT, as SC and compare its performance characteristics with PEDOT-based SC ISEs. PEDOT-C 14 has not been used in SC ISEs previously. The PEDOT-C 14 -based solid contact (SC) ion-selective electrodes (ISEs) (H + , K + , and Na + ) have outstanding performance characteristics (theoretical response slope, short equilibration time, excellent potential stability, etc.). Most importantly, PEDOT-C 14 -based SC pH sensors have no CO 2 interference, an essential pH sensors property when aimed for whole-blood analysis. The superhydrophobic properties (water contact angle: 136 ± 5°) of the PEDOT-C 14 SC prevent the detachment of the ion-selective membrane (ISM) from its SC and the accumulation of an aqueous film between the ISM and the SC. The accumulation of an aqueous film between the ISM and its SC has a detrimental effect on the sensor performance. Although there is a test for the presence of an undesirable water layer, if the conditions for this test are not selected properly, it does not provide an unambiguous answer. On the other hand, recording the potential drifts of SC electrodes with pH-sensitive membranes in samples with different CO 2 levels can effectively prove the presence or absence of a water layer in a short time period.

Potentiometric determination of ketotifen fumarate in pharmaceutical preparations and urine using carbon paste and PVC membrane selective electrodes.

PubMed

Frag, Eman Y Z; Mohamed, Gehad G; Khalil, Mohamed M; Hwehy, Mohammad M A

2011-01-01

This study compares between unmodified carbon paste (CPE; the paste has no ion pair) and polyvinyl chloride (PVC) membrane selective electrodes that were used in potentiometric determination of ketotifen fumarate (KTF), where sodium tetraphenylborate (NaTPB) was used as titrant. The performance characteristics of these sensors were evaluated according to IUPAC recommendations which reveal a fast, stable, and linear response for KTF over the concentration range of 10(-7) to 10(-2) mol L(-1). The electrodes show Nernstian slope value of 52.51 ± 0.20 and 51.51 ± 0.25 mV decade(-1) for CPE and PVC membrane electrodes at 30°C, respectively. The potential is nearly stable over the pH range 3.0-6.0 and 2.0-7.0 for CPE and PVC membrane electrodes, respectively. Selectivity coefficient values towards different inorganic cations, sugars, and amino acids reflect high selectivity of the prepared electrodes. The electrodes responses at different temperatures were also studied, and long operational lifetime of 12 and 5 weeks for CPE and PVC membrane electrodes, respectively, were found. These are used for determination of ketotifen fumarate using potentiometric titration, calibration, and standard addition methods in pure samples, its pharmaceutical preparations (Zaditen tablets), and biological fluid (urine). The direct potentiometric determination of KTF using the proposed sensors gave recoveries % of 98.97 ± 0.53 and 98.62 ± 0.74 with RSD 1.42 and 0.63% for CPE and PVC membrane selective electrodes, respectively. Validation of the method shows suitability of the proposed sensors for use in quality control assessment of KTF. The obtained results were in a good agreement with those obtained using the reported spectrophotometric method.

Potentiometric Determination of Ketotifen Fumarate in Pharmaceutical Preparations and Urine Using Carbon Paste and PVC Membrane Selective Electrodes

PubMed Central

Frag, Eman Y. Z.; Mohamed, Gehad G.; Khalil, Mohamed M.; Hwehy, Mohammad M. A.

2011-01-01

This study compares between unmodified carbon paste (CPE; the paste has no ion pair) and polyvinyl chloride (PVC) membrane selective electrodes that were used in potentiometric determination of ketotifen fumarate (KTF), where sodium tetraphenylborate (NaTPB) was used as titrant. The performance characteristics of these sensors were evaluated according to IUPAC recommendations which reveal a fast, stable, and linear response for KTF over the concentration range of 10−7 to 10−2 mol L−1. The electrodes show Nernstian slope value of 52.51 ± 0.20 and 51.51 ± 0.25 mV decade−1 for CPE and PVC membrane electrodes at 30°C, respectively. The potential is nearly stable over the pH range 3.0–6.0 and 2.0–7.0 for CPE and PVC membrane electrodes, respectively. Selectivity coefficient values towards different inorganic cations, sugars, and amino acids reflect high selectivity of the prepared electrodes. The electrodes responses at different temperatures were also studied, and long operational lifetime of 12 and 5 weeks for CPE and PVC membrane electrodes, respectively, were found. These are used for determination of ketotifen fumarate using potentiometric titration, calibration, and standard addition methods in pure samples, its pharmaceutical preparations (Zaditen tablets), and biological fluid (urine). The direct potentiometric determination of KTF using the proposed sensors gave recoveries % of 98.97 ± 0.53 and 98.62 ± 0.74 with RSD 1.42 and 0.63% for CPE and PVC membrane selective electrodes, respectively. Validation of the method shows suitability of the proposed sensors for use in quality control assessment of KTF. The obtained results were in a good agreement with those obtained using the reported spectrophotometric method. PMID:22013443

An improved method for constructing and selectively silanizing double-barreled, neutral liquid-carrier, ion-selective microelectrodes

PubMed Central

Deveau, Jason S.T.; Grodzinski, Bernard

2005-01-01

We describe an improved, efficient and reliable method for the vapour-phase silanization of multi-barreled, ion-selective microelectrodes of which the silanized barrel(s) are to be filled with neutral liquid ion-exchanger (LIX). The technique employs a metal manifold to exclusively and simultaneously deliver dimethyldichlorosilane to only the ion-selective barrels of several multi-barreled microelectrodes. Compared to previously published methods the technique requires fewer procedural steps, less handling of individual microelectrodes, improved reproducibility of silanization of the selected microelectrode barrels and employs standard borosilicate tubing rather than the less-conventional theta-type glass. The electrodes remain stable for up to 3 weeks after the silanization procedure. The efficacy of a double-barreled electrode containing a proton ionophore in the ion-selective barrel is demonstrated in situ in the leaf apoplasm of pea (Pisum) and sunflower (Helianthus). Individual leaves were penetrated to depth of ~150 μm through the abaxial surface. Microelectrode readings remained stable after multiple impalements without the need for a stabilizing PVC matrix. PMID:16136222

Validated electrochemical and chromatographic quantifications of some antibiotic residues in pharmaceutical industrial waste water.

PubMed

Ibrahim, Heba K; Abdel-Moety, Mona M; Abdel-Gawad, Sherif A; Al-Ghobashy, Medhat A; Kawy, Mohamed Abdel

2017-03-01

Realistic implementation of ion selective electrodes (ISEs) into environmental monitoring programs has always been a challenging task. This could be largely attributed to difficulties in validation of ISE assay results. In this study, the electrochemical response of amoxicillin trihydrate (AMX), ciprofloxacin hydrochloride (CPLX), trimethoprim (TMP), and norfloxacin (NFLX) was studied by the fabrication of sensitive membrane electrodes belonging to two types of ISEs, which are polyvinyl chloride (PVC) membrane electrodes and glassy carbon (GC) electrodes. Linear response for the membrane electrodes was in the concentration range of 10 -5 -10 -2  mol/L. For the PVC membrane electrodes, Nernstian slopes of 55.1, 56.5, 56.5, and 54.0 mV/decade were achieved over a pH 4-8 for AMX, CPLX, and NFLX, respectively, and pH 3-6 for TMP. On the other hand, for GC electrodes, Nernstian slopes of 59.1, 58.2, 57.0, and 58.2 mV/decade were achieved over pH 4-8 for AMX, CPLX, and NFLX, respectively, and pH 3-6 for TMP. In addition to assay validation to international industry standards, the fabricated electrodes were also cross-validated relative to conventional separation techniques; high performance liquid chromatography (HPLC), and thin layer chromatography (TLC)-densitometry. The HPLC assay was applied in concentration range of 0.5-10.0 μg/mL, for all target analytes. The TLC-densitometry was adopted over a concentration range of 0.3-1.0 μg/band, for AMX, and 0.1-0.9 μg/band, for CPLX, NFLX, and TMP. The proposed techniques were successfully applied for quantification of the selected drugs either in pure form or waste water samples obtained from pharmaceutical plants. The actual waste water samples were subjected to solid phase extraction (SPE) for pretreatment prior to the application of chromatographic techniques (HPLC and TLC-densitometry). On the other hand, the fabricated electrodes were successfully applied for quantification of the antibiotic residues in actual waste water samples without any pretreatment. This finding assures the suitability of the fabricated ISEs for environmental analysis.

PVC membrane, coated-wire, and carbon-paste ion-selective electrodes for potentiometric determination of galantamine hydrobromide in physiological fluids.

PubMed

Abdel-Haleem, Fatehy M; Saad, Mohamed; Barhoum, Ahmed; Bechelany, Mikhael; Rizk, Mahmoud S

2018-08-01

We report on highly-sensitive ion-selective electrodes (ISEs) for potentiometric determining of galantamine hydrobromide (GB) in physiological fluids. Galantamine hydrobromide (GB) was selected for this study due to its previous medical importance for treating Alzheimer's disease. Three different types of ISEs were investigated: PVC membrane electrode (PVCE), carbon-paste electrode (CPE), and coated-wire electrode (CWE). In the construction of these electrodes, galantaminium-reineckate (GR) ion-pair was used as a sensing species for GB in solutions. The modified carbon-paste electrode (MCPE) was prepared using graphene oxide (MCPE-GO) and sodium tetrakis (trifluoromethyl) phenyl borate (MCPE-STFPB) as ion-exchanger. The potentiometric modified CPEs (MCPE-GO and MCPE-STFPB) show an improved performance in term of Nernstian slope, selectivity, response time, and response stability compared to the unmodified CPE. The prepared electrodes PVCE, CWE, CPE, MCPE-GO and MCPE-STFPB show Nernstian slopes of 59.9, 59.5, 58.1, 58.3 and 57.0 mV/conc. decade, and detection limits of 5.0 × 10 -6 , 6.3 × 10 -6 , 8.0 × 10 -6 , 6.0 × 10 -6 and 8.0 × 10 -6  mol L -1 , respectively. The prepared ISEs also show high selectivity against cations (i.e. Na + , K + , NH 4 + , Ca 2+ , Al 3+ , Fe 3+ ), amino acids (i.e. glycine, L-alanine alanine), and sugars (i.e. fructose, glucose, maltose, lactose). The prepared ISEs are applicable for determining GB in spiked serums, urines, and pharmaceutical preparations, using a standard addition and a direct potentiometric method. The fast response time (<10 s), long lifetime (1-5 weeks), reversibility and stability of the measured signals facilitate the application of these sensors for routine analysis of the real samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Through-plane conductivities of membranes for nonaqueous redox flow batteries

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

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.; ...

2015-08-13

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« 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.

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.

Electrospray ion source with reduced analyte electrochemistry

DOEpatents

Kertesz, Vilmos [Knoxville, TN; Van Berkel, Gary [Clinton, TN

2011-08-23

An electrospray ion (ESI) source and method capable of ionizing an analyte molecule without oxidizing or reducing the analyte of interest. The ESI source can include an emitter having a liquid conduit, a working electrode having a liquid contacting surface, a spray tip, a secondary working electrode, and a charge storage coating covering partially or fully the liquid contacting surface of the working electrode. The liquid conduit, the working electrode and the secondary working electrode can be in liquid communication. The electrospray ion source can also include a counter electrode proximate to, but separated from, said spray tip. The electrospray ion source can also include a power system for applying a voltage difference between the working electrodes and a counter-electrode. The power system can deliver pulsed voltage changes to the working electrodes during operation of said electrospray ion source to minimize the surface potential of the charge storage coating.

Electrospray ion source with reduced analyte electrochemistry

DOEpatents

Kertesz, Vilmos; Van Berkel, Gary J

2013-07-30

An electrospray ion (ESI) source and method capable of ionizing an analyte molecule without oxidizing or reducing the analyte of interest. The ESI source can include an emitter having a liquid conduit, a working electrode having a liquid contacting surface, a spray tip, a secondary working electrode, and a charge storage coating covering partially or fully the liquid contacting surface of the working electrode. The liquid conduit, the working electrode and the secondary working electrode can be in liquid communication. The electrospray ion source can also include a counter electrode proximate to, but separated from, said spray tip. The electrospray ion source can also include a power system for applying a voltage difference between the working electrodes and a counter-electrode. The power system can deliver pulsed voltage changes to the working electrodes during operation of said electrospray ion source to minimize the surface potential of the charge storage coating.

Potentiometric flow injection system for determination of reductants using a polymeric membrane permanganate ion-selective electrode based on current-controlled reagent delivery.

PubMed

Song, Wenjing; Ding, Jiawang; Liang, Rongning; Qin, Wei

2011-10-17

A polymeric membrane permanganate-selective electrode has been developed as a current-controlled reagent release system for potentiometric detection of reductants in flow injection analysis. By applying an external current, diffusion of permanganate ions across the polymeric membrane can be controlled precisely. The permanganate ions released at the sample-membrane interface from the inner filling solution of the electrode are consumed by reaction with a reductant in the sample solution thus changing the measured membrane potential, by which the reductant can be sensed potentiometrically. Ascorbate, dopamine and norepinephrine have been employed as the model reductants. Under the optimized conditions, the potential peak heights are proportional to the reductant concentrations in the ranges of 1.0×10(-5) to 2.5×10(-7)M for ascorbate, of 1.0×10(-5) to 5.0×10(-7)M for dopamine, and of 1.0×10(-5) to 5.0×10(-7)M for norepinephrine, respectively with the corresponding detection limits of 7.8×10(-8), 1.0×10(-7) and 1.0×10(-7)M. The proposed system has been successfully applied to the determination of reductants in pharmaceutical preparations and vegetables, and the results agree well with those of iodimetric analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

Rapid Changes of Potassium Concentration at the Outer Surface of Exposed Single Neurons during Membrane Current Flow

PubMed Central

Neher, E.; Lux, H. D.

1973-01-01

K+-sensitive liquid ion-exchanger microelectrodes are shown to be capable of measuring concentration changes which occur on a millisecond time scale. However, some quaternary ammonium ions, such as tetraethylammonium and acetylcholine, are able to block electrode function when present in concentrations as low as 10-4 to 10-3 M. Changes in extracellular potassium concentration caused by spike activity or voltage clamp pulses of exposed single neurons of the snail Helix pomatia may be measured by these electrodes. Quantitative analysis shows that the total amount of excess potassium found in the vicinity of the cell a short time after a clamp pulse, is in relatively good agreement with the amount of potassium carried by the membrane current. PMID:4689624

Thermally Regenerative Battery with Intercalatable Electrodes and Selective Heating Means

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor); Narayanan, Sekharipuram R. (Inventor); Hickey, Gregory S. (Inventor)

2000-01-01

The battery contains at least one electrode such as graphite that intercalates a first species from the electrolyte disposed in a first compartment such as bromine to form a thermally decomposable complex during discharge. The other electrode can also be graphite which supplies another species such as lithium to the electrolyte in a second electrode compartment. The thermally decomposable complex is stable at room temperature but decomposes at elevated temperatures such as 50 C. to 150 C. The electrode compartments are separated by a selective ion permeable membrane that is impermeable to the first species. Charging is effected by selectively heating the first electrode.

Aptamer-based potentiometric measurements of proteins using ion-selective microelectrodes.

PubMed

Numnuam, Apon; Chumbimuni-Torres, Karin Y; Xiang, Yun; Bash, Ralph; Thavarungkul, Panote; Kanatharana, Proespichaya; Pretsch, Ernö; Wang, Joseph; Bakker, Eric

2008-02-01

We here report on the first example of an aptamer-based potentiometric sandwich assay of proteins. The measurements are based on CdS quantum dot labels of the secondary aptamer, which were determined with a novel solid-contact Cd2+-selective polymer membrane electrode after dissolution with hydrogen peroxide. The electrode exhibited cadmium ion detection limits of 100 pM in 100 mL samples and of 1 nM in 200 microL microwells, using a calcium-selective electrode as a pseudoreference electrode. As a prototype example, thrombin was measured in 200 microL samples with a lower detection limit of 0.14 nM corresponding to 28 fmol of analyte. The results show great promise for the potentiometric determination of proteins at very low concentrations in microliter samples.

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.

Manufacturing and actuation characterization of ionic polymer metal composites with silver as electrodes

NASA Astrophysics Data System (ADS)

Pandita, Surya D.; Lim, Hyoung Tae; Yoo, Youngtai; Park, Hoon Cheol

2006-03-01

Manufacturing and characterization of ionic polymer metal composites (IPMCs) with silver as electrodes have been investigated. Tollen's reagent that contains ion Ag(NH 3) II + was used as a raw material for silver deposition on the surfaces of the polymer membrane Nafion"R". Two types of inner solvents, namely common water based electrolyte solution (LiOH 1N) and ionic liquid were used and investigated. Compared to IPMCs with platinum electrodes, silver-plated IPMCs with water electrolyte showed higher conductivity. The actuation response of silver-plated IPMCs with the water based electrolyte was faster than that of platinum IPMCs. However, the silver electrode was too brittle and severely damaged during the solvent exchange process from water to ionic liquid, resulted in high resistance and hence very low actuation behavior.

Unique battery with a multi-functional, physicochemically active membrane separator/electrolyte-electrode monolith and a method making the same

DOEpatents

Gerald, II, Rex E; Ruscic, Katarina J; Sears, Devin N; Smith, Luis J; Klinger, Robert J; Rathke, Jerome W

2013-11-26

The invention relates to a unique battery having a physicochemically active membrane separator/electrolyte-electrode monolith and method of making the same. The Applicant's invented battery employs a physicochemically active membrane separator/electrolyte-electrode that acts as a separator, electrolyte, and electrode, within the same monolithic structure. The chemical composition, physical arrangement of molecules, and physical geometry of the pores play a role in the sequestration and conduction of ions. In one preferred embodiment, ions are transported via the ion-hoping mechanism where the oxygens of the Al.sub.2O.sub.3 wall are available for positive ion coordination (i.e. Li.sup.+). This active membrane-electrode composite can be adjusted to a desired level of ion conductivity by manipulating the chemical composition and structure of the pore wall to either increase or decrease ion conduction.

Unique battery with a multi-functional, physicochemically active membrane separator/electrolyte-electrode monolith and a method making the same

DOEpatents

Gerald II, Rex E.; Ruscic, Katarina J.; Sears, Devin N.; Smith, Luis J.; Klingler, Robert J.; Rathke, Jerome W.

2012-07-24

The invention relates to a unique battery having a physicochemically active membrane separator/electrolyte-electrode monolith and method of making the same. The Applicant's invented battery employs a physicochemically active membrane separator/electrolyte-electrode that acts as a separator, electrolyte, and electrode, within the same monolithic structure. The chemical composition, physical arrangement of molecules, and physical geometry of the pores play a role in the sequestration and conduction of ions. In one preferred embodiment, ions are transported via the ion-hoping mechanism where the oxygens of the Al₂O₃ wall are available for positive ion coordination (i.e. Li⁺). This active membrane-electrode composite can be adjusted to a desired level of ion conductivity by manipulating the chemical composition and structure of the pore wall to either increase or decrease ion conduction.

Construction of Uranyl Selective Electrode Based on Complex of Uranyl Ion with New Ligand Carboxybenzotriazole in PVC Matrix Membrane

NASA Astrophysics Data System (ADS)

Abu-Dalo, M. A.; Al-Rawashdeh, N. A. F.; Al-Mheidat, I. R.; Nassory, N. S.

2015-10-01

In the present study uranyl selective electrodes in polyvinyl chloride (PVC) matrix membrane were prepared based on a complex of uranyl ion (UO2) with carboxybenzotriazole (CBT) as ligand. The effect of the nature of plasticizer in PVC matrix were evaluated using three different plasticizers, these are dibutyl phthalate (DBP), dioctyl phthalate (DOP) and bis(2-ethylhexyl) sebacate (BHS). The results of this study indicated that the best plasticizer could be used is the DBP, which may be attributed to its lowest viscosity value compared to DOP and BHS. The electrodes with DBP as plasticizer exhibits a Nernstian response with a slope of 28.0 mV/ decade, over a wide range of concentration from 3.0×10-5-6.0×10-2 M and a detection limit of 4.0×10-6 M. It can be used in the pH range of 4.0-10.0 with a response time of less than 10 s for DBP and 25 s for both DOP and BHS. The effects of ions interferences on the electrode response were evaluated. The di- and tri-valent cations were found to interfere less than univalent cations, which was attributed to the high diffusion and the exchange rate between the univalent ions and the uranyl ion solution. The electrodes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron microscopy (SEM). The results of the standard addition method were satisfactory with errors less than 7%. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the uranly ion concentration in the field.

How do biological systems discriminate among physically similar ions?

PubMed

Diamond, J M

1975-10-01

This paper reviews the history of understanding how biological systems can discriminate so strikingly among physically similar ions, especially alkali cations. Appreciation of qualitative regularities ("permitted sequences") and quantitative regularities ("selectivity isotherms") in ion selectivity grew first from studies of ion exchangers and glass electrodes, then of biological systems such as enzymes and cell membranes, and most recently of lipid bilayers doped with model pores and carriers. Discrimination of ions depends on both electrostatic and steric forces. "Black-box" studies on intact biological membranes have in some cases yielded molecular clues to the structure of the actual biological pores and carriers. Major current problems involve the extraction of these molecules; how to do it, what to do when it is achieved, and how (and if) it is relevant to the central problems of membrane function. Further advances are expected soon from studies of rate barriers within membranes, of voltage-dependent ("excitable") conducting channels, and of increasingly complex model systems and biological membranes.

Liquid Junction and Membrane Potentials of the Squid Giant Axon

PubMed Central

Cole, Kenneth S.; Moore, John W.

1960-01-01

The potential differences across the squid giant axon membrane, as measured with a series of microcapillary electrodes filled with concentrations of KCl from 0.03 to 3.0 M or sea water, are consistent with a constant membrane potential and the liquid junction potentials calculated by the Henderson equation. The best value for the mobility of an organic univalent ion, such as isethionate, leads to a probably low, but not impossible, axoplasm specific resistance of 1.2 times sea water and to a liquid junction correction of 4 mv. for microelectrodes filled with 3 M KCl. The errors caused by the assumptions of proportional mixing, unity activity coefficients, and a negligible internal fixed charge cannot be estimated but the results suggest that the cumulative effect of them may not be serious. PMID:13811119

Polyion selective polymeric membrane-based pulstrode as a detector in flow-injection analysis.

PubMed

Bell-Vlasov, Andrea K; Zajda, Joanna; Eldourghamy, Ayman; Malinowska, Elzbieta; Meyerhoff, Mark E

2014-04-15

A method for the detection of polyions using fully reversible polyion selective polymeric membrane type pulstrodes as detectors in a flow-injection analysis (FIA) system is examined. The detection electrode consists of a plasticized polymeric membrane doped with 10 wt % of tridodecylmethylammonium-dinonylnaphthalene sulfonate (TDMA/DNNS) ion-exchanger salt. The pulse sequence used involves a short (1 s) galvanostatic pulse, an open-circuit pulse (0.5 s) during which the EMF of the cell is measured, and a longer (15 s) potentiostatic pulse to return the membrane to its original chemical composition. It is shown that total pulse sequence times can be optimized to yield reproducible real-time detection of injected samples of protamine and heparin at up to 20 samples/h. Further, it is shown that the same membrane detector can be employed for FIA detection of both polycations at levels ≥10 μg/mL and polyanions at levels of ≥40 μg/mL by changing the direction of the galvanostatic pulse. The methodology described may also be applicable in the detection of polyionic species at low levels in other flowing configurations, such as in liquid chromatography and capillary electrophoresis.

The Role of Ion Exchange Membranes in Membrane Capacitive Deionisation.

PubMed

Hassanvand, Armineh; Wei, Kajia; Talebi, Sahar; Chen, George Q; Kentish, Sandra E

2017-09-14

Ion-exchange membranes (IEMs) are unique in combining the electrochemical properties of ion exchange resins and the permeability of a membrane. They are being used widely to treat industrial effluents, and in seawater and brackish water desalination. Membrane Capacitive Deionisation (MCDI) is an emerging, energy efficient technology for brackish water desalination in which these ion-exchange membranes act as selective gates allowing the transport of counter-ions toward carbon electrodes. This article provides a summary of recent developments in the preparation, characterization, and performance of ion exchange membranes in the MCDI field. In some parts of this review, the most relevant literature in the area of electrodialysis (ED) is also discussed to better elucidate the role of the ion exchange membranes. We conclude that more work is required to better define the desalination performance of the proposed novel materials and cell designs for MCDI in treating a wide range of feed waters. The extent of fouling, the development of cleaning strategies, and further techno-economic studies, will add value to this emerging technique.

ELECTROCHEMICAL TREATMENT AND RECYCLING OF SPENT PERCHLORATE-CONTAMINATED ION-EXCHANGE REGENERATION BRINE - PHASE I

EPA Science Inventory

Eltron Research & Development, Inc. (Eltron) proposes to develop an ion-selective, polymer membrane electrode capable of detecting perchlorate in water at low parts per billion (ppb) concentrations. With the discovery of perchlorate contamination in an increasing number of...

Ytterbium-selective polymeric membrane electrode based on substituted urea and thiourea as a suitable carrier.

PubMed

Singh, A K; Jain, A K; Mehtab, Sameena

2007-08-06

Plasticized membranes using 1-phenyl-3-(2-thiazolyl)-2-thiourea (PTT) and 1-phenyl-3-(2-thiazolyl)-2-urea (PTU) have been prepared and explored as ytterbium ion-selective sensors. Effect of various plasticizers, viz. chloronaphthalene (CN), o-nitrophenyloctyl ether (o-NPOE), dibutylphthalate (DBP), dioctylsebacate (DOS) and anion excluders, sodium tetraphenylborate (NaTPB) and oleic acid (OA) was studied and improved membrane performance was observed. Optimum performance was noted with membrane of PTT having composition of PTT (3.5):PVC (80):DOS (160):NaTPB (1.5) in mg. The sensor works satisfactorily in the concentration range 1.2x10(-7) to 1.0x10(-2) M (detection limit 5.5x10(-8) M) with a Nernstian slope of 19.7 mV decade(-1) of activity. Wide pH range (3.0-8.0), fast response time (10 s), non-aqueous tolerance (up to 20%) and adequate shelf life (12 weeks) indicate the vital utility of the proposed sensor. The proposed electrode comparatively shows good selectivity for Yb3+ ion with respect to alkali, alkaline earth, transition and rare earth metals ions and can be used for its determination in binary mixtures and sulfite determination in white and red wine samples.

Lithium-Ion Battery Program Status

NASA Technical Reports Server (NTRS)

Surampudi, S.; Huang, C. K.; Smart, M.; Davies, E.; Perrone, D.; Distefano, S.; Halpert, G.

1996-01-01

The objective of this program is to develop rechargeable Li-ion cells for future NASA missions. Applications that would benefit from this project are: new millenium spacecraft; rovers; landers; astronaut equipment; and planetary orbiters. The approach of this program is: select electrode materials and electrolytes; identify failure modes and mechanisms and enhance cycle life; demonstrate Li-ion cell technology with liquid electrolyte; select candidate polymer electrolytes for Li-ion polymer cells; and develop Li-ion polymer cell technology.

Integrated potentiometric detector for use in chip-based flow cells

PubMed

Tantra; Manz

2000-07-01

A new kind of potentiometric chip sensor for ion-selective electrodes (ISE) based on a solvent polymeric membrane is described. The chip sensor is designed to trap the organic cocktail inside the chip and to permit sample solution to flow past the membrane. The design allows the sensor to overcome technical problems of ruggedness and would therefore be ideal for industrial processes. The sensor performance for a Ba2+-ISE membrane based on a Vogtle ionophore showed electrochemical behavior similar to that observed in conventional electrodes and microelectrode arrangements.

Electroanalytical and naked eye determination of Cu(2+) ion in various environmental samples using 5-amino-1,3,4-thiadiazole-2-thiol based Schiff bases.

PubMed

Bandi, Koteswara Rao; Singh, Ashok Kumar; Upadhyay, Anjali

2014-01-01

Novel polydentate Schiff bases 4-(5-mercapto-1,3,4-thiadiazol-2-ylimino)pentan-2-one (S1) and (2-(indol-3-yl)vinyl)-1,3,4-thiadiazole-2-thiol (S2) were synthesized and explored as Cu(2+) selective polymeric membrane electrodes (PME) using different plasticizers and anionic excluders. The potentiometric data revealed that the PME having the membrane composition (S2: NaTPB: TBP: PVC as 4: 2: 58: 36 (w/w; mg)) is shown to have good results. Thus the coated graphite electrode (CGE) with the same composition as the best PME was also fabricated and investigated as Cu(2+) selective electrode. It was found that CGE showed better response characteristics than PME with respect to low detection limit (1.2×10(-8)molL(-1)), near Nernstian slope (29.8±0.4mV decade(-1) of activity), wide working concentration range (6.4×10(-8)-1.0×10(-1)molL(-1)), long shelf life (90days) and fast response time (9s). The CGE was used successfully as an indicator electrode for the potentiometric determination of Cu(2+) ion against EDTA and also used to quantify Cu(2+) ion in soil, water, medicinal plants, vegetables and edible oil samples. The Schiff base S2 is used as chemosensor for the selective determination of Cu(2+) ion. © 2013.

Fabrication of novel coated pyrolytic graphite electrodes for the selective nano-level monitoring of Cd²⁺ ions in biological and environmental samples using polymeric membrane of newly synthesized macrocycle.

PubMed

Sahani, Manoj Kumar; Singh, A K; Jain, A K; Upadhyay, Anjali; Kumar, Amit; Singh, Udai P; Narang, Shikha

2015-02-20

Novel 5-amino-1,3,4-thiadiazole-2-thiol unit based macrocyclic ionophore 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1(4,7).1(10,13)]henicosa-4(20),10(21),16(19)-triene-6,12,18-trithione (M1), was synthesized and characterized. Preliminary studies on M1 have showed that it has more the affinity toward Cd(2+) ion. Thus, the macrocyclic ionophore (M1) was used as electroactive material in the fabrication of PVC-membrane electrodes such as polymeric membrane electrode (PME), coated graphite electrode (CGE) and coated pyrolytic graphite electrode (CPGE) were prepared and its performance characteristic were compared with. The electroanalytical studies performed on PME, CGE and CPGE revealed that CPGE having membrane composition M1:PVC:1-CN:NaTPB in the ratio of 7:37:54:2 exhibits the best potentiometric characteristics in terms of detection limit of 7.58×10(-9) mol L(-1), Nernstian slope of 29.6 mV decade(-1) of activity. The sensor was found to be independent of pH in the range 2.5-8.5. The sensor showed a fast response time of 10s and could be used over a period of 4 months without any significant divergence in its potentiometric characteristics. The sensor has been employed for monitoring of the Cd(2+) ion in real samples and also used as an indicator electrode in the potentiometric titration of Cd(2+) ion with EDTA. Copyright © 2014. Published by Elsevier B.V.

Synthesis and characterization of bis nitrato[4-hydroxyacetophenonesemicarbazone) nickel(II) complex as ionophore for thiocyanate-selective electrode.

PubMed

Chandra, Sulekh; Hooda, Sunita; Tomar, Praveen Kumar; Malik, Amrita; Kumar, Ankit; Malik, Sakshi; Gautam, Seema

2016-05-01

The PVC based-ion selective electrode viz., bis nitrato[4-hydroxyacetophenone semicarbazone] nickel(II) as an ionophore was prepared for the determination of thiocyanate ion. The ionophore was characterized by FT-IR, UV-vis, XRD, magnetic moment and elemental analysis (CHN). On the basis of spectral studies an octahedral geometry has been assigned. The best performance was obtained with a membrane composition of 31% PVC, 63% 2-nitrophenyl octylether, 4.0% ionophore and 2.0% trioctylmethyl ammonium chloride. The electrode exhibited an excellent Nernstian response to SCN(-) ion ranging from 1.0 × 10(-7) to 1.0 × 10(-1)M with a detection limit of 8.6 × 10(-8)M and a slope of -59.4 ± 0.2 mV/decade over a wide pH range (1.8-10.7) with a fast response time (6s) at 25 °C. The proposed electrode showed high selectivity for thiocyanate ion over a number of common inorganic and organic anions. It was successfully applied to direct determination of thiocyanate in biological (urine and saliva) samples in order to distinguish between smokers and non-smokers, environmental samples and as an indicator electrode for titration of thiocyanate ions with AgNO3 solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Biomimetic membranes and methods of making biomimetic membranes

DOEpatents

Rempe, Susan; Brinker, Jeffrey C.; Rogers, David Michael; Jiang, Ying-Bing; Yang, Shaorong

2016-11-08

The present disclosure is directed to biomimetic membranes and methods of manufacturing such membranes that include structural features that mimic the structures of cellular membrane channels and produce membrane designs capable of high selectivity and high permeability or adsorptivity. The membrane structure, material and chemistry can be selected to perform liquid separations, gas separation and capture, ion transport and adsorption for a variety of applications.

Ion permeability of artificial membranes evaluated by diffusion potential and electrical resistance measurements.

PubMed

Shlyonsky, Vadim

2013-12-01

In the present article, a novel model of artificial membranes that provides efficient assistance in teaching the origins of diffusion potentials is proposed. These membranes are made of polycarbonate filters fixed to 12-mm plastic rings and then saturated with a mixture of creosol and n-decane. The electrical resistance and potential difference across these membranes can be easily measured using a low-cost volt-ohm meter and home-made Ag/AgCl electrodes. The advantage of the model is the lack of ionic selectivity of the membrane, which can be modified by the introduction of different ionophores to the organic liquid mixture. A membrane treated with the mixture containing valinomycin generates voltages from -53 to -25 mV in the presence of a 10-fold KCl gradient (in to out) and from -79 to -53 mV in the presence of a bi-ionic KCl/NaCl gradient (in to out). This latter bi-ionic gradient potential reverses to a value from +9 to +20 mV when monensin is present in the organic liquid mixture. Thus, the model can be build stepwise, i.e., all factors leading to the development of diffusion potentials can be introduced sequentially, helping students to understand the quantitative relationships of ionic gradients and differential membrane permeability in the generation of cell electrical signals.

Synthesis of Silver Embedded Poly(o-Anisidine) Molybdophosphate Nano Hybrid Cation-Exchanger Applicable for Membrane Electrode

PubMed Central

Khan, Anish; Khan, Aftab Aslam Parwaz; Asiri, Abdullah M.; Rub, Malik Abdul

2014-01-01

Poly(o-anisidine) molybdophosphate was expediently obtained by sol-gel mixing of Poly(o-anisidine) into the inorganic matrices of molybdophosphate, which was allowed to react with silver nitrate to the formation of poly(o-anisidine) molybdophosphate embedded silver nano composite. The composite was characterized by Fourier Transform Infrared Spectroscopy, X-ray powder diffraction, UV-Vis Spectrophotometry, Fluorescence Spectroscopy, Scanning Electron Microscopy/Energy-dispersive X-ray Spectroscopy and Thermogravimertic Analysis. Ion exchange capacity and distribution studies were carried out to understand the ion-exchange capabilities of the nano composite. On the basis of highest distribution studies, this nano composite cation exchanger was used as preparation of heavy metal ion selective membrane. Membrane was characterized for its performance as porosity and swelling later on was used for the preparation of membrane electrode for Hg(II), having better linear range, wide working pH range (2–4.5) with fast response in the real environment. PMID:24805257

Fast Potentiometric Analysis of Lead in Aqueous Medium under Competitive Conditions Using an Acridono-Crown Ether Neutral Ionophore.

PubMed

Golcs, Ádám; Horváth, Viola; Huszthy, Péter; Tóth, Tünde

2018-05-03

Lead is a particularly toxic heavy metal that is present above acceptable levels in the water of many countries. This article describes a quick detection method of lead(II) ions using a polyvinyl chloride (PVC)-based ion-selective membrane electrode containing an acridono-crown ether ionophore by potentiometry. The electrochemical cell exhibits a Nernstian response for lead(II) ions between the concentration range of 10 −4 to 10 −2 M, and can be used in the pH range of 4⁻7. The applicability of this sensor was verified by measuring a multicomponent aqueous sample. Under the given conditions, this electrode is suitable for the selective quantitative analysis of lead(II) ions in the presence of many additional metal ions.

Real-time two-dimensional imaging of potassium ion distribution using an ion semiconductor sensor with charged coupled device technology.

PubMed

Hattori, Toshiaki; Masaki, Yoshitomo; Atsumi, Kazuya; Kato, Ryo; Sawada, Kazuaki

2010-01-01

Two-dimensional real-time observation of potassium ion distributions was achieved using an ion imaging device based on charge-coupled device (CCD) and metal-oxide semiconductor technologies, and an ion selective membrane. The CCD potassium ion image sensor was equipped with an array of 32 × 32 pixels (1024 pixels). It could record five frames per second with an area of 4.16 × 4.16 mm(2). Potassium ion images were produced instantly. The leaching of potassium ion from a 3.3 M KCl Ag/AgCl reference electrode was dynamically monitored in aqueous solution. The potassium ion selective membrane on the semiconductor consisted of plasticized poly(vinyl chloride) (PVC) with bis(benzo-15-crown-5). The addition of a polyhedral oligomeric silsesquioxane to the plasticized PVC membrane greatly improved adhesion of the membrane onto Si(3)N(4) of the semiconductor surface, and the potential response was stabilized. The potential response was linear from 10(-2) to 10(-5) M logarithmic concentration of potassium ion. The selectivity coefficients were K(K(+),Li(+))(pot) = 10(-2.85), K(K(+),Na(+))(pot) = 10(-2.30), K(K(+),Rb(+))(pot) =10(-1.16), and K(K(+),Cs(+))(pot) = 10(-2.05).

Calcium-selective electrodes based on photo-cured polyurethane-acrylate membranes covalently attached to methacrylate functionalized poly(3,4-ethylenedioxythiophene) as solid-contact.

PubMed

Ocaña, Cristina; Abramova, Natalia; Bratov, Andrey; Lindfors, Tom; Bobacka, Johan

2018-08-15

We report here the fabrication of solid-contact calcium-selective electrodes (Ca 2+ -SCISEs) made of a polyurethane acrylate ion-selective membrane (ISM) that was covalently attached to the underlying ion-to-electron transducer (solid-contact). Methacrylate-functionalized poly(3,4-ethylenedioxythiophene) (Meth-PEDOT) and Meth-PEDOT films containing either multiwalled carbon nanotubes (MWCNT) or carboxylated MWCNT (cMWCNT) were used as solid contacts. The solid contacts were deposited by drop-casting on screen-printed electrodes and characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and potentiometry. Covalent binding between the solid contact and the ISM was obtained via photopolymerization in order to increase the robustness of the Ca 2+ -SCISEs. The performance of the Ca 2+ -SCISEs was studied by measuring their potentiometric response and their sensitivity to light, oxygen and carbon dioxide. Meth-PEDOT was found to be a promising solid-contact material to develop low-cost and easy to prepare ISEs. Copyright © 2018 Elsevier B.V. All rights reserved.

The new wave of ion-selective electrodes

PubMed Central

Pretsch, Ernö

2007-01-01

During the last decade, the capabilities of potentiometric analysis have changed fundamentally in that the lower limit of detection (LOD) of ion-selective electrodes (ISEs) has improved by a factor of up to one million and the discrimination factor of interferences from ions by up to one billion. These spectacular improvements are related to the control of ion fluxes through the ion-selective membrane. Nowadays, ISEs can be used for trace measurements in environmental samples. However, by reducing the volume of the samples, the LOD in terms of the amount of analytes has been reduced to the attomole range. This is promising for bioanalysis using metal nanoparticle labels. Other recent progress includes the excellent fundamental understanding of the working mechanism, the introduction of a novel kind of calibration procedure that reduces the demands on signal stability and reproducibility, and the advent of pulsed amperometric methods. PMID:12175191

Potentiometric sensors using cotton yarns, carbon nanotubes and polymeric membranes.

PubMed

Guinovart, Tomàs; Parrilla, Marc; Crespo, Gastón A; Rius, F Xavier; Andrade, Francisco J

2013-09-21

A simple and generalized approach to build electrochemical sensors for wearable devices is presented. Commercial cotton yarns are first turned into electrical conductors through a simple dyeing process using a carbon nanotube ink. These conductive yarns are then partially coated with a suitable polymeric membrane to build ion-selective electrodes. Potentiometric measurements using these yarn-potentiometric sensors are demonstrated. Examples of yarns that can sense pH, K(+) and NH4(+) are presented. In all cases, these sensing yarns show limits of detection and linear ranges that are similar to those obtained with lab-made solid-state ion-selective electrodes. Through the immobilization of these sensors in a band-aid, it is shown that this approach could be easily implemented in a wearable device. Factors affecting the performance of the sensors and future potential applications are discussed.

On the nature of liquid junction and membrane potentials.

PubMed

Perram, John W; Stiles, Peter J

2006-09-28

Whenever a spatially inhomogeneous electrolyte, composed of ions with different mobilities, is allowed to diffuse, charge separation and an electric potential difference is created. Such potential differences across very thin membranes (e.g. biomembranes) are often interpreted using the steady state Goldman equation, which is usually derived by assuming a spatially constant electric field. Through the fundamental Poisson equation of electrostatics, this implies the absence of free charge density that must provide the source of any such field. A similarly paradoxical situation is encountered for thick membranes (e.g. in ion-selective electrodes) for which the diffusion potential is normally interpreted using the Henderson equation. Standard derivations of the Henderson equation appeal to local electroneutrality, which is also incompatible with sources of electric fields, as these require separated charges. We analyse self-consistent solutions of the Nernst-Planck-Poisson equations for a 1 : 1-univalent electrolyte to show that the Goldman and Henderson steady-state membrane potentials are artefacts of extraneous charges created in the reservoirs of electrolyte solution on either side of the membrane, due to the unphysical nature of the usual (Dirichlet) boundary conditions assumed to apply at the membrane-electrolyte interfaces. We also show, with the aid of numerical simulations, that a transient electric potential difference develops in any confined, but initially non-uniform, electrolyte solution. This potential difference ultimately decays to zero in the real steady state of the electrolyte, which corresponds to thermodynamic equilibrium. We explain the surprising fact that such transient potential differences are well described by the Henderson equation by using a computer algebra system to extend previous steady-state singular perturbation theories to the time-dependent case. Our work therefore accounts for the success of the Henderson equation in analysing experimental liquid-junction potentials.

Selective observation of charge storing ions in supercapacitor electrode materials.

PubMed

Forse, Alexander C; Griffin, John M; Grey, Clare P

2018-02-01

Nuclear magnetic resonance (NMR) spectroscopy has emerged as a useful technique for probing the structure and dynamics of the electrode-electrolyte interface in supercapacitors, as ions inside the pores of the carbon electrodes can be studied separately from bulk electrolyte. However, in some cases spectral resolution can limit the information that can be obtained. In this study we address this issue by showing how cross polarisation (CP) NMR experiments can be used to selectively observe the in-pore ions in supercapacitor electrode materials. We do this by transferring magnetisation from 13 C nuclei in porous carbons to nearby nuclei in the cations ( 1 H) or anions ( 19 F) of an ionic liquid. Two-dimensional NMR experiments and CP kinetics measurements confirm that in-pore ions are located within Ångströms of sp 2 -hybridised carbon surfaces. Multinuclear NMR experiments hold promise for future NMR studies of supercapacitor systems where spectral resolution is limited. Copyright © 2017 University of Cambridge. Published by Elsevier Inc. All rights reserved.

NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

The Role of Ion Exchange Membranes in Membrane Capacitive Deionisation

PubMed Central

Hassanvand, Armineh; Wei, Kajia; Talebi, Sahar

2017-01-01

Ion-exchange membranes (IEMs) are unique in combining the electrochemical properties of ion exchange resins and the permeability of a membrane. They are being used widely to treat industrial effluents, and in seawater and brackish water desalination. Membrane Capacitive Deionisation (MCDI) is an emerging, energy efficient technology for brackish water desalination in which these ion-exchange membranes act as selective gates allowing the transport of counter-ions toward carbon electrodes. This article provides a summary of recent developments in the preparation, characterization, and performance of ion exchange membranes in the MCDI field. In some parts of this review, the most relevant literature in the area of electrodialysis (ED) is also discussed to better elucidate the role of the ion exchange membranes. We conclude that more work is required to better define the desalination performance of the proposed novel materials and cell designs for MCDI in treating a wide range of feed waters. The extent of fouling, the development of cleaning strategies, and further techno-economic studies, will add value to this emerging technique. PMID:28906442

Simple and fast method for fabrication of endoscopic implantable sensor arrays.

PubMed

Tahirbegi, I Bogachan; Alvira, Margarita; Mir, Mònica; Samitier, Josep

2014-06-26

Here we have developed a simple method for the fabrication of disposable implantable all-solid-state ion-selective electrodes (ISE) in an array format without using complex fabrication equipment or clean room facilities. The electrodes were designed in a needle shape instead of planar electrodes for a full contact with the tissue. The needle-shape platform comprises 12 metallic pins which were functionalized with conductive inks and ISE membranes. The modified microelectrodes were characterized with cyclic voltammetry, scanning electron microscope (SEM), and optical interferometry. The surface area and roughness factor of each microelectrode were determined and reproducible values were obtained for all the microelectrodes on the array. In this work, the microelectrodes were modified with membranes for the detection of pH and nitrate ions to prove the reliability of the fabricated sensor array platform adapted to an endoscope.

Apparatus for Pumping a Fluid

NASA Technical Reports Server (NTRS)

van Boeyen, Roger W. (Inventor); Reeh, Jonathan A. (Inventor); Kesmez, Mehmet (Inventor); Heselmeyer, Eric A. (Inventor); Parkey, Jeffrey S. (Inventor)

2016-01-01

An electrochemically actuated pump and an electrochemical actuator for use with a pump. The pump includes one of various stroke volume multiplier configurations with the pressure of a pumping fluid assisting actuation of a driving fluid bellows. The electrochemical actuator has at least one electrode fluidically coupled to the driving fluid chamber of the first pump housing and at least one electrode fluidically coupled to the driving fluid chamber of the second pump housing. Accordingly, the electrochemical actuator selectively pressurizes hydrogen gas within a driving fluid chamber. The actuator may include a membrane electrode assembly including an ion exchange membrane with first and second catalyzed electrodes in contact with opposing sides of the membrane, and first and second hydrogen gas chambers in fluid communication with the first and second electrodes, respectively. A controller may reverse the polarity of a voltage source electrically coupled to the current collectors.

Development of taste sensor system for differentiation of Indonesian herbal medicines

NASA Astrophysics Data System (ADS)

Kaltsum, U.; Triyana, K.; Siswanta, D.

2014-09-01

In Indonesia, herbal medicines are usually produced by small and medium enterprises which are relatively low in quality control. The purpose of this paper is to report that we have developed a taste sensor system with global selectivity, i.e., electronic tongue (e-tongue) for differentiation of Indonesian herbal medicines. The e-tongue was composed of five kinds of ion selective electrodes as working electrodes, data acquisition system, and pattern recognition system. Each ion selective electrode (ISE) was built by attaching lipid/polymer membrane. For this purpose, the five kinds of membranes were built by mixing lipid, plasticizer (nitrophenyl octyl ether/NPOE), polyvinyl chloride (PVC), and tetrahydrofuran (THF). In this study, we employed five kinds of lipid, namely oleic acid (OA), dioctyl phosphate (DOP), decyl alcohol (DA), dodecylamine (DDC), and trioctyl methyl ammonium chloride (TOMA). In this case, the membranes transform information of taste substances into electric signal. The five kinds of Indonesian herbal medicine were purchased from local supermarket in Yogyakarta, i.e., kunyit asam (made from turmeric and tamarind), beras kencur (made from rice and kencur), jahe wangi (made from ginger and fragrance), sirih wangi (made from betel leaf), and temulawak (made from Javanese ginger). Prior to detecting the taste from the Indonesian herbal medicine samples, each ion selective electrode was tested with five basic taste samples, i.e., for saltiness, sweetness, umami, bitterness, and sourness. All ISEs showed global selectivity to all samples. Furthermore, the array of ISEs showed specific response pattern to each Indonesian herbal medicine. For pattern recognition system, we employed principle component analysis (PCA). As a result, the e-tongue was able to differentiate five kinds of Indonesian herbal medicines, proven by the total variance of first and second principle components is about 93%. For the future, the e-tongue may be developed for quality control application in herbal medicine industries.

Development of taste sensor system for differentiation of Indonesian herbal medicines

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

Kaltsum, U., E-mail: um-mik@yahoo.co.id; Triyana, K., E-mail: triyana@ugm.ac.id; Siswanta, D., E-mail: triyana@ugm.ac.id

In Indonesia, herbal medicines are usually produced by small and medium enterprises which are relatively low in quality control. The purpose of this paper is to report that we have developed a taste sensor system with global selectivity, i.e., electronic tongue (e-tongue) for differentiation of Indonesian herbal medicines. The e-tongue was composed of five kinds of ion selective electrodes as working electrodes, data acquisition system, and pattern recognition system. Each ion selective electrode (ISE) was built by attaching lipid/polymer membrane. For this purpose, the five kinds of membranes were built by mixing lipid, plasticizer (nitrophenyl octyl ether/NPOE), polyvinyl chloride (PVC),more » and tetrahydrofuran (THF). In this study, we employed five kinds of lipid, namely oleic acid (OA), dioctyl phosphate (DOP), decyl alcohol (DA), dodecylamine (DDC), and trioctyl methyl ammonium chloride (TOMA). In this case, the membranes transform information of taste substances into electric signal. The five kinds of Indonesian herbal medicine were purchased from local supermarket in Yogyakarta, i.e., kunyit asam (made from turmeric and tamarind), beras kencur (made from rice and kencur), jahe wangi (made from ginger and fragrance), sirih wangi (made from betel leaf), and temulawak (made from Javanese ginger). Prior to detecting the taste from the Indonesian herbal medicine samples, each ion selective electrode was tested with five basic taste samples, i.e., for saltiness, sweetness, umami, bitterness, and sourness. All ISEs showed global selectivity to all samples. Furthermore, the array of ISEs showed specific response pattern to each Indonesian herbal medicine. For pattern recognition system, we employed principle component analysis (PCA). As a result, the e-tongue was able to differentiate five kinds of Indonesian herbal medicines, proven by the total variance of first and second principle components is about 93%. For the future, the e-tongue may be developed for quality control application in herbal medicine industries.« less

New equivalent-electrical circuit model and a practical measurement method for human body impedance.

PubMed

Chinen, Koyu; Kinjo, Ichiko; Zamami, Aki; Irei, Kotoyo; Nagayama, Kanako

2015-01-01

Human body impedance analysis is an effective tool to extract electrical information from tissues in the human body. This paper presents a new measurement method of impedance using armpit electrode and a new equivalent circuit model for the human body. The lowest impedance was measured by using an LCR meter and six electrodes including armpit electrodes. The electrical equivalent circuit model for the cell consists of resistance R and capacitance C. The R represents electrical resistance of the liquid of the inside and outside of the cell, and the C represents high frequency conductance of the cell membrane. We propose an equivalent circuit model which consists of five parallel high frequency-passing CR circuits. The proposed equivalent circuit represents alpha distribution in the impedance measured at a lower frequency range due to ion current of the outside of the cell, and beta distribution at a high frequency range due to the cell membrane and the liquid inside cell. The calculated values by using the proposed equivalent circuit model were consistent with the measured values for the human body impedance.

Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon

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

Soto, Fernando A.; Yan, Pengfei; Engelhard, Mark H.

Solid-electrolyte interphase (SEI) films with controllable properties are highly desirable for improving battery performance. In this paper, a combined experimental and theoretical approach is used to study SEI films formed on hard carbon in Li- and Na-ion batteries. It is shown that a stable SEI layer can be designed by precycling an electrode in a desired Li- or Na-based electrolyte, and that ionic transport can be kinetically controlled. Selective Li- and Na-based SEI membranes are produced using Li- or Na-based electrolytes, respectively. The Na-based SEI allows easy transport of Li ions, while the Li-based SEI shuts off Na-ion transport. Na-ionmore » storage can be manipulated by tuning the SEI layer with film-forming electrolyte additives, or by preforming an SEI layer on the electrode surface. The Na specific capacity can be controlled to < 25 mAh g(-1); approximate to 1/10 of the normal capacity (250 mAh g(-1)). Unusual selective/ preferential transport of Li ions is demonstrated by preforming an SEI layer on the electrode surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion-selective conductors using electrochemical approaches.« less

Development of Nanostructured Water Treatment Membranes Based on Thermotropic Liquid Crystals: Molecular Design of Sub-Nanoporous Materials.

PubMed

Sakamoto, Takeshi; Ogawa, Takafumi; Nada, Hiroki; Nakatsuji, Koji; Mitani, Masato; Soberats, Bartolome; Kawata, Ken; Yoshio, Masafumi; Tomioka, Hiroki; Sasaki, Takao; Kimura, Masahiro; Henmi, Masahiro; Kato, Takashi

2018-01-01

Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self-organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported. Membranes with preserved 1D or 3D self-organized sub-nanopores are obtained by photopolymerization of ionic columnar or bicontinuous cubic liquid crystals. These membranes show salt rejection ability, ion selectivity, and excellent water permeability. The relationships between the structures and the transport properties of water molecules and ionic solutes in the sub-nanopores in the membranes are examined by molecular dynamics simulations. The results suggest that the volume of vacant space in the nanochannel greatly affects the water and ion permeability.

Development of Nanostructured Water Treatment Membranes Based on Thermotropic Liquid Crystals: Molecular Design of Sub‐Nanoporous Materials

PubMed Central

Ogawa, Takafumi; Nakatsuji, Koji; Mitani, Masato; Soberats, Bartolome; Kawata, Ken; Yoshio, Masafumi; Tomioka, Hiroki; Sasaki, Takao; Kimura, Masahiro

2017-01-01

Abstract Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self‐organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported. Membranes with preserved 1D or 3D self‐organized sub‐nanopores are obtained by photopolymerization of ionic columnar or bicontinuous cubic liquid crystals. These membranes show salt rejection ability, ion selectivity, and excellent water permeability. The relationships between the structures and the transport properties of water molecules and ionic solutes in the sub‐nanopores in the membranes are examined by molecular dynamics simulations. The results suggest that the volume of vacant space in the nanochannel greatly affects the water and ion permeability. PMID:29375969

Aqueous-Processed, High-Capacity Electrodes for Membrane Capacitive Deionization.

PubMed

Jain, Amit; Kim, Jun; Owoseni, Oluwaseye M; Weathers, Cierra; Caña, Daniel; Zuo, Kuichang; Walker, W Shane; Li, Qilin; Verduzco, Rafael

2018-05-15

Membrane capacitive deionization (MCDI) is a low-cost technology for desalination. Typically, MCDI electrodes are fabricated using a slurry of nanoparticles in an organic solvent along with polyvinylidene fluoride (PVDF) polymeric binder. Recent studies of the environmental impact of CDI have pointed to the organic solvents used in the fabrication of CDI electrodes as key contributors to the overall environmental impact of the technology. Here, we report a scalable, aqueous processing approach to prepare MCDI electrodes using water-soluble polymer poly(vinyl alcohol) (PVA) as a binder and ion-exchange polymer. Electrodes are prepared by depositing aqueous slurry of activated carbon and PVA binder followed by coating with a thin layer of PVA-based cation- or anion-exchange polymer. When coated with ion-exchange layers, the PVA-bound electrodes exhibit salt adsorption capacities up to 14.4 mg/g and charge efficiencies up to 86.3%, higher than typically achieved for activated carbon electrodes with a hydrophobic polymer binder and ion-exchange membranes (5-13 mg/g). Furthermore, when paired with low-resistance commercial ion-exchange membranes, salt adsorption capacities exceed 18 mg/g. Our overall approach demonstrates a simple, environmentally friendly, cost-effective, and scalable method for the fabrication of high-capacity MCDI electrodes.

Design and construction of new potentiometric sensors for determination of Al3+ ion based on (Z)-2-(2-methyl benzylidene)-1-(2,4-dinitrophenyl) hydrazine.

PubMed

Mizani, F; Salmanzadeh Ardabili, S; Ganjaliab, M R; Faridbod, F; Payehghadr, M; Azmoodeh, M

2015-04-01

(Z)-2-(2-methyl benzylidene)-1-(2,4-dinitrophenyl) hydrazine (L) was used as an active component of PVC membrane electrode (PME), coated graphite electrode (CGE) and coated silver wire electrode (CWE) for sensing Al(3+) ion. The electrodes exhibited linear Nernstian responses to Al(3+) ion in the concentration range of 1.0×10(-6) to 1.0×10(-1)M (for PME, LOD=8.8×10(-7)M), 5.5×10(-7) to 2.0×10(-1)M (for CWE, LOD=3.3×10(-7)M) and 1.5×10(-7) to 1.0×10(-1)M (for CGE, LOD=9.2×10(-8)M). The best performances were observed with the membranes having the composition of L:PVC:NPOE:NaTPB in the ratio of 5:35:57:3 (w/w; mg). The electrodes have a response time of 6s and an applicable pH range of 3.5-9.1. The sensors have a lifetime of about 15weeks and exhibited excellent selectivity over a number of mono-, bi-, and tri-valent cations including alkali, alkaline earth metal, heavy and transition metal ions. Analytical utility of the proposed sensor has been further tested by using it as an indicator electrode in the potentiometric titration of Al(3+) with EDTA. The electrode was also successfully applied for the determination of Al(3+) ion in real and pharmaceutical samples. Copyright © 2015 Elsevier B.V. All rights reserved.

A Ho(III) potentiometric polymeric membrane sensor based on a new four dentate neutral ion carrier.

PubMed

Zamani, Hassan Ali; Zanganeh-Asadabadi, Abbas; Rohani, Mitra; Zabihi, Mohammad Saleh; Fadaee, Javad; Ganjali, Mohammad Reza; Faridbod, Farnoush; Meghdadi, Soraia

2013-03-01

In this research, we report a new Ho(3+)-PVC membrane electrode based on N-(4,5-dimethyl-2-(picolinamido)phenyl)picolinamide (H(2)Me(2)bpb) as a suitable ion carrier. Poly vinylchloride (PVC)-based membrane composed of H(2)Me(2)bpb with oleic acid (OA) as anionic additives, and o-nitrophenyloctyl ether (NPOE) as plasticized solvent mediator. The sensor exhibits a Nernstian slope of 20.1 ± 0.2 mV decade(-1) over the concentration range of 1.0 × 10(-6) to 1.0 × 1(-2) mol L(-1), and a detection limit of 5.0 × 10(-7) mol L(-1) of Ho(3+) ions. The potentiometric response of the sensor is independent of the solution pH in the range of 3.5-9.4. It has a very short response time, in the whole concentration range (<10s), and can be used for at least eight weeks. The proposed electrode shows a good selectivity towards Ho(3+) ions over a wide variety of cations, including alkali, alkaline earth, transition and heavy metal ions. To assess its analytical applicability the proposed Ho(3+) sensor was successfully applied as an indicator electrode in the titration of Ho(3+) ion solutions in certified reference materials, alloy samples and for the determination of the fluoride ion in two mouthwash preparations. Copyright © 2012 Elsevier B.V. All rights reserved.

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

PubMed Central

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

2013-01-01

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

Carbon Nanotube-Based Ion Selective Sensors for Wearable Applications.

PubMed

Roy, Soumyendu; David-Pur, Moshe; Hanein, Yael

2017-10-11

Wearable electronics offer new opportunities in a wide range of applications, especially sweat analysis using skin sensors. A fundamental challenge in these applications is the formation of sensitive and stable electrodes. In this article we report the development of a wearable sensor based on carbon nanotube (CNT) electrode arrays for sweat sensing. Solid-state ion selective electrodes (ISEs), sensitive to Na + ions, were prepared by drop coating plasticized poly(vinyl chloride) (PVC) doped with ionophore and ion exchanger on CNT electrodes. The ion selective membrane (ISM) filled the intertubular spaces of the highly porous CNT film and formed an attachment that was stronger than that achieved with flat Au, Pt, or carbon electrodes. Concentration of the ISM solution used influenced the attachment to the CNT film, the ISM surface morphology, and the overall performance of the sensor. Sensitivity of 56 ± 3 mV/decade to Na + ions was achieved. Optimized solid-state reference electrodes (REs), suitable for wearable applications, were prepared by coating CNT electrodes with colloidal dispersion of Ag/AgCl, agarose hydrogel with 0.5 M NaCl, and a passivation layer of PVC doped with NaCl. The CNT-based REs had low sensitivity (-1.7 ± 1.2 mV/decade) toward the NaCl solution and high repeatability and were superior to bare Ag/AgCl, metals, carbon, and CNT films, reported previously as REs. CNT-based ISEs were calibrated against CNT-based REs, and the short-term stability of the system was tested. We demonstrate that CNT-based devices implemented on a flexible support are a very attractive platform for future wearable technology devices.

Phoenix Mars Lander's Chemistry Lab in a Box

NASA Technical Reports Server (NTRS)

2007-01-01

The wet chemistry laboratory on NASA's Phoenix Mars Lander has four teacup-size beakers. This photograph shows one of them. The laboratory is part of the spacecraft's Microscopy, Electrochemistry and Conductivity Analyzer.

Each beaker will be used only once, for assessing soluble chemicals in a sample of Martian soil by mixing water with the sample to a soupy consistency and keeping it warm enough to remain liquid during the analysis.

On the inner surface of the beaker are 26 sensors, mostly electrodes behind selectively permeable membranes or gels. Some sensors will give information about the acidity or alkalinity of the soil sample. Others will gauge concentrations of such ions as chlorides, bromides, magnesium, calcium and potassium. Comparisons of the concentrations of water-soluble ions in soil samples from different depths below the surface of the landing site may provide clues to the history of the water in the soil.

Simple and Fast Method for Fabrication of Endoscopic Implantable Sensor Arrays

PubMed Central

Tahirbegi, I. Bogachan; Alvira, Margarita; Mir, Mònica; Samitier, Josep

2014-01-01

Here we have developed a simple method for the fabrication of disposable implantable all-solid-state ion-selective electrodes (ISE) in an array format without using complex fabrication equipment or clean room facilities. The electrodes were designed in a needle shape instead of planar electrodes for a full contact with the tissue. The needle-shape platform comprises 12 metallic pins which were functionalized with conductive inks and ISE membranes. The modified microelectrodes were characterized with cyclic voltammetry, scanning electron microscope (SEM), and optical interferometry. The surface area and roughness factor of each microelectrode were determined and reproducible values were obtained for all the microelectrodes on the array. In this work, the microelectrodes were modified with membranes for the detection of pH and nitrate ions to prove the reliability of the fabricated sensor array platform adapted to an endoscope. PMID:24971473

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

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

1998-01-01

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

A novel EIS field effect structures coated with TESUD-PPy-PVC-dibromoaza[7]helicene matrix for potassium ions detection.

PubMed

Tounsi, Moncef; Ben Braiek, Mourad; Barhoumi, Houcine; Baraket, Abdoullatif; Lee, Michael; Zine, Nadia; Maaref, Abderrazak; Errachid, Abdelhamid

2016-04-01

In this work, we describe the development of new Aza[7]helicene-containing PVC-based membranes for the K(+) ions quantification. Here, silicon nitride-based structures (Si-p/SiO2/Si3N4) were developed and the surface was activated, functionalized with an aldehyde-silane (11-(Triethoxysilyl)undecanal (TESUD)), functionalized with polypyrrole (PPy), and coated with the polyvinylchloride (PVC)-membrane containing the Aza[7]helicene as ionophore. All stages of functionalization process have been thoroughly studied by contact angle measurements (CAMs) and atomic force microscopy (AFM). The developed ion-selective electrode (ISE) was then applied using electrochemical impedance spectroscopy (EIS) for the detection of potassium ions. A linear range was observed between 1.0 × 10(-8) M to 1.0 × 10(-3) M and a detection limit of 1.0 × 10(-8) M was observed. The EIS results have showed a good sensitivity to potassium ion using this novel technique. The target helicene exhibited good solubility and excellent thermal stability with a high decomposition temperature (Td > 300 °C) and it indicates that helicene may be a promising material as ionophore for ion-selective electrodes (ISEs) elaboration. Copyright © 2016 Elsevier B.V. All rights reserved.

Recent advances in the use of ionic liquids for electrochemical sensing.

PubMed

Silvester, Debbie S

2011-12-07

Ionic Liquids are salts that are liquid at (or just above) room temperature. They possess several advantageous properties (e.g. high intrinsic conductivity, wide electrochemical windows, low volatility, high thermal stability and good solvating ability), which make them ideal as non-volatile electrolytes in electrochemical sensors. This mini-review article describes the recent uses of ionic liquids in electrochemical sensing applications (covering the last 3 years) in the context of voltammetric sensing at solid/liquid, liquid/liquid interfaces and carbon paste electrodes, as well as their use in gas sensing, ion-selective electrodes, and for detecting biological molecules, explosives and chemical warfare agents. A comment on the future direction and challenges in this field is also presented.

Structure and Orientation of Bovine Lactoferrampin in the Mimetic Bacterial Membrane as Revealed by Solid-State NMR and Molecular Dynamics Simulation

PubMed Central

Tsutsumi, Atsushi; Javkhlantugs, Namsrai; Kira, Atsushi; Umeyama, Masako; Kawamura, Izuru; Nishimura, Katsuyuki; Ueda, Kazuyoshi; Naito, Akira

2012-01-01

Bovine lactoferrampin (LFampinB) is a newly discovered antimicrobial peptide found in the N1-domain of bovine lactoferrin (268–284), and consists of 17 amino-acid residues. It is important to determine the orientation and structure of LFampinB in bacterial membranes to reveal the antimicrobial mechanism. We therefore performed 13C and 31P NMR, 13C-31P rotational echo double resonance (REDOR), potassium ion-selective electrode, and quartz-crystal microbalance measurements for LFampinB with mimetic bacterial membrane and molecular-dynamics simulation in acidic membrane. 31P NMR results indicated that LFampinB caused a defect in mimetic bacterial membranes. Ion-selective electrode measurements showed that ion leakage occurred for the mimetic bacterial membrane containing cardiolipin. Quartz-crystal microbalance measurements revealed that LFampinB had greater affinity to acidic phospholipids than that to neutral phospholipids. 13C DD-MAS and static NMR spectra showed that LFampinB formed an α-helix in the N-terminus region and tilted 45° to the bilayer normal. REDOR dephasing patterns between carbonyl carbon nucleus in LFampinB and phosphorus nuclei in lipid phosphate groups were measured by 13C-31P REDOR and the results revealed that LFampinB is located in the interfacial region of the membrane. Molecular-dynamics simulation showed the tilt angle to be 42° and the rotation angle to be 92.5° for Leu3, which are in excellent agreement with the experimental values. PMID:23083717

Streaming potentials in gramicidin channels measured with ion-selective microelectrodes.

PubMed Central

Tripathi, S; Hladky, S B

1998-01-01

Streaming potentials have been measured for gramicidin channels with a new method employing ion-selective microelectrodes. It is shown that ideally ion-selective electrodes placed at the membrane surface record the true streaming potential. Using this method for ion concentrations below 100 mM, approximately seven water molecules are transported whenever a sodium, potassium, or cesium ion, passes through the channel. This new method confirms earlier measurements (Rosenberg, P.A., and A. Finkelstein. 1978. Interaction of ions and water in gramicidin A channels. J. Gen. Physiol. 72:327-340) in which the streaming potentials were calculated as the difference between electrical potentials measured in the presence of gramicidin and in the presence of the ion carriers valinomycin and nonactin. PMID:9635745

Solid-contact potentiometric polymer membrane microelectrodes for the detection of silver ions at the femtomole level

PubMed Central

Rubinova, Nastassia; Chumbimuni-Torres, Karin; Bakker, Eric

2010-01-01

In recent years, ion-selective electrodes based on polymer membranes have been shown to exhibit detection limits that are often in the nanomolar concentration range, and thus drastically lower than traditionally accepted. Since potentiometry is less dependent on scaling laws that other established analytical techniques, their performance in confined sample volumes is explored here. Solid-contact silver-selective microelectrodes, with a sodium-selective microelectrode as a reference, were inserted into a micropipette tip used as a 50-μl sample. The observed potential stabilities, reproducibilities and detection limits were attractive and largely matched that for large 100-ml samples. This should pave the way for further experiments to detecting ultra-small total ion concentrations by potentiometry, especially when used as a transducer after an amplification step in bioanalysis. PMID:20543910

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

Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai

The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturatedmore » moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.« less

Development of a pH sensing membrane electrode based on a new calix[4]arene derivative.

PubMed

Kormalı Ertürün, H Elif; Demirel Özel, Ayça; Sayın, Serkan; Yılmaz, Mustafa; Kılıç, Esma

2015-01-01

A new pH sensing poly(vinyl chloride) (PVC) membrane electrode was developed by using recently synthesized 5,17-bis(4-benzylpiperidine-1-yl)methyl-25,26,27,28-tetrahydroxy calix[4]arene as an ionophore. The effects of membrane composition, inner filling solution and conditioning solution on the potential response of the proposed pH sensing membrane electrode were investigated. An optimum membrane composition of 3% ionophore, 67% o-nitrophenyl octyl ether (o-NPOE) as plasticizer, 30% PVC was found. The electrode exhibited a near-Nernstian slope of 58.7±1.1 mV pH(-1) in the pH range 1.9-12.7 at 20±1 °C. It showed good selectivity for H(+) ions in the presence of some cations and anions and a longer lifetime of at least 12 months when compared with the other PVC membrane pH electrodes reported in the literature. Having a wide working pH range, it was not only applied as a potentiometric indicator electrode in various acid-base titrations, but also successfully employed in different real samples. It has good reproducibility and repeatability with a response time of 6-7s. Compared to traditional glass pH electrode, it exhibited excellent potentiometric response after being used in fluoride-containing media. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrochemical sample matrix elimination for trace-level potentiometric detection with polymeric membrane ion-selective electrodes.

PubMed

Chumbimuni-Torres, Karin Y; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-08-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultratrace level (subnanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth-coated electrode, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte.

Electrochemical Sample Matrix Elimination for Trace Level Potentiometric Detection with Polymeric Membrane Ion-Selective Electrodes

PubMed Central

Chumbimuni-Torres, Karin Y.; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-01-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultra-trace level (sub-nanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination (EMPM) of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth coated electrodes, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte. PMID:18570385

Progress in Development of Improved Ion-Channel Biosensors

NASA Technical Reports Server (NTRS)

Nadeau, Jay L.; White, Victor E.; Maurer, Joshua A.; Dougherty, Dennis A.

2008-01-01

Further improvements have recently been made in the development of the devices described in Improved Ion-Channel Biosensors (NPO-30710), NASA Tech Briefs, Vol. 28, No. 10 (October 2004), page 30. As discussed in more detail in that article, these sensors offer advantages of greater stability, greater lifetime, and individual electrical addressability, relative to prior ion-channel biosensors. In order to give meaning to a brief description of the recent improvements, it is necessary to recapitulate a substantial portion of the text of the cited previous article. The figure depicts one sensor that incorporates the recent improvements, and can be helpful in understanding the recapitulated text, which follows: These sensors are microfabricated from silicon and other materials compatible with silicon. Typically, the sensors are fabricated in arrays in silicon wafers on glass plates. Each sensor in the array can be individually electrically addressed, without interference with its neighbors. Each sensor includes a well covered by a thin layer of silicon nitride, in which is made a pinhole for the formation of a lipid bilayer membrane. In one stage of fabrication, the lower half of the well is filled with agarose, which is allowed to harden. Then the upper half of the well is filled with a liquid electrolyte (which thereafter remains liquid) and a lipid bilayer is painted over the pinhole. The liquid contains a protein that forms an ion channel on top of the hardened agarose. The combination of enclosure in the well and support by the hardened agarose provides the stability needed to keep the membrane functional for times as long as days or even weeks. An electrode above the well, another electrode below the well, and all the materials between the electrodes together constitute a capacitor. What is measured is the capacitive transient current in response to an applied voltage pulse. One notable feature of this sensor, in comparison with prior such sensors, is a relatively thick dielectric layer between the top of the well and the top electrode. This layer greatly reduces the capacitance of an aperture across which the ion channels are formed, thereby increasing the signal-to-noise ratio. The use of a relatively large aperture with agarose support makes it possible to form many ion channels instead of only one, thereby further increasing the signal-to-noise ratio and effectively increasing the size of the available ionic reservoir. The relatively large reservoir makes it possible to measure AC rather than DC. This concludes the recapitulation from the cited previous article.

Effect of porosity and tortuosity of electrodes on carbon polymer soft actuators

NASA Astrophysics Data System (ADS)

S, Sunjai Nakshatharan; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2018-01-01

This work presents an electro-mechanical model and simulation of ionic electroactive polymer soft actuators with a porous carbon electrode, polymer membrane, and ionic liquid electrolyte. An attempt is made to understand the effects of specific properties of the porous electrodes such as porosity and tortuosity on the charge dynamics and mechanical performance of the actuator. The model uses porous electrode theory to study the electrochemical response of the system. The mechanical response of the whole laminate is attributed to the evolution of local stresses caused by diffusion of ions (diffusion-induced stresses or chemical stresses). The model indicates that in actuators with porous electrode, the diffusion coefficient of ions, conductivity of the electrodes, and ionic conductivity in both electrodes and separator are altered significantly. In addition, the model leads to an obvious deduction that the ions that are highly active in terms of mobility will dominate the whole system in terms of resulting mechanical deformation direction and rate of deformation. Finally, to validate the model, simulations are conducted using the finite element method, and the outcomes are compared with the experimental data. Significant effort has been put forward to experimentally measure the key parameters essential for the validation of the model. The results show that the model developed is able to well predict the behavior of the actuator, providing a comprehensive understanding of charge dynamics in ionic polymer actuator with porous electrodes.

A reagentless amperometric biosensor for alcohol detection in column liquid chromatography based on co-immobilized peroxidase and alcohol oxidase in carbon paste.

PubMed

Johansson, K; Jönsson-Pettersson, G; Gorton, L; Marko-Varga, G; Csöregi, E

1993-12-01

A reagentless carbon paste electrode chemically modified with covalently bound alcohol oxidase and horse-radish peroxidase was examined as a selective sensor in flow injection and column liquid chromatography. A combination of carbodiimide, glutaraldehyde, and polyethyleneimine was used for immobilizing the enzymes in the paste. The surface of the electrodes was protected by first forming a layer of electropolymerized ortho-phenylenediamine followed by deposition of a cation exchange membrane (Eastman AQ 29D). The electrodes were used for detection of hydrogen peroxide, methanol, ethanol, propanol, isopropanol, and butanol. Preliminary investigations of the use of this sensor for bioprocess control are reported.

On the Dynamical Regimes of Pattern-Accelerated Electroconvection.

PubMed

Davidson, Scott M; Wessling, Matthias; Mani, Ali

2016-03-03

Recent research has established that electroconvection can enhance ion transport at polarized surfaces such as membranes and electrodes where it would otherwise be limited by diffusion. The onset of such overlimiting transport can be influenced by the surface topology of the ion selective membranes as well as inhomogeneities in their electrochemical properties. However, there is little knowledge regarding the mechanisms through which these surface variations promote transport. We use high-resolution direct numerical simulations to develop a comprehensive analysis of electroconvective flows generated by geometric patterns of impermeable stripes and investigate their potential to regularize electrokinetic instabilities. Counterintuitively, we find that reducing the permeable area of an ion exchange membrane, with appropriate patterning, increases the overall ion transport rate by up to 80%. In addition, we present analysis of nonpatterned membranes, and find a novel regime of electroconvection where a multivalued current is possible due to the coexistence of multiple convective states.

Advanced membrane electrode assemblies for fuel cells

DOEpatents

Kim, Yu Seung; Pivovar, Bryan S.

2012-07-24

A method of preparing advanced membrane electrode assemblies (MEA) for use in fuel cells. A base polymer is selected for a base membrane. An electrode composition is selected to optimize properties exhibited by the membrane electrode assembly based on the selection of the base polymer. A property-tuning coating layer composition is selected based on compatibility with the base polymer and the electrode composition. A solvent is selected based on the interaction of the solvent with the base polymer and the property-tuning coating layer composition. The MEA is assembled by preparing the base membrane and then applying the property-tuning coating layer to form a composite membrane. Finally, a catalyst is applied to the composite membrane.

Advanced membrane electrode assemblies for fuel cells

DOEpatents

Kim, Yu Seung; Pivovar, Bryan S

2014-02-25

A method of preparing advanced membrane electrode assemblies (MEA) for use in fuel cells. A base polymer is selected for a base membrane. An electrode composition is selected to optimize properties exhibited by the membrane electrode assembly based on the selection of the base polymer. A property-tuning coating layer composition is selected based on compatibility with the base polymer and the electrode composition. A solvent is selected based on the interaction of the solvent with the base polymer and the property-tuning coating layer composition. The MEA is assembled by preparing the base membrane and then applying the property-tuning coating layer to form a composite membrane. Finally, a catalyst is applied to the composite membrane.

Hybrid capacitive deionization with anion-exchange membranes for lithium extraction

NASA Astrophysics Data System (ADS)

Siekierka, Anna; Bryjak, Marek

2017-11-01

Lithium is considered to be a critical material for various industrial fields. We present our studies on extraction lithium from diluted aqueous solution by novel hybrid system based on a membrane capacitive deionization and batteries desalination. Hybrid CDI is comprised by a lithium selective adsorbent, activated carbon electrode and anion-exchange membranes. Here, we demonstrated implication of various type of anion-exchange membranes and influence their properties on effective capacity and energy requirements in charge/discharge steps. We described a configuration with anion-exchange membrane characterized by adsorption capacity of 35 mg/g of Li+ with 0.08Wh/g and removal efficiency of 60 % of lithium ions, using novel selective desalination technique.

High-field modulated ion-selective field-effect-transistor (FET) sensors with sensitivity higher than the ideal Nernst sensitivity.

PubMed

Chen, Yi-Ting; Sarangadharan, Indu; Sukesan, Revathi; Hseih, Ching-Yen; Lee, Geng-Yen; Chyi, Jen-Inn; Wang, Yu-Lin

2018-05-29

Lead ion selective membrane (Pb-ISM) coated AlGaN/GaN high electron mobility transistors (HEMT) was used to demonstrate a whole new methodology for ion-selective FET sensors, which can create ultra-high sensitivity (-36 mV/log [Pb 2+ ]) surpassing the limit of ideal sensitivity (-29.58 mV/log [Pb 2+ ]) in a typical Nernst equation for lead ion. The largely improved sensitivity has tremendously reduced the detection limit (10 -10  M) for several orders of magnitude of lead ion concentration compared to typical ion-selective electrode (ISE) (10 -7  M). The high sensitivity was obtained by creating a strong filed between the gate electrode and the HEMT channel. Systematical investigation was done by measuring different design of the sensor and gate bias, indicating ultra-high sensitivity and ultra-low detection limit obtained only in sufficiently strong field. Theoretical study in the sensitivity consistently agrees with the experimental finding and predicts the maximum and minimum sensitivity. The detection limit of our sensor is comparable to that of Inductively-Coupled-Plasma Mass Spectrum (ICP-MS), which also has detection limit near 10 -10  M.

Rapid automated method for on-site determination of sulfadiazine in fish farming: a stainless steel veterinary syringe coated with a selective membrane of PVC serving as a potentiometric detector in a flow-injection-analysis system.

PubMed

Almeida, S A A; Amorim, L R; Heitor, A H; Montenegro, M C B S M; Barbosa, J; Sá, L C; Sales, M G F

2011-12-01

Sulfadiazine is an antibiotic of the sulfonamide group and is used as a veterinary drug in fish farming. Monitoring it in the tanks is fundamental to control the applied doses and avoid environmental dissemination. Pursuing this goal, we included a novel potentiometric design in a flow-injection assembly. The electrode body was a stainless steel needle veterinary syringe of 0.8-mm inner diameter. A selective membrane of PVC acted as a sensory surface. Its composition, the length of the electrode, and other flow variables were optimized. The best performance was obtained for sensors of 1.5-cm length and a membrane composition of 33% PVC, 66% o-nitrophenyloctyl ether, 1% ion exchanger, and a small amount of a cationic additive. It exhibited Nernstian slopes of 61.0 mV decade(-1) down to 1.0 × 10(-5) mol L(-1), with a limit of detection of 3.1 × 10(-6) mol L(-1) in flowing media. All necessary pH/ionic strength adjustments were performed online by merging the sample plug with a buffer carrier of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, pH 4.9. The sensor exhibited the advantages of a fast response time (less than 15 s), long operational lifetime (60 days), and good selectivity for chloride, nitrite, acetate, tartrate, citrate, and ascorbate. The flow setup was successfully applied to the analysis of aquaculture waters. The analytical results were validated against those obtained with liquid chromatography-tandem mass spectrometry procedures. The sampling rate was about 84 samples per hour and recoveries ranged from 95.9 to 106.9%.

Biomimetic supercontainers for size-selective electrochemical sensing of molecular ions

NASA Astrophysics Data System (ADS)

Netzer, Nathan L.; Must, Indrek; Qiao, Yupu; Zhang, Shi-Li; Wang, Zhenqiang; Zhang, Zhen

2017-04-01

New ionophores are essential for advancing the art of selective ion sensing. Metal-organic supercontainers (MOSCs), a new family of biomimetic coordination capsules designed using sulfonylcalix[4]arenes as container precursors, are known for their tunable molecular recognition capabilities towards an array of guests. Herein, we demonstrate the use of MOSCs as a new class of size-selective ionophores dedicated to electrochemical sensing of molecular ions. Specifically, a MOSC molecule with its cavities matching the size of methylene blue (MB+), a versatile organic molecule used for bio-recognition, was incorporated into a polymeric mixed-matrix membrane and used as an ion-selective electrode. This MOSC-incorporated electrode showed a near-Nernstian potentiometric response to MB+ in the nano- to micro-molar range. The exceptional size-selectivity was also evident through contrast studies. To demonstrate the practical utility of our approach, a simulated wastewater experiment was conducted using water from the Fyris River (Sweden). It not only showed a near-Nernstian response to MB+ but also revealed a possible method for potentiometric titration of the redox indicator. Our study thus represents a new paradigm for the rational design of ionophores that can rapidly and precisely monitor molecular ions relevant to environmental, biomedical, and other related areas.

Composite electrolytes of polyethylene oxides/garnets interfacially wetted by ionic liquid for room-temperature solid-state lithium battery

NASA Astrophysics Data System (ADS)

Huo, Hanyu; Zhao, Ning; Sun, Jiyang; Du, Fuming; Li, Yiqiu; Guo, Xiangxin

2017-12-01

Paramount attention has been paid on solid polymer electrolytes due to their potential in enhancement of energy density as well as improvement of safety. Herein, the composite electrolytes consisting of Li-salt-free polyethylene oxides and 200 nm-sized Li6.4La3Zr1.4Ta0.6O12 particles interfacially wetted by [BMIM]TF2N of 1.8 μL cm-2 have been prepared. Such wetted ionic liquid remains the solid state of membrane electrolytes and decreases the interface impedance between the electrodes and the electrolytes. There is no release of the liquid phase from the PEO matrix when the pressure of 5.0 × 104 Pa being applied for 24 h. The interfacially wetted membrane electrolytes show the conductivity of 2.2 × 10-4 S cm-1 at 20 °C, which is one order of magnitude greater than that of the membranes without the wetted ionic liquids. The conduction mechanism is related to a large number of lithium ions releasing from Li6.4La3Zr1.4Ta0.6O12 particles and the improved conductive paths along the ion-liquid-wetted interfaces between the polymer matrix and ceramic grains. When the membranes being used in the solid-state LiFePO4/Li and LiFe0.15Mn0.85PO4/Li cells at 25 °C, the excellent rate capability and superior cycle stability has been shown. The results provide a new prospect for solid polymer electrolytes used for room-temperature solid-state lithium batteries.

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

NASA Astrophysics Data System (ADS)

Brikner, Natalya; Lozano, Paulo C.

2012-11-01

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

Novel PVC-membrane electrode for flow injection potentiometric determination of Biperiden in pharmaceutical preparations.

PubMed

Khaled, Elmorsy; El-Sabbagh, Inas A; El-Kholy, N G; Ghahni, E Y Abdel

2011-12-15

The construction and performance characteristics of Biperiden (BP) polyvinyl chloride (PVC) electrodes are described. Different methods for electrode fabrication are tested including; incorporation of BP-ion pairs (BP-IPs), incorporation of ion pairing agents, or soaking the plain electrode in BP-ion pairs suspension solution. Electrode matrices were optimized referring to the effect of modifier content and nature, plasticizer and the method of modification. The proposed electrodes work satisfactorily in the BP concentration range from 10(-5) to 10(-2)mol L(-1), with fast response time (7s) and adequate operational lifetime (28 days). The electrode potential is pH independent within the range 2.0-7.0, with good selectivity towards BP in presence of various interfering species. The developed electrodes have been applied for potentiometric determination of BP in pharmaceutical formulation under batch and flow injection analysis (FIA) conditions. FIA offers the advantages of accuracy and automation feasibility with high sampling frequency. The dissolution profile for Akineton tablets (2mg BP/tablet) was studied using the proposed electrode in comparison with the official methods. Copyright © 2011 Elsevier B.V. All rights reserved.

Functional membranes. Present and future

NASA Technical Reports Server (NTRS)

Kunitake, T.

1982-01-01

The present situation and the future development of the functional membrane are discussed. It is expected that functional membranes will play increasingly greater roles in the chemical industry of the coming decade. These membranes are formed from polymer films, liquid membranes or bilayer membranes. The two most important technologies based on the polymeric membrane are reverse osmosis and ion exchange. The liquid membrane is used for separation of ionic species; an extension of the solvent extraction process. By using appropriate ligands and ionophores, highly selective separations are realized. The active transport is made possible if the physical and chemical potentials are applied to the transport process. More advanced functional membranes may be designed on the basis of the synthetic bilayer membrane.

BioMEMS for mitochondria medicine

NASA Astrophysics Data System (ADS)

Padmaraj, Divya

A BioMEMS device to study cell-mitochondrial physiological functionalities was developed. The pathogenesis of many diseases including obesity, diabetes and heart failure as well as aging has been linked to functional defects of mitochondria. The synthesis of Adenosine Tri Phosphate (ATP) is determined by the electrical potential across the inner mitochondrial membrane and by the pH difference due to proton flux across it. Therefore, electrical characterization by E-fields with complementary chemical testing was used here. The BioMEMS device was fabricated as an SU-8 based microfluidic system with gold electrodes on SiO2/Si wafers for electromagnetic interrogation. Ion Sensitive Field Effect Transistors (ISFETs) were incorporated for proton studies important in the electron transport chain, together with monitoring Na+, K+ and Ca++ ions for ion channel studies. ISFETs are chemically sensitive Metal Oxide Semiconductor Field Effect Transistor (MOSFET) devices and their threshold voltage is directly proportional to the electrolytic H+ ion variation. These ISFETs (sensitivity ˜55 mV/pH for H+) were further realized as specific ion sensitive Chemical Field Effect Transistors (CHEMFETs) by depositing a specific ion sensitive membrane on the gate. Electrodes for dielectric spectroscopy studies of mitochondria were designed as 2- and 4-probe structures for optimized operation over a wide frequency range. In addition, to limit polarization effects, a 4-electrode set-up with unique meshed pickup electrodes (7.5x7.5 mum2 loops with 4 mum wires) was fabricated. Sensitivity of impedance spectroscopy to membrane potential changes was confirmed by studying the influence of uncouplers and glucose on mitochondria. An electrical model was developed for the mitochondrial sample, and its frequency response correlated with impedance spectroscopy experiments of sarcolemmal mitochondria. Using the mesh electrode structure, we obtained a reduction of 83.28% in impedance at 200 Hz. COMSOL simulations of selected electrical structures in this sensor were compared with experimental results to better understand the physical system. A broadband permittivity analysis tool consisting of lumped and distributed structures was also developed. The frequency range of this device is from 100 Hz to 40 GHz and utilizes an interdigitated capacitor and coplanar waveguide. The simultaneous measurement of membrane potential, ion concentrations and pH would enhance diagnostics and studies of mitochondrial diseases.

Electro-convective versus electroosmotic instability in concentration polarization.

PubMed

Rubinstein, Isaak; Zaltzman, Boris

2007-10-31

Electro-convection is reviewed as a mechanism of mixing in the diffusion layer of a strong electrolyte adjacent to a charge-selective solid, such as an ion exchange (electrodialysis) membrane or an electrode. Two types of electro-convection in strong electrolytes may be distinguished: bulk electro-convection, due to the action of the electric field upon the residual space charge of a quasi-electro-neutral bulk solution, and convection induced by electroosmotic slip, due to electric forces acting in the thin electric double layer of either quasi-equilibrium or non-equilibrium type near the solid/liquid interface. According to recent studies, the latter appears to be the likely source of mixing in the diffusion layer, leading to 'over-limiting' conductance in electrodialysis. Electro-convection near a planar uniform charge selective solid/liquid interface sets on as a result of hydrodynamic instability of one-dimensional steady state electric conduction through such an interface. We compare the results of linear stability analysis obtained for instabilities of this kind appearing in the full electro-convective and limiting non-equilibrium electroosmotic formulations. The short- and long-wave aspects of these instabilities are discussed along with the wave number selection principles.

Hydrodynamics of spatially inhomogeneous real membranes

NASA Astrophysics Data System (ADS)

Kirii, V. A.; Shelistov, V. S.; Demekhin, E. A.

2017-07-01

Electrokinetic processes in the vicinity of inhomogeneous ion-selective surfaces (electrodes, membranes, microchannels, and nanochannels) consisting of alternating conducting and nonconducting regions in the presence of a normal-to-surface electric current are numerically studied. An increase in the electric current density is observed in the case of some particular alternation of conducting and nonconducting regions of the surface. The current-voltage characteristics of homogeneous and inhomogeneous electric membranes are found to be in qualitative agreement. Various physical phenomena leading to the emergence of a supercritical current in homogeneous and inhomogeneous membranes are detected.

The Analysis of Cyanide and Its Breakdown Products in Biological Samples

DTIC Science & Technology

2010-01-01

simultaneous GC-mass spectrometric (MS) analysis of cyanide and thiocyanate, and Funazo et al. (53) quantita- tively methylated cyanide and thiocyanate for...selective membrane electrode for thiocyanate ion based on a bis-taurine- salicylic binuclear copper(II) complex as ionophore. Chinese Journal of Chemistry

Space water electrolysis: Space Station through advance missions

NASA Technical Reports Server (NTRS)

Davenport, Ronald J.; Schubert, Franz H.; Grigger, David J.

1991-01-01

Static Feed Electrolyzer (SFE) technology can satisfy the need for oxygen (O2) and Hydrogen (H2) in the Space Station Freedom and future advanced missions. The efficiency with which the SFE technology can be used to generate O2 and H2 is one of its major advantages. In fact, the SFE is baselined for the Oxygen Generation Assembly within the Space Station Freedom's Environmental Control and Life Support System (ECLSS). In the conventional SFE process an alkaline electrolyte is contained within the matrix and is sandwiched between two porous electrodes. The electrodes and matrix make up a unitized cell core. The electrolyte provides the necessary path for the transport of water and ions between the electrodes, and forms a barrier to the diffusion of O2 and H2. A hydrophobic, microporous membrane permits water vapor to diffuse from the feed water to the cell core. This membrane separates the liquid feed water from the product H2, and, therefore, avoids direct contact of the electrodes by the feed water. The feed water is also circulated through an external heat exchanger to control the temperature of the cell.

A solvated electron lithium electrode for secondary batteries

NASA Astrophysics Data System (ADS)

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

1986-09-01

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

SUPPORTED LIX-84 LIQUID MEMBRANES FOR METAL ION SEPARATION: A STUDY ON METAL ION SORPTION EQUILIBRIUM AND KINETICS

EPA Science Inventory

Supported 2-hydroxy-5-nonyl-acetophenone oxime (LIX-84) liquid membranes have potential applications for the removal (or recovery) of copper ions from waste streams. But, the stability of such a liquid membrane remains the major hurdle for its practical applications. Inorganic su...

Determination of volatile bases in seafood using the ammonia ion selective electrode: collaborative study.

PubMed

Ellis, P C; Pivarnik, L F; Thiam, M; Ellis, P C; Pivarnik, L F; Thiam, M

2000-01-01

Nine collaborating laboratories tested a combination of 23 seafood samples for volatile bases using an ammonia ion selective electrode. Results were reported as mg NH3/100 g fish, but the method reflected levels of both ammonia and trimethylamine, which permeated the ammonia membrane. The 23 samples were broken down into 8 blind duplicate pairs, 2 Youden matched pairs, and 3 single samples covering fresh to spoiled product ranging from 8 to 82 mg NH3/100 g. Seven species were evaluated: Atlantic cod, squid, Atlantic halibut, gray sole, monkfish, dogfish, and Atlantic mackerel. The ammonia electrode assay was performed on an aqueous homogenate consisting of 95 mL distilled water and 5.0 g sample tissue. Alkaline ion strength adjusting solution (2 mL) was added to the homogenate to liberate ammonia that was sensed by the ion specific electrode and measured on a precalibrated portable meter. Repeatability standard deviations (RSDr) ranged from 4.2 to 17%; reproducibility standard deviations (RSDR) ranged from 8.8 to 21%. A standard ammonium chloride solution was provided to all laboratories to spike 3 different samples at 10 mg NH3/100 g. Recoveries of added ammonia as ammonium chloride for fresh, borderline, and spoiled samples were 88.6, 107, and 128%, respectively.

Use of marker ion and cationic surfactant plastic membrane electrode for potentiometric titration of cationic polyelectrolytes.

PubMed

Masadome, Takashi; Imato, Toshihiko

2003-07-04

A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to stearyltrimethylammonium (STA) ion is applied to the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by potentiometric titration, using a potassium poly (vinyl sulfate) (PVSK) solution as a titrant. The end-point of the titration is detected as the potential change of the plasticized PVC membrane electrode caused by decrease in the concentration of STA ion added to the sample solution as a marker ion due to the ion association reaction between the STA ion and PVSK. The effects of the concentration of STA ion, coexisting electrolytes in the sample solution and pH of the sample on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2x10(-5) to 4x10(-4) N for Cat-floc, glycol chitosan, and methylglycol chitosan.

Method for improving the durability of ion insertion materials

DOEpatents

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

2002-01-01

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

Static gas-liquid interfacial direct current discharge plasmas using ionic liquid cathode

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

Kaneko, T.; CREST/JST, Tokyo 102-0075; Baba, K.

Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we have succeeded in creating the static and stable gas (plasmas)-liquid (ionic liquids) interfacial field using a direct current discharge under a low gas pressure condition. It is clarified that the ionic liquid works as a nonmetal liquid electrode, and furthermore, a secondary electron emission coefficient of the ionic liquid is larger than that of conventional metal electrodes. The plasma potential structure of the gas-liquid interfacial region, and resultant interactions between the plasma and the ionic liquid are revealed by changingmore » a polarity of the electrode in the ionic liquid. By utilizing the ionic liquid as a cathode electrode, the positive ions in the plasma region are found to be irradiated to the ionic liquid. This ion irradiation causes physical and chemical reactions at the gas-liquid interfacial region without the vaporization of the ionic liquid.« less

Improved durability of proton exchange membrane fuel cells by introducing Sn (IV) oxide into electrodes using an ion exchange method

NASA Astrophysics Data System (ADS)

Poulsen, M. G.; Larsen, M. J.; Andersen, S. M.

2017-03-01

Electrodes of Proton Exchange Membrane Fuel Cells (PEMFCs), consisting of catalyst-coated gas diffusion layers, were subjected to an optimized ion exchange procedure, in which tin (IV) oxide (SnO2) nanoparticles were introduced into them. Both methanol and sulfuric acid were tested as ion exchange solvents. SnO2 has previously been shown to exhibit radical scavenging abilities towards radicals inside the electrocatalyst layers. Its presence inside the electrodes was confirmed using X-ray photoelectron spectroscopy and X-ray fluorescence. After exposure to an accelerated stress test in a three-electrode setup, the electrodes containing SnO2 were found to have retained approximately 73.0% of their original Pt, while only 53.2% was retained in electrodes treated identically, but without Sn. Similarly, the SnO2-treated electrodes also experienced a smaller loss in electrochemical surface area in comparison to before the accelerated stress test. A membrane electrode assembly (MEA) constructed with a SnO2-containing anode was evaluated over 500 h. The results showed remarkably reduced OCV decay rate and end of test hydrogen crossover compared to the control MEA, indicating that SnO2 aids in impeding membrane thinning and pinhole formation. The results point toward a positive effect of SnO2 on fuel cell durability, by reducing the degradation of the membrane as well as of the ionomer in the electrocatalyst layer.

Study directed at development of an implantable biotelemetry ion detector

NASA Technical Reports Server (NTRS)

Hanley, L. D.; Kress, D.

1971-01-01

A literature search was conducted to currently update known information in the field of ion-selective electrodes. The review attempts to identify present trends in cation and anions selective electrodes pertinent to the area of bioimplantable units. An electronic circuit was designed to provide the high impedance interface between the ion-selective sensors and signal-processing equipment. The resulting design emphasized the need for low power and miniaturization. Many of the circuits were constructed and used to evaluate the ion-selective electrodes. A cuvette capable of holding the ion-selective and the reference electrodes was designed and constructed. This equipment was used to evaluate commercially available ion-selective electrodes and the electrodes designed and constructed in the study. The results of the electrode tests are included.

Fabrication Methods for Adaptive Deformable Mirrors

NASA Technical Reports Server (NTRS)

Toda, Risaku; White, Victor E.; Manohara, Harish; Patterson, Keith D.; Yamamoto, Namiko; Gdoutos, Eleftherios; Steeves, John B.; Daraio, Chiara; Pellegrino, Sergio

2013-01-01

Previously, it was difficult to fabricate deformable mirrors made by piezoelectric actuators. This is because numerous actuators need to be precisely assembled to control the surface shape of the mirror. Two approaches have been developed. Both approaches begin by depositing a stack of piezoelectric films and electrodes over a silicon wafer substrate. In the first approach, the silicon wafer is removed initially by plasmabased reactive ion etching (RIE), and non-plasma dry etching with xenon difluoride (XeF2). In the second approach, the actuator film stack is immersed in a liquid such as deionized water. The adhesion between the actuator film stack and the substrate is relatively weak. Simply by seeping liquid between the film and the substrate, the actuator film stack is gently released from the substrate. The deformable mirror contains multiple piezoelectric membrane layers as well as multiple electrode layers (some are patterned and some are unpatterned). At the piezolectric layer, polyvinylidene fluoride (PVDF), or its co-polymer, poly(vinylidene fluoride trifluoroethylene P(VDF-TrFE) is used. The surface of the mirror is coated with a reflective coating. The actuator film stack is fabricated on silicon, or silicon on insulator (SOI) substrate, by repeatedly spin-coating the PVDF or P(VDFTrFE) solution and patterned metal (electrode) deposition. In the first approach, the actuator film stack is prepared on SOI substrate. Then, the thick silicon (typically 500-micron thick and called handle silicon) of the SOI wafer is etched by a deep reactive ion etching process tool (SF6-based plasma etching). This deep RIE stops at the middle SiO2 layer. The middle SiO2 layer is etched by either HF-based wet etching or dry plasma etch. The thin silicon layer (generally called a device layer) of SOI is removed by XeF2 dry etch. This XeF2 etch is very gentle and extremely selective, so the released mirror membrane is not damaged. It is possible to replace SOI with silicon substrate, but this will require tighter DRIE process control as well as generally longer and less efficient XeF2 etch. In the second approach, the actuator film stack is first constructed on a silicon wafer. It helps to use a polyimide intermediate layer such as Kapton because the adhesion between the polyimide and silicon is generally weak. A mirror mount ring is attached by using adhesive. Then, the assembly is partially submerged in liquid water. The water tends to seep between the actuator film stack and silicon substrate. As a result, the actuator membrane can be gently released from the silicon substrate. The actuator membrane is very flat because it is fixed to the mirror mount prior to the release. Deformable mirrors require extremely good surface optical quality. In the technology described here, the deformable mirror is fabricated on pristine substrates such as prime-grade silicon wafers. The deformable mirror is released by selectively removing the substrate. Therefore, the released deformable mirror surface replicates the optical quality of the underlying pristine substrate.

Introduction to polymer-based solid-contact ion-selective electrodes-basic concepts, practical considerations, and current research topics.

PubMed

Bieg, Christoph; Fuchsberger, Kai; Stelzle, Martin

2017-01-01

This review aims at providing an introductory overview for researchers new to the field of ion-selective electrodes. Both state of the art technology and novel developments towards solid-contact reference (sc-RE) and solid-contact ion selective electrodes (sc-ISE) are discussed. This technology has potentially widespread and important applications provided certain performance criteria can be met. We present basic concepts, operation principles, and theoretical considerations with regard to their function. Analytical performance and suitability of sc-RE and sc-ISE for a given application depend on critical parameters, which are discussed in this review. Comprehensive evaluation of sensor performance along this set of parameters is considered indispensable to allow for a well-founded comparison of different technologies. Methods and materials employed in the construction of sc-RE and sc-ISE, in particular the solid contact and the polymer membrane composite, are presented and discussed in detail. Operation principles beyond potentiometry are mentioned, which would further extend the field of ISE application. Finally, we conclude by directing the reader to important areas for further scientific research and development work considered particularly critical and promising for advancing this field in sensor R&D. Graphical Abstract ᅟ.

Miniature Bipolar Electrostatic Ion Thruster

NASA Technical Reports Server (NTRS)

Hartley, Frank T.

2006-01-01

The figure presents a concept of a bipolar miniature electrostatic ion thruster for maneuvering a small spacecraft. The ionization device in the proposed thruster would be a 0.1-micron-thick dielectric membrane with metal electrodes on both sides. Small conical holes would be micromachined through the membrane and electrodes. An electric potential of the order of a volt applied between the membrane electrodes would give rise to an electric field of the order of several mega-volts per meter in the submicron gap between the electrodes. An electric field of this magnitude would be sufficient to ionize all the molecules that enter the holes. In a thruster-based on this concept, one or more propellant gases would be introduced into such a membrane ionizer. Unlike in larger prior ion thrusters, all of the propellant molecules would be ionized. This thruster would be capable of bipolar operation. There would be two accelerator grids - one located forward and one located aft of the membrane ionizer. In one mode of operation, which one could denote the forward mode, positive ions leaving the ionizer on the backside would be accelerated to high momentum by an electric field between the ionizer and an accelerator grid. Electrons leaving the ionizer on the front side would be ejected into free space by a smaller accelerating field. The equality of the ion and electron currents would eliminate the need for an additional electron- or ion-emitting device to keep the spacecraft charge-neutral. In another mode of operation, which could denote the reverse mode, the polarities of the voltages applied to the accelerator grids and to the electrodes of the membrane ionizer would be the reverse of those of the forward mode. The reversal of electric fields would cause the ion and electrons to be ejected in the reverse of their forward mode directions, thereby giving rise to thrust in the direction opposite that of the forward mode.

Microstructure of room temperature ionic liquids at stepped graphite electrodes

DOE PAGES

Feng, Guang; Li, Song; Zhao, Wei; ...

2015-07-14

Molecular dynamics simulations of room temperature ionic liquid (RTIL) [emim][TFSI] at stepped graphite electrodes were performed to investigate the influence of the thickness of the electrode surface step on the microstructure of interfacial RTILs. A strong correlation was observed between the interfacial RTIL structure and the step thickness in electrode surface as well as the ion size. Specifically, when the step thickness is commensurate with ion size, the interfacial layering of cation/anion is more evident; whereas, the layering tends to be less defined when the step thickness is close to the half of ion size. Furthermore, two-dimensional microstructure of ionmore » layers exhibits different patterns and alignments of counter-ion/co-ion lattice at neutral and charged electrodes. As the cation/anion layering could impose considerable effects on ion diffusion, the detailed information of interfacial RTILs at stepped graphite presented here would help to understand the molecular mechanism of RTIL-electrode interfaces in supercapacitors.« less

Coated-Wire Ion Selective Electrodes and Their Application to the Teaching Laboratory.

ERIC Educational Resources Information Center

Martin, Charles R.; Freiser, Henry

1980-01-01

Describes the procedures for construction of a nitrate coated-wire ion selective electrode and suggests experiments for evaluation of electrode response and illustration of typical analytical applications of ion selective electrodes. (CS)

Mechanically Tunable, Readily Processable Ion Gels by Self-Assembly of Block Copolymers in Ionic Liquids.

PubMed

Lodge, Timothy P; Ueki, Takeshi

2016-01-01

Room temperature ionic liquids are of great interest for many advanced applications, due to the combination of attractive physical properties with essentially unlimited tunability of chemical structure. High chemical and thermal stability, favorable ionic conductivity, and complete nonvolatility are just some of the most important physical characteristics that make ionic liquids promising candidates for emerging technologies. Examples include separation membranes, actuators, polymer gel electrolytes, supercapacitors, ion batteries, fuel cell membranes, sensors, printable plastic electronics, and flexible displays. However, in these and other applications, it is essential to solidify the ionic liquid, while retaining the liquid state properties of interest. A broadly applicable solidification strategy relies on gelation by addition of suitable triblock copolymers with the ABA architecture, producing ion gels or ionogels. In this paradigm, the A end blocks are immiscible with the ionic liquid, and consequently self-assemble into micellar cores, while some fraction of the well-solvated B midblocks bridge between micelles, forming a percolating network. The chemical structures of the A and B repeat units, the molar mass of the blocks, and the concentration of the copolymer in the ionic liquid are all independently tunable to attain desired property combinations. In particular, the modulus of the resulting ion gel can be readily varied between 100 Pa and 1 MPa, with little sacrifice of the transport properties of the ionic liquid, such as ionic conductivity or gas diffusivity. Suitable A blocks can impart thermoreversible gelation (with solidification either on heating or cooling) or even photoreversible gelation. By virtue of the nonvolatility of ionic liquids, a wide range of processing strategies can be employed directly to prepare ion gels in thin or thick film forms, including solvent casting, spin coating, aerosol jet printing, photopatterning, and transfer printing. For higher modulus ion gels it is even possible to employ a manual "cut and stick" strategy for easy device fabrication. Ion gels prepared from common triblock copolymers, for example, with A = polystyrene and B = poly(ethylene oxide) or poly(methyl methacrylate), in imidazolium based ionic liquids provide exceptional performance in membranes for separating CO 2 from N 2 or CH 4 . The same materials also are the best available gate dielectrics for printed plastic electronics, because their high capacitance endows organic transistors with milliamp output currents for sub-1 V applied bias, with switching speeds that can go well beyond 100 kHz, while being amenable to large area roll-to-roll printing. Incorporation of well-designed electroluminescent (e.g., Ru(bpy) 3 -based) or electrochromic (e.g., viologen-based) moieties into ion gels held between transparent electrodes yields flexible color displays operating with sub-1 V dc inputs.

Ion Fluxes in Giant Excised Cardiac Membrane Patches Detected and Quantified with Ion-selective Microelectrodes

PubMed Central

Kang, Tong Mook; Markin, Vladislav S.; Hilgemann, Donald W.

2003-01-01

We have used ion-selective electrodes (ISEs) to quantify ion fluxes across giant membrane patches by measuring and simulating ion gradients on both membrane sides. Experimental conditions are selected with low concentrations of the ions detected on the membrane side being monitored. For detection from the cytoplasmic (bath) side, the patch pipette is oscillated laterally in front of an ISE. For detection on the extracellular (pipette) side, ISEs are fabricated from flexible quartz capillary tubing (tip diameters, 2–3 microns), and an ISE is positioned carefully within the patch pipette with the tip at a controlled distance from the mouth of the patch pipette. Transport activity is then manipulated by solution changes on the cytoplasmic side. Ion fluxes can be quantified by simulating the ion gradients with appropriate diffusion models. For extracellular (intrapatch pipette) recordings, ion diffusion coefficients can be determined from the time courses of concentration changes. The sensitivity and utility of the methods are demonstrated with cardiac membrane patches by measuring (a) potassium fluxes via ion channels, valinomycin, and Na/K pumps; (b) calcium fluxes mediated by Na/Ca exchangers; (c) sodium fluxes mediated by gramicidin and Na/K pumps; and (d) proton fluxes mediated by an unknown electrogenic mechanism. The potassium flux-to-current ratio for the Na/K pump is approximately twice that determined for potassium channels and valinomycin, as expected for a 3Na/2K pump stoichiometery (i.e., 2K/charge moved). For valinomycin-mediated potassium currents and gramicidin-mediated sodium currents, the ion fluxes calculated from diffusion models are typically 10–15% smaller than expected from the membrane currents. As presently implemented, the ISE methods allow reliable detection of calcium and proton fluxes equivalent to monovalent cation currents <1 pA in magnitude, and they allow detection of sodium and potassium fluxes equivalent to <5 pA currents. The capability to monitor ion fluxes, independent of membrane currents, should facilitate studies of both electrogenic and electroneutral ion–coupled transporters in giant patches. PMID:12668735

Pulsed voltage electrospray ion source and method for preventing analyte electrolysis

DOEpatents

Kertesz, Vilmos [Knoxville, TN; Van Berkel, Gary [Clinton, TN

2011-12-27

An electrospray ion source and method of operation includes the application of pulsed voltage to prevent electrolysis of analytes with a low electrochemical potential. The electrospray ion source can include an emitter, a counter electrode, and a power supply. The emitter can include a liquid conduit, a primary working electrode having a liquid contacting surface, and a spray tip, where the liquid conduit and the working electrode are in liquid communication. The counter electrode can be proximate to, but separated from, the spray tip. The power system can supply voltage to the working electrode in the form of a pulse wave, where the pulse wave oscillates between at least an energized voltage and a relaxation voltage. The relaxation duration of the relaxation voltage can range from 1 millisecond to 35 milliseconds. The pulse duration of the energized voltage can be less than 1 millisecond and the frequency of the pulse wave can range from 30 to 800 Hz.

An accurate and stable nitrate-selective electrode for the in situ determination of nitrate in agricultural drainage waters.

PubMed

Le Goff, Thierry; Braven, Jim; Ebdon, Les; Chilcottt, Neil P; Scholefield, David; Wood, John W

2002-04-01

A field evaluation of a novel nitrate-ion selective electrode (ISE) was undertaken by continuous immersion over a period of 5 months in agricultural drainage weirs. The nitrate sensor N,N,N-triallyl leucine betaine was covalently attached to polystyrene-block-polybutadiene-block-polystyrene (SBS) using a free radical initiated co-polymerisation, to produce a rubbery membrane which was incorporated into a commercially available electrode body. A measurement unit was constructed comprising the nitrate-ISEs, a reference electrode and a temperature probe connected through a pre-amplifier to a data-logger and battery supply. A temperature correction algorithm was developed to accomodate the temperature changes encountered in the drainage weirs. The nitrate results obtained with the ISEs at hourly intervals compared very favourably (R2 = 0.99) with those obtained with laboratory automated chemical determinations made on contemporaneous samples of drainage in a concentration range 0.47-16 ppm nitrate-N. The ISEs did not require re-calibration and no deterioration in performance or fouling of the membrane surface was observed over four months of deployment.

A polymeric liquid membrane electrode responsive to 3,3',5,5'-tetramethylbenzidine oxidation for sensitive peroxidase/peroxidase mimetic-based potentiometric biosensing.

PubMed

Wang, Xuewei; Yang, Yangang; Li, Long; Sun, Mingshuang; Yin, Haogen; Qin, Wei

2014-05-06

The oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) has great utility in bioanalysis such as peroxidase/peroxidase mimetic-based biosensing. In this paper, the behaviors of TMB oxidation intermediates/products in liquid/liquid biphasic systems have been investigated for the first time. The free radical, charge transfer complex, and diimine species generated by TMB oxidation are all positively charged under acidic and near-neutral conditions. Electron paramagnetic resonance and visible absorbance spectroscopy data demonstrate that these cationic species can be effectively transferred from an aqueous phase into a water-immiscible liquid phase functionalized by an appropriate cation exchanger. Accordingly, sensitive potential responses of TMB oxidation have been obtained on a cation exchanger-doped polymeric liquid membrane electrode under mildly acidic and near-neutral conditions. By using the membrane electrode responsive to TMB oxidations, two sensitive potentiometric biosensing schemes including the peroxidase-labeled sandwich immunoassay and G-quadruplex DNAzyme-based DNA hybridization assay have been developed. The obtained detection limits for the target antigen and DNA are 0.02 ng/mL and 0.1 nM, respectively. Coupled with other advantages such as low cost, high reliability, and ease of miniaturization and integration, the proposed polymeric liquid membrane electrode holds great promise as a facile and efficient transducer for TMB oxidation and related biosensing applications.

Trifluorostyrene containing compounds, and their use in polymer electrolyte membranes

DOEpatents

Choudhury, Biswajit [Kingston, CA; Roelofs, Mark Gerrit [Hockessin, DE; Yang,; Zhen-Yu, [Hockessin, DE

2009-07-21

A fluorinated ion exchange polymer is prepared by grafting a monomer onto a base polymer, wherein the grafting monomer is selected from the group consisting of structure 1a, 1b and mixture thereof; ##STR00001## wherein Y is selected from the group consisting of --R.sub.FSO.sub.2F, --R.sub.FSO.sub.3M, --R.sub.SO.sub.2NH.sub.2 and --R.sub.FSO.sub.2N(M)SO.sub.2R.sup.2.sub.F, where in M is hydrogen, an alkali cation or ammonium; and R.sub.F and R.sup.2.sub.F are perfluorinated or partially fluorinated, and may optionally include ether oxygens; and n is between 1 and 2 for 1a, or n is between 1 and 3 for 1b. These ion exchange polymers are useful is preparing catalyst coated membranes and membrane electrode assemblies for fuel cells.

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

ISE-based sensor array system for classification of foodstuffs

NASA Astrophysics Data System (ADS)

Ciosek, Patrycja; Sobanski, Tomasz; Augustyniak, Ewa; Wróblewski, Wojciech

2006-01-01

A system composed of an array of polymeric membrane ion-selective electrodes and a pattern recognition block—a so-called 'electronic tongue'—was used for the classification of liquid samples: milk, fruit juice and tonic. The task of this system was to automatically recognize a brand of the product. To analyze the measurement set-up responses various non-parametric classifiers such as k-nearest neighbours, a feedforward neural network and a probabilistic neural network were used. In order to enhance the classification ability of the system, standard model solutions of salts were measured (in order to take into account any variation in time of the working parameters of the sensors). This system was capable of recognizing the brand of the products with accuracy ranging from 68% to 100% (in the case of the best classifier).

Design of a Selective and Sensitive PVC-Membrane Potentiometric Sensor for Strontium Ion Based on 1,10-Diaza-5,6-benzo-4,7-dioxacyclohexadecane-2,9-dione as a Neutral Ionophore

PubMed Central

Shamsipur, Mojtaba; Kazemi, Sayed Yahya; Sharghi, Hashem

2007-01-01

A novel PVC membrane sensor for the Sr2+ ion based on 1,10-diaza-5,6-benzo-4,7-dioxacyclohexadecane-2,9-dione has been prepared. The sensor possesses a Nernstian slope of 30.0 ± 0.6 mV decade-1 over a wide linear concentration range of 1.6 × 10-6-3.0 ×10-3 M with a detection limit of 6.3 ×10-7 M. It has a fast response time of <15 s and can be used for at least two months without any considerable divergence in potential. The potentiometric response is independent of the pH of test solution in the pH range 4.3-9.4. The proposed electrode shows good selectivities over a variety of alkali, alkaline earth, and transition metal ions.

Versatile Miniature Tunable Liquid Lenses Using Transparent Graphene Electrodes.

PubMed

Shahini, Ali; Xia, Jinjun; Zhou, Zhixian; Zhao, Yang; Cheng, Mark Ming-Cheng

2016-02-16

This paper presents, for the first time, versatile and low-cost miniature liquid lenses with graphene as electrodes. Tunable focal length is achieved by changing the droplet curvature using electrowetting on dielectric (EWOD). Ionic liquid and KCl solution are utilized as lens liquid on the top of a flexible Teflon-coated PDMS/parylene membrane. Transparent and flexible, graphene allows transmission of visible light as well as large deformation of the polymer membrane to achieve requirements for different lens designs and to increase the field of view without damaging of electrodes. The tunable range for the focal length is between 3 and 7 mm for a droplet with a volume of 3 μL. The visualization of bone marrow dendritic cells is demonstrated by the liquid lens system with a high resolution (456 lp/mm).

An all-solid-state reference electrode based on the layer-by-layer polymer coating.

PubMed

Kwon, Nak-Hyun; Lee, Kyung-Sun; Won, Mi-Sook; Shim, Yoon-Bo

2007-09-01

A solid-state reference electrode (SSRE) was fabricated by layering a silicone rubber (SR) film containing KCl on an AgCl surface, then a perfluorinated ionomer film, and finally a polyurethane-based membrane containing an ionophore, a lipophilic ionic additive, and a plasticizer, respectively. The addition of SiCl4 to the polyurethane-based membrane layer enhanced the strength of the membrane in an aqueous solution. The morphologies of the membranes were studied separately by SEM. The fabrication of the Ag/AgCl electrode through this layer-by-layer polymer coating improved the electrode stability enormously. In addition, the potential drift of the SSRE according to the pH of the medium was minimized by introducing a H+-ion-selective ionophore (tridodecylamine; TDDA) into the outmost polymer membrane. The cyclic voltammetric and potentiometric responses using the SSRE and a conventional reference electrode, respectively, were consistent. The SSRE exhibited little potential variation even in the case of the addition of very high concentrations of various salts, such as Na salicylate, LiCl, KCl, CaCl2, MgCl2, KNO3, NaCl, and NaHCO3. The practicability of the proposed SSRE was tested for the determination of blood pH and pCO2 in a flow cell system. The SSRE fabricated in the present study was stable over two years.

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.

Semi-solid electrodes having high rate capability

DOEpatents

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

2016-07-05

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

Semi-solid electrodes having high rate capability

DOEpatents

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

2015-11-10

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

Development of large-surface Nafion-metal composite actuator and its electrochemical characterization

NASA Astrophysics Data System (ADS)

Noh, Taegeun; Tak, Yong Suk; Nam, Jaedo; Jeon, Jaewook; Kim, Hunmo; Choi, Hyoukryeol; Bae, Sang Sik

2001-07-01

Behaviors of nafion-based actuators are significantly affected by interfacial area between electrode and polymer electrolyte. Replication method was utilized to manufacture a large surface-area composite actuator. Etched aluminum foil was used as a template for replication using liquid nafion solution. Measurement of double layer charging and scanning electron microscopy indicated that interfacial area was greatly increased by replication method. Higher surface area induced a better bending performance of ionic polymer metal composite (IPMC). In parallel, the effect of cations on IPMC was interpreted with constant current experiment, linear sweep voltammetry and electrochemical impedance spectroscopy. For univalent cations, ion size is the most influencing parameter on ionic mobility inside membrane. However, ion-ion interaction affects an ionic mobility for divalent cations.

Free-Standing Bilayered Nanoparticle Superlattice Nanosheets with Asymmetric Ionic Transport Behaviors.

PubMed

Rao, Siyuan; Si, Kae Jye; Yap, Lim Wei; Xiang, Yan; Cheng, Wenlong

2015-11-24

Natural cell membranes can directionally and selectively regulate the ion transport, which is critical for the functioning of living cells. Here, we report on the fabrication of an artificial membrane based on an asymmetric nanoparticle superlattice bilayered nanosheet, which exhibits similar ion transport characteristics. The superlattice nanosheets were fabricated via a drying-mediated self-assembly of polystyrene-capped gold nanoparticles at the liquid-air interface. By adopting a layer-by-layer assembly process, an asymmetric nanomembrane could be obtained consisting of two nanosheets with different nanoparticle size. The resulting nanomembranes exhibit an asymmetric ion transport behavior, and diode-like current-voltage curves were observed. The asymmetric ion transport is attributed to the cone-like nanochannels formed within the membranes, upon which a simulation map was established to illustrate the relationship between the channel structure and the ionic selectivity, in consistency with our experimental results. Our superlattice nanosheet-based design presents a promising strategy for the fabrication of next-generation smart nanomembranes for rationally and selectively regulating the ion transport even at a large ion flux, with potential applications in a wide range of fields, including biosensor devices, energy conversion, biophotonics, and bioelectronics.

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

Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus and methods

DOEpatents

Zaromb, Solomon

2001-01-01

Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity .gtoreq.10.sup.-4 (ohm-cm).sup.-1, and preferably .gtoreq.0.01 (ohm-cm).sup.-1. The conductivity may be due predominantly to Ag+ ions, as in Ag.sub.2 WO.sub.4.4AgI, or to F- ions, as in Ce.sub.0.95 Ca.sub.0.05 F.sub.2.95. Electrical contacts serve to connect the electrodes to potentiostating and detecting circuitry which controls the potential of the sensing electrode relative to the reference electrode, detects the signal generated by the sensor, and indicates the detected signal.

Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus

DOEpatents

Zaromb, Solomon

1994-01-01

Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity .gtoreq.10.sup.-4 (ohm-cm).sup.-1, and preferably .gtoreq.0.01 (ohm-cm).sup.-1. The conductivity may be due predominantly to Ag+ ions, as in Ag.sub.2 WO.sub.4.4AgI, or to F- ions, as in Ce.sub.0.95 Ca.sub.0.05 F.sub.2.95. Electrical contacts serve to connect the electrodes to potentiostating and detecting circuitry which controls the potential of the sensing electrode relative to the reference electrode, detects the signal generated by the sensor, and indicates the detected signal.

Performance of single chamber biocatalyzed electrolysis with different types of ion exchange membranes.

PubMed

Rozendal, René A; Hamelers, Hubertus V M; Molenkamp, Redmar J; Buisman, Cees J N

2007-05-01

In this paper hydrogen production through biocatalyzed electrolysis was studied for the first time in a single chamber configuration. Single chamber biocatalyzed electrolysis was tested in two configurations: (i) with a cation exchange membrane (CEM) and (ii) with an anion exchange membrane (AEM). Both configurations performed comparably and produced over 0.3 m3 H2/m3 reactor liquid volume/day at 1.0 V applied voltage (overall hydrogen efficiencies around 23%). Analysis of the water that permeated through the membrane revealed that a large part of potential losses in the system were associated with a pH gradient across the membrane (CEM DeltapH=6.4; AEM DeltapH=4.4). These pH gradient associated potential losses were lower in the AEM configuration (CEM 0.38 V; AEM 0.26 V) as a result of its alternative ion transport properties. This benefit of the AEM, however, was counteracted by the higher cathode overpotentials occurring in the AEM configuration (CEM 0.12 V at 2.39 A/m2; AEM 0.27 V at 2.15 A/m2) as a result of a less effective electroless plating method for the AEM membrane electrode assembly (MEA).

Microfabricated Patch Clamp Electrodes for Improved Ion Channel Protein Measurements

NASA Astrophysics Data System (ADS)

Klemic, James; Klemic, Kathryn; Reed, Mark; Sigworth, Frederick

2002-03-01

Ion channels are trans-membrane proteins that underlie many cell functions including hormone and neurotransmitter release, muscle contraction and cell signaling cascades. Ion channel proteins are commonly characterized via the patch clamp method in which an extruded glass tube containing ionic solution, manipulated by an expert technician, is brought into contact with a living cell to record ionic current through the cell membrane. Microfabricated planar patch electrodes, micromolded in the silicone elastomer poly-dimethylsiloxane (PDMS) from microlithographically patterned structures, have been developed that improve on this method. Microfabrication techniques allow arrays of patch electrodes to be fabricated, increasing the throughput of the measurement technique. Planar patch electrodes readily allow the automation of cell sealing, further increasing throughput. Microfabricated electrode arrays may be readily integrated with microfluidic structures to allow fast, in situ solution exchange. Miniaturization of the electrode geometry should increase both the signal to noise and the bandwidth of the measurement. Microfabricated patch electrode arrays have been fabricated and measurements have been taken.

Cast and 3D printed ion exchange membranes for monolithic microbial fuel cell fabrication

NASA Astrophysics Data System (ADS)

Philamore, Hemma; Rossiter, Jonathan; Walters, Peter; Winfield, Jonathan; Ieropoulos, Ioannis

2015-09-01

We present novel solutions to a key challenge in microbial fuel cell (MFC) technology; greater power density through increased relative surface area of the ion exchange membrane that separates the anode and cathode electrodes. The first use of a 3D printed polymer and a cast latex membrane are compared to a conventionally used cation exchange membrane. These new techniques significantly expand the geometric versatility available to ion exchange membranes in MFCs, which may be instrumental in answering challenges in the design of MFCs including miniaturisation, cost and ease of fabrication. Under electrical load conditions selected for optimal power transfer, peak power production (mean 10 batch feeds) was 11.39 μW (CEM), 10.51 μW (latex) and 0.92 μW (Tangoplus). Change in conductivity and pH of anolyte were correlated with MFC power production. Digital and environmental scanning electron microscopy show structural changes to and biological precipitation on membrane materials following long term use in an MFC. The cost of the novel membranes was lower than the conventional CEM. The efficacy of two novel membranes for ion exchange indicates that further characterisation of these materials and their fabrication techniques, shows great potential to significantly increase the range and type of MFCs that can be produced.

Organic non-aqueous cation-based redox flow batteries

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

Zhang, Lu; Huang, Jinhua; Burrell, Anthony

The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturatedmore » moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.« less

A novel sensor for monitoring of iron(III) ions based on porphyrins.

PubMed

Vlascici, Dana; Fagadar-Cosma, Eugenia; Popa, Iuliana; Chiriac, Vlad; Gil-Agusti, Mayte

2012-01-01

Three A(3)B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10(-7)-1 × 10(-1) M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples.

Preparation of polyacrylonitrile nanofibrous membrane for fabrication of separator of lithium ion batteries

NASA Astrophysics Data System (ADS)

Arifeen, W. U.; Dong, T.; Kurniawan, R.; Ko, T. J.

2018-03-01

In this paper, the manufacturing process and morphology of nano fibrous membranes are discussed. These membranes are explored as separators in rechargeable lithium ion batteries. The function of separator is to allow the flow of ions while protecting the physical contact between positive and negative electrode. Therefore, the porosity, mechanical strength and thermal stability of separators possess significant importance. The separators are manufactured by electrospinning process and later the morphology is studied with the help of scanning electron microscope (SEM) images. The separator is prepared by polyacrylonitrile (PAN) and then exposed to the hot plate. The uniform, continuous and dense nano fibrous membrane is prepared with the help of electrospinning process providing the prevention of physical contact between electrode and stable enough to work in high temperatures leading to high performance lithium ion batteries separators.

Internal gas and liquid distributor for electrodeionization device

DOEpatents

Lin, YuPo J.; Snyder, Seth W.; Henry, Michael P.; Datta, Saurav

2016-05-17

The present invention provides a resin-wafer electrodeionization (RW-EDI) apparatus including cathode and anode electrodes separated by a plurality of porous solid ion exchange resin wafers, which when in use are filled with an aqueous fluid. The apparatus includes one or more wafers comprising a basic ion exchange medium, and preferably includes one or more wafers comprising an acidic ion exchange medium. The wafers are separated from one another by ion exchange membranes. The gas and aqueous fluid are introduced into each basic wafer via a porous gas distributor which disperses the gas as micro-sized bubbles laterally throughout the distributor before entering the wafer. The fluid within the acidic and/or basic ion exchange wafers preferably includes, or is in contact with, a carbonic anhydrase (CA) enzyme or inorganic catalyst to facilitate conversion of bicarbonate ion to carbon dioxide within the acidic medium.

Investigating microstructural evolution during the electroreduction of UO2 to U in LiCl-KCl eutectic using focused ion beam tomography

NASA Astrophysics Data System (ADS)

Brown, L. D.; Abdulaziz, R.; Tjaden, B.; Inman, D.; Brett, D. J. L.; Shearing, P. R.

2016-11-01

Reprocessing of spent nuclear fuels using molten salt media is an attractive alternative to liquid-liquid extraction techniques. Pyroelectrochemical processing utilizes direct, selective, electrochemical reduction of uranium dioxide, followed by selective electroplating of a uranium metal. Thermodynamic prediction of the electrochemical reduction of UO2 to U in LiCl-KCl eutectic has shown to be a function of the oxide ion activity. The pO2- of the salt may be affected by the microstructure of the UO2 electrode. A uranium dioxide filled "micro-bucket" electrode has been partially electroreduced to uranium metal in molten lithium chloride-potassium chloride eutectic. This partial electroreduction resulted in two distinct microstructures: a dense UO2 and a porous U metal structure were characterised by energy dispersive X-ray spectroscopy. Focused ion beam tomography was performed on five regions of this electrode which revealed an overall porosity ranging from 17.36% at the outer edge to 3.91% towards the centre, commensurate with the expected extent of reaction in each location. The pore connectivity was also seen to reduce from 88.32% to 17.86% in the same regions and the tortuosity through the sample was modelled along the axis of propagation of the electroreduction, which was seen to increase from a value of 4.42 to a value of infinity (disconnected pores). These microstructural characteristics could impede the transport of O2- ions resulting in a change in the local pO2- which could result in the inability to perform the electroreduction.

Automatic Gain Control in Mass Spectrometry using a Jet Disrupter Electrode in an Electrodynamic Ion Funnel

PubMed Central

Page, Jason S.; Bogdanov, Bogdan; Vilkov, Andrey N.; Prior, David C.; Buschbach, Michael A.; Tang, Keqi; Smith, Richard D.

2007-01-01

We report on the use of a jet disrupter electrode in an electrodynamic ion funnel as an electronic valve to regulate the intensity of the ion beam transmitted through the interface of a mass spectrometer in order to perform automatic gain control (AGC). The ion flux is determined by either directly detecting the ion current on the conductance limiting orifice of the ion funnel or using a short mass spectrometry acquisition. Based upon the ion flux intensity, the voltage of the jet disrupter is adjusted to alter the transmission efficiency of the ion funnel to provide a desired ion population to the mass analyzer. Ion beam regulation by an ion funnel is shown to provide control to within a few percent of a targeted ion intensity or abundance. The utility of ion funnel AGC was evaluated using a protein tryptic digest analyzed with liquid chromatography Fourier transform ion cyclotron resonance (LC-FTICR) mass spectrometry. The ion population in the ICR cell was accurately controlled to selected levels, which improved data quality and provided better mass measurement accuracy. PMID:15694774

In Situ Probing of Ion Ordering at an Electrified Ionic Liquid/Au Interface

DOE PAGES

Sitaputra, Wattaka; Stacchiola, Dario; Wishart, James F.; ...

2017-05-12

Charge transport at the interface of electrodes and ionic liquids is critical for the use of the latter as electrolytes. In this study, a room-temperature ionic liquid, 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (EMMIM TFSI), is investigated in situ under applied bias voltage with a novel method using low-energy electron and photoemission electron microscopy. Changes in photoelectron yield as a function of bias applied to electrodes provide a direct measure of the dynamics of ion reconfiguration and electrostatic responses of the EMMIM TFSI. Finally, long-range and correlated ionic reconfigurations that occur near the electrodes are found to be a function of temperature and thickness,more » which, in turn, relate to ionic mobility and different configurations for out-of-plane ordering near the electrode interfaces, with a critical transition in ion mobility for films thicker than three monolayers.« less

Cycling Performance of the Iron-Chromium Redox Energy Storage System

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N. H.; Johnson, J. A.

1985-01-01

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Cycling performance of the iron-chromium redox energy storage system

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N. H.; Johnson, J. A.

1985-01-01

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Selective recovery of salt from coal gasification brine by nanofiltration membranes.

PubMed

Li, Kun; Ma, Wencheng; Han, Hongjun; Xu, Chunyan; Han, Yuxing; Wang, Dexin; Ma, Weiwei; Zhu, Hao

2018-06-20

The selective extraction and concentration of salt from coal gasification brine (CGB) by nanofiltration membranes is a promising technology to achieve near-zero liquid discharge of coal gasification wastewater. To investigate the feasibility of recovery of salts and the interaction of organic compounds, multivalent ions and monovalent ions on the rejection ratio, three nanofiltration membranes (OWNF1, NF270 and Desal-5 DK) with an 1812 spiral-wound module were used in crossflow filtration. The rejection mechanism was analyzed by comparing the rejection performance as a function of the operation pressure (increasing from 1.0 MPa to 2.5 MPa), the concentration (increasing from 10,000 mg/L to 25,000 mg/L) and pH values (increasing from 3.0 to 10.0). The concentrations of anions and cations were determined using an ion chromatographic analyzer and an inductively coupled plasma emission spectrometer, respectively. The results show that the rejection of sulfate and the chemical oxygen demand were higher than 92.12% and 78.84%, respectively, at appropriate operation, while negative rejection of chloride was observed in the CGB. The decreasing rejection of organic compounds was due to swelling of the membrane pore in high-concentration solutions. Meanwhile, the organic compounds weakened the negative charge of the membrane active layer, consequently decreasing the ion rejection. More than 85% of the sodium chloride could be recovered, indicating that this technology is suitable for resource recovery from CGB and near-zero liquid discharge of coal gasification industry. Copyright © 2018 Elsevier Ltd. All rights reserved.

MEMBRANE POTENTIAL OF THE SQUID GIANT AXON DURING CURRENT FLOW

PubMed Central

Cole, Kenneth S.; Curtis, Howard J.

1941-01-01

The squid giant axon was placed in a shallow narrow trough and current was sent in at two electrodes in opposite sides of the trough and out at a third electrode several centimeters away. The potential difference across the membrane was measured between an inside fine capillary electrode with its tip in the axoplasm between the pair of polarizing electrodes, and an outside capillary electrode with its tip flush with the surface of one polarizing electrode. The initial transient was roughly exponential at the anode make and damped oscillatory at the sub-threshold cathode make with the action potential arising from the first maximum when threshold was reached. The constant change of membrane potential, after the initial transient, was measured as a function of the total polarizing current and from these data the membrane potential is obtained as a function of the membrane current density. The absolute value of the resting membrane resistance approached at low polarizing currents is about 23 ohm cm.2. This low value is considered to be a result of the puncture of the axon. The membrane was found to be an excellent rectifier with a ratio of about one hundred between the high resistance at the anode and the low resistance at the cathode for the current range investigated. On the assumption that the membrane conductance is a measure of its ion permeability, these experiments show an increase of ion permeability under a cathode and a decrease under an anode. PMID:19873234

An Easily Constructed Salicylate-Ion-Selective Electrode for Use in the Instructional Laboratory.

ERIC Educational Resources Information Center

Creager, Stephen E.; And Others

1995-01-01

Describes an electrode, selective for the salicylate ion, that can be prepared and used by undergraduate students. Discusses the preparation of the electrode, typical response characteristics obtained, and results of a limited study using the electrode to estimate the selectivity coefficient for an interfering ion and to determine the amount of…

Dissolution testing and potentiometric determination of famciclovir in pure, dosage forms and biological fluids.

PubMed

Rezk, Mohamed S; El Nashar, Rasha M

2013-02-01

The performance characteristics of two new plastic membrane ion selective electrodes (ISEs) used for the determination of famciclovir (Fcv) based on the ion associate of Fcv with phosphotungstic acid (PTA) or phosphomolybdic acid (PMA) are described. Different experimental conditions as type of plasticizer to be incorporated in the membrane, life span, effect of soaking, pH, temperature, and interferences were studied. Both electrodes showed similar performance under these conditions, exhibiting Nernstian slopes of S (Fcv-PTA)=58.60±0.84 mV/decade and S (Fcv-PMA)=58.77±0.68 mV/decade within a usable concentration range of 10⁻⁵-10⁻² [Fcv/M] at 298/K. Famciclovir was assayed potentiometrically in its pure solution, pharmaceutical preparations and biological fluids (urine and plasma) using proposed electrodes under batch and flow injection analysis (FIA) conditions with a recovery % ranging between 96.76% and 102.83% having RSD of 0.66%-1.81%. The electrodes were also successfully applied in the determination of the dissolution profile of Fcv tablets and the results came in agreement with the validated results of the HPLC method obtained from the quality control unit of the company producing the tablets. Copyright © 2012 Elsevier B.V. All rights reserved.

Relation between the ion size and pore size for an electric double-layer capacitor.

PubMed

Largeot, Celine; Portet, Cristelle; Chmiola, John; Taberna, Pierre-Louis; Gogotsi, Yury; Simon, Patrice

2008-03-05

The research on electrochemical double layer capacitors (EDLC), also known as supercapacitors or ultracapacitors, is quickly expanding because their power delivery performance fills the gap between dielectric capacitors and traditional batteries. However, many fundamental questions, such as the relations between the pore size of carbon electrodes, ion size of the electrolyte, and the capacitance have not yet been fully answered. We show that the pore size leading to the maximum double-layer capacitance of a TiC-derived carbon electrode in a solvent-free ethyl-methylimmidazolium-bis(trifluoro-methane-sulfonyl)imide (EMI-TFSI) ionic liquid is roughly equal to the ion size (approximately 0.7 nm). The capacitance values of TiC-CDC produced at 500 degrees C are more than 160 F/g and 85 F/cm(3) at 60 degrees C, while standard activated carbons with larger pores and a broader pore size distribution present capacitance values lower than 100 F/g and 50 F/cm(3) in ionic liquids. A significant drop in capacitance has been observed in pores that were larger or smaller than the ion size by just an angstrom, suggesting that the pore size must be tuned with sub-angstrom accuracy when selecting a carbon/ion couple. This work suggests a general approach to EDLC design leading to the maximum energy density, which has been now proved for both solvated organic salts and solvent-free liquid electrolytes.

Organoboron compounds as Lewis acid receptors of fluoride ions in polymeric membranes.

PubMed

Jańczyk, Martyna; Adamczyk-Woźniak, Agnieszka; Sporzyński, Andrzej; Wróblewski, Wojciech

2012-07-06

Newly synthesized organoboron compounds - 4-octyloxyphenylboronic acid (OPBA) and pinacol ester of 2,4,6-trifluorophenylboronic acid (PE-PBA) - were applied as Lewis acid receptors of fluoride anions. Despite enhanced selectivity, the polymer membrane electrodes containing the lipophilic receptor OPBA exhibited non-Nernstian slopes of the responses toward fluoride ions in acidic conditions. Such behavior was explained by the lability of the B-O bond in the boronic acids, and the OH(-)/F(-) exchange at higher fluoride content in the sample solution. In consequence, the stoichiometry of the OPBA-fluoride complexes in the membrane could vary during the calibration, changing the equilibrium concentration of the primary anion in membrane and providing super-Nernstian responses. The proposed mechanism was supported by (19)F NMR studies, which indicated that the fluoride complexation proceeds more effectively in acidic solution leading mainly to PhBF(3)(-) species. Finally, the performances of the membranes based on the phenylboronic acid pinacol ester, with a more stable B-O bond, were tested. As it was expected, Nernstian fluoride responses were recorded for such membranes with worsened fluoride selectivity. Copyright © 2012 Elsevier B.V. All rights reserved.

Immobilization of ionophore and surface characterization studies of the titanium(III) ion in a PVC-membrane sensor.

PubMed

Rezayi, Majid; Heng, Lee Yook; Kassim, Anuar; Ahmadzadeh, Saeid; Abdollahi, Yadollah; Jahangirian, Hossein

2012-01-01

Novel ionophores comprising various hydroxide and amine structures were immobilized onto poly(vinyl chloride) (PVC) matrices, and these were examined to determine Ti(III) selectivity. To predict the selectivity of Ti(III), a PVC membrane was used to investigate the binding of Ti(III) to c-methylcalix[4]resorcinarene (CMCR). The study showed that the chelating ligand, CMCR, was coordinated selectively to Ti(III) at eight coordination sites involving the oxygen atoms at the interface of the membrane/solution. The membrane was prepared, based on CMCR as an ionophore, sodium tetrakis(4-fluorophenyl) borate (NaTFPB) as a lipophilic ionic additive, and dioctylphthalate (DOP) as a plasticizer. The immobilization of the ionophore and surface characterization studies revealed that the performance of CMCR-immobilized PVC was equivalent to that of mobile ionophores in supported liquid membranes (SLMs). The strengths of the ion-ionophore (CMCR-Ti(OH)(OH(2))(5) (2+)) interactions and the role of ionophores on membranes were studied via UV-Vis, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and and X-ray diffraction (XRD).

Recycling positive-electrode material of a lithium-ion battery

DOEpatents

Sloop, Steven E.

2017-11-21

Examples are disclosed of methods to recycle positive-electrode material of a lithium-ion battery. In one example, the positive-electrode material is heated under pressure in a concentrated lithium hydroxide solution. After heating, the positive-electrode material is separated from the concentrated lithium hydroxide solution. After separating, the positive electrode material is rinsed in a basic liquid. After rinsing, the positive-electrode material is dried and sintered.

Design and fabrication of nanoelectrodes for applications with scanning electrochemical microscopy

NASA Astrophysics Data System (ADS)

Thakar, Rahul

Scanning electrochemical microscope (SECM) was introduced two decades ago and has since emerged as a powerful research tool to investigate localized electrochemical reactions at the surface of material and biological samples. The ability to obtain chemical information at a surface differentiates SECM from competing scanning probe microscopy (SPM) techniques. Although, chemical specificity is a unique advantage offered by SECM, inherent limitations due to a slow feedback response, and challenges associated with production of smaller electrodes have remained major drawbacks. Initially in this research, SECM was utilized as a characterization and investigative tool. Later, advances in SECM imaging were achieved with design and production of multifunctional nanoelectrodes. At first, platinum based nanoelectrodes were fabricated for use as electrochemical probes to investigate local electron transfer at chemically-modified surfaces. Further, micron and sub-micron platinum electrodes with chemically modified shrouds were prepared and characterized with voltammetric measurements. Studies reveal experimental evidence for the presence of edge-effects that are typically associated with submicron electrodes. Interestingly, we observed selectivity of these electrodes based on hydrophobic/ hydrophilic character. Through vapor deposition of parylene over microstructured material, single-pore membranes and porous membrane arrays were produced. Pore size characterization within porous membranes was performed with templated growth of micro/nanostructures. Characterization of transport properties of ions and redox-active molecules through hydrophobic parylene membranes was investigated with ion conductance microscopy and SECM, individually. Parylene is an insulative material that is chemically resistant, deposits conformally over high-aspect ratio objects and also converts into conductive carbon at high-temperature pyrolysis. Motivated by these results we identified a unique strategy to fabricate parylene based carbon electrodes Here, we have developed a unique strategy to obtain carbon based nanoelectrodes from vapor deposition of parylene over pulled glass nanopipettes. With this approach, multiple electrode geometries were constructed and the application of individual geomtery with SECM is demonstrated. In particular, enhanced spatial resolution and electrochemical information were obtained with the use of carbon ring/nanopore electrodes. Practical implications of edge-effects observed with carbon ring/nanopore electrodes is discussed with substrate generation tip collection (SG/TC) SECM Carbon ring/nanopore electrodes have also enabled the use of SECM in conjunction with ion conductance microscopy to alleviate the issue of poor feedback response. This has further helped in deconvolution of electrochemcial and topographical signals. Although, use of carbon nanoelectrodes is discussed with specific applications to electrochemcial microscopy, these probes have wide utility in electroanalytical applications. Initial proof-of-concept experiments along with future directions for this work are presented.

Electrodeionization Using Microseparated Bipolar Membranes

NASA Technical Reports Server (NTRS)

Lyons, Donald; Jackson, George; Andrews, Craig C.; Tennakoon, Charles L, K.; Singh, Waheguru; Hitchens, G. Duncan; Jabs, Harry; Chepin, James F.; Archer, Shivaun; Gonzalez-Martinez, Anukia;

Conducting polymer ultracapacitor

DOEpatents

Shi, Steven Z.; Davey, John R.; Gottesfeld, Shimshon; Ren, Xiaoming

2002-01-01

A sealed ultracapacitor assembly is formed with first and second electrodes of first and second conducting polymers electrodeposited on porous carbon paper substrates, where the first and second electrodes each define first and second exterior surfaces and first and second opposing surfaces. First and second current collector plates are bonded to the first and second exterior surfaces, respectively. A porous membrane separates the first and second opposing surfaces, with a liquid electrolyte impregnating the insulating membrane. A gasket formed of a thermoplastic material surrounds the first and second electrodes and seals between the first and second current collector plates for containing the liquid electrolyte.

Measuring calcium, potassium, and nitrate in plant nutrient solutions using ion-selective electrodes in hydroponic greenhouse of some vegetables.

PubMed

Vardar, Gökay; Altıkatoğlu, Melda; Ortaç, Deniz; Cemek, Mustafa; Işıldak, İbrahim

2015-01-01

Generally, the life cycle of plants depends on the uptake of essential nutrients in a balanced manner and on toxic elements being under a certain concentration. Lack of control of nutrient levels in nutrient solution can result in reduced plant growth and undesired conditions such as blossom-end rot. In this study, sensitivity and selectivity tests for various polyvinylchloride (PVC)-based ion-selective membranes were conducted to identify those suitable for measuring typical concentration ranges of macronutrients, that is, NO(3-), K(+), and Ca(2+), in hydroponic solutions. The sensitivity and selectivity of PVC-membrane-based ion-selective sensors prepared with tetradodecylammoniumnitrate for NO(3-), valinomycin for K(+), and Ca ionophore IV for Ca(2+) were found to be satisfactory for measuring NO(3-), K(+), and Ca(2+) ions in nutrient solutions over typical ranges of hydroponic concentrations. Potassium, calcium, and nitrate levels that were utilized by cucumber and tomato seedlings in the greenhouse were different. The findings show that tomato plants consumed less amounts of nitrate than cucumber plants over the first 2 months of their growth. We also found that the potassium intake was higher than other nutritional elements tested for all plants. © 2014 International Union of Biochemistry and Molecular Biology, Inc.

Potentiometric detection of chemical vapors using molecularly imprinted polymers as receptors

PubMed Central

Liang, Rongning; Chen, Lusi; Qin, Wei

2015-01-01

Ion-selective electrode (ISE) based potentiometric gas sensors have shown to be promising analytical tools for detection of chemical vapors. However, such sensors are only capable of detecting those vapors which can be converted into ionic species in solution. This paper describes for the first time a polymer membrane ISE based potentiometric sensing system for sensitive and selective determination of neutral vapors in the gas phase. A molecularly imprinted polymer (MIP) is incorporated into the ISE membrane and used as the receptor for selective adsorption of the analyte vapor from the gas phase into the sensing membrane phase. An indicator ion with a structure similar to that of the vapor molecule is employed to indicate the change in the MIP binding sites in the membrane induced by the molecular recognition of the vapor. The toluene vapor is used as a model and benzoic acid is chosen as its indicator. Coupled to an apparatus manifold for preparation of vapor samples, the proposed ISE can be utilized to determine volatile toluene in the gas phase and allows potentiometric detection down to parts per million levels. This work demonstrates the possibility of developing a general sensing principle for detection of neutral vapors using ISEs. PMID:26215887

Measurement of intracellular chloride in guinea-pig vas deferens by ion analysis, 36chloride and micro-electrodes

PubMed Central

Aickin, C. Claire; Brading, Alison F.

1982-01-01

1. Cl-sensitive micro-electrodes were used to measure the intracellular Cl activity (aCli) in smooth muscle cells of the guinea-pig vas deferens. The values obtained were compared with those of intracellular Cl (Cli) found by both ion analysis and 36Cl efflux. 2. Various combinations of filling solution for recording membrane potential (Em), and type of micro-electrode were tested. The most successful, which allowed continuous recording of aCli for several hours, was a double-barrelled electrode using the reference liquid ion exchanger (RLIE; Thomas & Cohen, 1981). However, aCli measured both by simultaneous impalements of separate cells with Cl-sensitive and conventional micro-electrodes, and by double-barrelled micro-electrodes, was about 42 mM in normal Krebs solution. This is five times higher than the value from a passive distribution. ECl was about -24 mV, more than 40 mV positive to Em. 3. On complete removal of extracellular Cl (Clo), aCli fell to an apparent level of about 3 mM. If this represents interference from other anions, the maximum error in ECl measured in normal Krebs solution is 2·5 mV. Replacement of Clo caused a rapid increase in aCli. This must be caused by an active transport of Cl- ions into the cell against their electrochemical gradient. 4. The stabilized values of aCli measured at different levels of Clo agree surprisingly well with aCli estimated from ion analysis and 36Cl efflux, assuming that the intracellular activity coefficient was the same as measured in the normal Krebs solution. The relationship of aCli to Clo was hyperbolic. 5. It is concluded that Cl-sensitive micro-electrodes accurately measure aCli in smooth muscle cells. The remarkable agreement between the direct and indirect methods of measuring Cli suggests that Cl- ions are not bound to a significant extent and that the compartment seen by the micro-electrodes is probably representative of the whole cell. PMID:7108787

Coupling fiber optics to a permeation liquid membrane for heavy metal sensor development.

PubMed

Ueberfeld, Jörn; Parthasarathy, Nalini; Zbinden, Hugo; Gisin, Nicolas; Buffle, Jacques

2002-02-01

We present the first sensing system for metal ions based on the combination of separation/preconcentration by a permeation liquid membrane (PLM) and fluorescence detection with an optical fiber. As a model, a system for the detection of Cu(II) ions was developed. The wall of a polypropylene hollow fiber serves as support for the permeable liquid membrane. The lumen of the fiber contains the strip solution in which Cu(II) is accumulated. Calcein, a fluorochromic dye, acts as stripping agent and at the same time as metal indicator. The quenching of the calcein fluorescence upon metal accumulation in the strip phase is detected with a multimode optical fiber, which is incorporated into the lumen. Fluorescence is excited with a blue LED and detected with a photon counter. Taking advantage of the high selectivity and sensitivity of PLM preconcentration, a detection limit for Cu(II) of approximately 50 nM was achieved. Among five tested heavy metal ions, Pb(II) was the only major interfering species. The incorporation of small silica optical fibers into the polypropylene capillary allows for real-time monitoring of the Cu(II) accumulation process.

Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes

DOE PAGES

Dyatkin, Boris; Mamontov, Eugene; Cook, Kevin M.; ...

2015-12-24

Our study analyzed the dynamics of ionic liquid electrolyte inside of defunctionalized, hydrogenated, and aminated pores of carbide-derived carbon supercapacitor electrodes. The approach tailors surface functionalities and tunes nanoporous structures to decouple the influence of pore wall composition on capacitance, ionic resistance, and long-term cyclability. Moreover, quasi-elastic neutron scattering probes the self-diffusion properties and electrode-ion interactions of electrolyte molecules confined in functionalized pores. Room-temperature ionic liquid interactions in confined pores are strongest when the hydrogen-containing groups are present on the surface. This property translates into higher capacitance and greater ion transport through pores during electrochemical cycling. Aminated pores, unlike hydrogenatedmore » pores, do not favorably interact with ionic liquid ions and, subsequently, are outperformed by defunctionalized surfaces.« less

Positive electrode current collector for liquid metal cells

DOEpatents

Shimotake, Hiroshi; Bartholme, Louis G.

1984-01-01

A current collector for the positive electrode of an electrochemical cell with a positive electrode including a sulfide. The cell also has a negative electrode and a molten salt electrolyte including halides of a metal selected from the alkali metals and the alkaline earth metals in contact with both the positive and negative electrodes. The current collector has a base metal of copper, silver, gold, aluminum or alloys thereof with a coating thereon of iron, nickel, chromium or alloys thereof. The current collector when subjected to cell voltage forms a sulfur-containing compound on the surface thereby substantially protecting the current collector from further attack by sulfur ions during cell operation. Both electroless and electrolytic processes may be used to deposit coatings.

Selective removal of cesium by ammonium molybdophosphate - polyacrylonitrile bead and membrane.

PubMed

Ding, Dahu; Zhang, Zhenya; Chen, Rongzhi; Cai, Tianming

2017-02-15

The selective removal of radionuclides with extremely low concentrations from environmental medium remains a big challenge. Ammonium molybdophosphate possess considerable selectivity towards cesium ion (Cs + ) due to the specific ion exchange between Cs + and NH 4 + . Ammonium molybdophosphate - polyacrylonitrile (AMP-PAN) membrane was successfully prepared for the first time in this study. Efficient removal of Cs + (95.7%, 94.1% and 91.3% of 1mgL -1 ) from solutions with high ionic strength (400mgL -1 of Na + , Ca 2+ or K + ) was achieved by AMP-PAN composite. Multilayer chemical adsorption process was testified through kinetic and isotherm studies. The estimated maximum adsorption capacities even reached 138.9±21.3mgg -1 . Specifically, the liquid film diffusion was identified as the rate-limiting step throughout the removal process. Finally, AMP-PAN membrane could eliminate Cs + from water effectively through the filtration adsorption process. Copyright © 2016 Elsevier B.V. All rights reserved.

Liquid metal electric pump

DOEpatents

Abbin, J.P.; Andraka, C.E.; Lukens, L.L.; Moreno, J.B.

1992-01-14

An electrical pump for pumping liquid metals to high pressures in high temperature environments without the use of magnets or moving mechanical parts. The pump employs a non-porous solid electrolyte membrane, typically ceramic, specific to the liquid metal to be pumped. A DC voltage is applied across the thickness of the membrane causing ions to form and enter the membrane on the electrically positive surface, with the ions being neutralized on the opposite surface. This action provides pumping of the liquid metal from one side of the non-porous solid electrolyte membrane to the other. 3 figs.

Liquid metal electric pump

DOEpatents

Abbin, Joseph P.; Andraka, Charles E.; Lukens, Laurance L.; Moreno, James B.

1992-01-01

An electrical pump for pumping liquid metals to high pressures in high temperature environments without the use of magnets or moving mechanical parts. The pump employs a non-porous solid electrolyte membrane, typically ceramic, specific to the liquid metal to be pumped. A DC voltage is applied across the thickness of the membrane causing ions to form and enter the membrane on the electrically positive surface, with the ions being neutralized on the opposite surface. This action provides pumping of the liquid metal from one side of the non-porous solid electrolyte membrane to the other.

Application of a taste evaluation system to the monitoring of Kimchi fermentation.

PubMed

Kim, Namsoo; Park, Kyung-Rim; Park, In-Seon; Cho, Yong-Jin; Bae, Young Min

2005-05-15

As an objective method, taste evaluation with an instrument is able to supplement the subjective sensory evaluation and to be applied to the optimization of food processing. Kimchi, a Korean traditional pickle fermented with lactic acid bacteria, is expanding its consumption worldwide. The fermentation control of it has been routinely done by measuring titratable acidity and pH. In this study, an eight-channel taste evaluation system was prepared, followed by an application to the monitoring of Kimchi fermentation. Eight polymer membranes which individually responded to cationic or anionic substances were prepared by mixing electroactive materials such as tri-n-octylmethylammonium chloride, bis(2-ethylhexyl)sebacate as the plasticizer and polyvinyl chloride in the ratio of 1:66:33. Each membrane prepared was separately installed onto the sensitive area of an ion-selective electrode to produce the respective taste sensor. The eight-channel sensor array and a double junction reference electrode were connected to a 16-channel high input impedance amplifier. The amplified sensor signals were stored to a personal computer via a multi-channel A/D converter. Two sensor groups composed of the cation-selective and anion-selective polymer membrane electrodes showed characteristic concentration-dependency to various artificial taste substances. As a whole, the response potentials of the sensor array increased during the fermentation period at 4, 10 and 25 degrees C. Even the response potentials of the anion-selective taste sensors slightly increased possibly due to the protonation of anions by liberated H+ ions, thereby leading to a decrease in the anion concentration. When the signal data were interpreted by principal component analysis (PCA), the first PC at 4 degrees C explained most of the total data variance. A close correlation was found between the values of titratable acidity and the first PC, which indicated a possible applicability of the multi-channel taste sensor of this study to the process monitoring of various pickle.

Electrochemical Device Comprising an Electrically-Conductive, Selectively-Permeable Membrane

NASA Technical Reports Server (NTRS)

Laicer, Castro S. T. (Inventor); Mittelsteadt, Cortney K. (Inventor); Harrison, Katherine E. (Inventor); McPheeters, Bryn M. (Inventor)

2017-01-01

An electrochemical device, such as a fuel cell or an electrolyzer. In one embodiment, the electrochemical device includes a membrane electrode assembly (MEA), an anodic gas diffusion medium in contact with the anode of the MEA, a cathodic gas diffusion medium in contact with the cathode, a first bipolar plate in contact with the anodic gas diffusion medium, and a second bipolar plate in contact with the cathodic gas diffusion medium. Each of the bipolar plates includes an electrically-conductive, non-porous, liquid-permeable, substantially gas-impermeable membrane in contact with its respective gas diffusion medium, the membrane including a solid polymer electrolyte and a non-particulate, electrically-conductive material, such as carbon nanotubes, carbon nanofibers, and/or metal nanowires. In addition, each bipolar plate also includes an electrically-conductive fluid chamber in contact with the electrically-conductive, selectively-permeable membrane and further includes a non-porous and electrically-conductive plate in contact with the fluid chamber.

Ion-Gated Gas Separation through Porous Graphene

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

Tian, Ziqi; Mahurin, Shannon M.; Dai, Sheng

Porous graphene holds great promise as an atom-thin, high-permeance membrane for gas separation, but to precisely control the pore size at three to five angstroms proves challenging. Here we propose an ion-gated graphene membrane comprising a monolayer of ionic liquid coated porous graphene to dynamically modulate the pore size to achieve selective gas separation. This approach enables the otherwise non-selective large pores on the order of 1 nm in size to be selective for gases whose diameters range from three to four angstroms. We show from molecular dynamics simulations that CO 2, N 2 and CH 4 all can permeatemore » through a 1-nm pore in graphene without any selectivity. But when a monolayer of [emim][BF 4] is deposited on the porous graphene, CO 2 has much higher permeance than the other two gases. We find that the anion dynamically modulates the pore size by hovering above the pore and provides affinity for CO 2 while the larger cation (which cannot go through the pore) holds the anion in place via electrostatic attraction. This composite membrane is especially promising for CO 2/CH 4 separation, with a CO 2/CH 4 selectivity of about 42 and CO 2 permeance ~105 GPU (gas permeation unit). We further demonstrate that selectivity and permeance can be tuned by the anion size. The present work points toward a promising direction of using the atom-thin ionic-liquid/porous-graphene hybrid membrane for high-permeance, selective gas separation that allows a greater flexibility in substrate pore size control.« less

Ion-Gated Gas Separation through Porous Graphene

DOE PAGES

Tian, Ziqi; Mahurin, Shannon M.; Dai, Sheng; ...

2017-02-10

Porous graphene holds great promise as an atom-thin, high-permeance membrane for gas separation, but to precisely control the pore size at three to five angstroms proves challenging. Here we propose an ion-gated graphene membrane comprising a monolayer of ionic liquid coated porous graphene to dynamically modulate the pore size to achieve selective gas separation. This approach enables the otherwise non-selective large pores on the order of 1 nm in size to be selective for gases whose diameters range from three to four angstroms. We show from molecular dynamics simulations that CO 2, N 2 and CH 4 all can permeatemore » through a 1-nm pore in graphene without any selectivity. But when a monolayer of [emim][BF 4] is deposited on the porous graphene, CO 2 has much higher permeance than the other two gases. We find that the anion dynamically modulates the pore size by hovering above the pore and provides affinity for CO 2 while the larger cation (which cannot go through the pore) holds the anion in place via electrostatic attraction. This composite membrane is especially promising for CO 2/CH 4 separation, with a CO 2/CH 4 selectivity of about 42 and CO 2 permeance ~105 GPU (gas permeation unit). We further demonstrate that selectivity and permeance can be tuned by the anion size. The present work points toward a promising direction of using the atom-thin ionic-liquid/porous-graphene hybrid membrane for high-permeance, selective gas separation that allows a greater flexibility in substrate pore size control.« less

Molecular Transport in Ionic Polymer Membranes Under an Applied Voltage

DTIC Science & Technology

2013-11-22

in Porous Carbon Electrodes in Supercapacitors Using in Situ Infrared Spectroelectrochemistry, Journal of the American Chemical Society (08 2013...3. Ion Dynamics in Porous Carbon Electrodes in Supercapacitors Using in situ Infrared Spectroelectrochemistry Electrochemical double layer...capacitors (EDLC), or supercapacitors , rely on electrosorption of ions by porous carbon electrodes and offer a higher power and a longer cyclic

Multi-block sulfonated poly(phenylene) copolymer proton exchange membranes

DOEpatents

Fujimoto, Cy H [Albuquerque, NM; Hibbs, Michael [Albuquerque, NM; Ambrosini, Andrea [Albuquerque, NM

2012-02-07

Improved multi-block sulfonated poly(phenylene) copolymer compositions, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cells, in electrode casting solutions and electrodes. The multi-block architecture has defined, controllable hydrophobic and hydrophilic segments. These improved membranes have better ion transport (proton conductivity) and water swelling properties.

Ion-ion correlations across and between electrified graphene layers

NASA Astrophysics Data System (ADS)

Mendez-Morales, Trinidad; Burbano, Mario; Haefele, Matthieu; Rotenberg, Benjamin; Salanne, Mathieu

2018-05-01

When an ionic liquid adsorbs onto a porous electrode, its ionic arrangement is deeply modified due to a screening of the Coulombic interactions by the metallic surface and by the confinement imposed upon it by the electrode's morphology. In particular, ions of the same charge can approach at close contact, leading to the formation of a superionic state. The impact of an electrified surface placed between two liquid phases is much less understood. Here we simulate a full supercapacitor made of the 1-butyl-3-methylimidazolium hexafluorophosphate and nanoporous graphene electrodes, with varying distances between the graphene sheets. The electrodes are held at constant potential by allowing the carbon charges to fluctuate. Under strong confinement conditions, we show that ions of the same charge tend to adsorb in front of each other across the graphene plane. These correlations are allowed by the formation of a highly localized image charge on the carbon atoms between the ions. They are suppressed in larger pores, when the liquid adopts a bilayer structure between the graphene sheets. These effects are qualitatively similar to the recent templating effects which have been reported during the growth of nanocrystals on a graphene substrate.

Capacitive Neutralization Dialysis for Direct Energy Generation.

PubMed

Liu, Yue; Zhang, Yi; Ou-Yang, Wei; Bastos Sales, Bruno; Sun, Zhuo; Liu, Fei; Zhao, Ran

2017-08-15

Capacitive neutralization dialysis energy (CNDE) is proposed as a novel energy-harvesting technique that is able to utilize waste acid and alkaline solutions to produce electrical energy. CNDE is a modification based on neutralization dialysis. It was found that a higher NaCl concentration led to a higher open-circuit potential when the concentrations of acid and alkaline solutions were fixed. Upon closing of the circuit, the membrane potential was used as a driving force to move counter ions into the electrical double layers at the electrode-liquid interface, thereby creating an ionic current. Correspondingly, in the external circuit, electrons flow through an external resistor from one electrode to the other, thereby generating electrical energy directly. The influence of external resistances was studied to achieve greater energy extraction, with the maximum output of 110 mW/m 2 obtained by employing an external resistance of 5 Ω together with the AC-coated electrode.

Combinatorial screening of potentiometric Pb(II) sensors from polysulfoaminoanthraquinone solid ionophore.

PubMed

Huang, Mei-Rong; Ding, Yong-Bo; Li, Xin-Gui

2014-03-10

A potentiometric Pb(II)-selective sensor was fabricated by a combinatorial screening of electrically conducting polysulfoaminoanthraquinone (PSA) nanoparticles as a solid ionophore, ion exchangers (oleic acid (OA) and NaTPB), plasticizers in a polyvinyl chloride (PVC) matrix, membrane thickness, inner filling ion species, and concentration. The membrane sensor with the composition of PSA/PVC/DOP (dioctyl phthalate)/OA (1.0:33:61:5.0) exhibited the best performance, including a slope of 29.3 mV decade(-1) in the concentration range 10(-6.3)-10(-1.6) M, detection limit of 1.6 × 10(-7) M, response time of 16 s, lifetime of five months, and good response reversibility. The proposed sensor has demonstrated good selectivity for Pb(II) over other monovalent, divalent and trivalent interfering ions, and could be used in a pH range of 3.62-5.22. The Pb(II) sensor has been successfully applied for the determination of Pb(II) concentration in real-world samples and also as an indicator electrode for potentiometric titration of lead ions.

A Novel Sensor for Monitoring of Iron(III) Ions Based on Porphyrins

PubMed Central

Vlascici, Dana; Fagadar-Cosma, Eugenia; Popa, Iuliana; Chiriac, Vlad; Gil-Agusti, Mayte

2012-01-01

Three A3B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10−7–1 × 10−1 M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples. PMID:22969395

Biredox ionic liquids: new opportunities toward high performance supercapacitors.

PubMed

Bodin, C; Mourad, E; Zigah, D; Le Vot, S; Freunberger, S A; Favier, F; Fontaine, O

2018-01-01

Nowadays commercial supercapacitors are based on purely capacitive storage at the porous carbons that are used for the electrodes. However, the limits that capacitive storage imposes on energy density calls to investigate new materials to improve the capacitance of the device. This new type of electrodes (e.g., RuO 2 , MnO 2 …) involves pseudo-capacitive faradaic redox processes with the solid material. Ion exchange with solid materials is, however, much slower than the adsorption process in capacitive storage and inevitably leads to significant loss of power. Faradaic process in the liquid state, in contrast can be similarly fast as capacitive processes due to the fast ion transport. Designing new devices with liquid like dynamics and improved specific capacitance is challenging. We present a new approach to increase the specific capacitance using biredox ionic liquids, where redox moieties are tethered to the electrolyte ions, allowing high redox concentrations and significant pseudo-capacitive storage in the liquid state. Anions and cations are functionalized with anthraquinone (AQ) and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) moieties, respectively. Glassy carbon, carbon-onion, and commercial activated carbon electrodes that exhibit different double layer structures and thus different diffusion dynamics were used to simultaneously study the electrochemical response of biredox ionic liquids at the positive and negative electrode.

Environmentally-friendly aqueous Li (or Na)-ion battery with fast electrode kinetics and super-long life

PubMed Central

Dong, Xiaoli; Chen, Long; Liu, Jingyuan; Haller, Servane; Wang, Yonggang; Xia, Yongyao

2016-01-01

Current rechargeable batteries generally display limited cycle life and slow electrode kinetics and contain environmentally unfriendly components. Furthermore, their operation depends on the redox reactions of metal elements. We present an original battery system that depends on the redox of I−/I3− couple in liquid cathode and the reversible enolization in polyimide anode, accompanied by Li+ (or Na+) diffusion between cathode and anode through a Li+/Na+ exchange polymer membrane. There are no metal element–based redox reactions in this battery, and Li+ (or Na+) is only used for charge transfer. Moreover, the components (electrolyte/electrode) of this system are environment-friendly. Both electrodes are demonstrated to have very fast kinetics, which gives the battery a supercapacitor-like high power. It can even be cycled 50,000 times when operated within the electrochemical window of 0 to 1.6 V. Such a system might shed light on the design of high-safety and low-cost batteries for grid-scale energy storage. PMID:26844298

Environmentally-friendly aqueous Li (or Na)-ion battery with fast electrode kinetics and super-long life.

PubMed

Dong, Xiaoli; Chen, Long; Liu, Jingyuan; Haller, Servane; Wang, Yonggang; Xia, Yongyao

2016-01-01

Current rechargeable batteries generally display limited cycle life and slow electrode kinetics and contain environmentally unfriendly components. Furthermore, their operation depends on the redox reactions of metal elements. We present an original battery system that depends on the redox of I(-)/I3 (-) couple in liquid cathode and the reversible enolization in polyimide anode, accompanied by Li(+) (or Na(+)) diffusion between cathode and anode through a Li(+)/Na(+) exchange polymer membrane. There are no metal element-based redox reactions in this battery, and Li(+) (or Na(+)) is only used for charge transfer. Moreover, the components (electrolyte/electrode) of this system are environment-friendly. Both electrodes are demonstrated to have very fast kinetics, which gives the battery a supercapacitor-like high power. It can even be cycled 50,000 times when operated within the electrochemical window of 0 to 1.6 V. Such a system might shed light on the design of high-safety and low-cost batteries for grid-scale energy storage.

Beyond flexible batteries: aesthetically versatile, printed rechargeable power sources for smart electronics

NASA Astrophysics Data System (ADS)

Lee, Sang-Young

2017-05-01

Forthcoming wearable/flexible electronics with compelling shape diversity and mobile usability have garnered significant attention as a kind of disruptive technology to drastically change our daily lives. From a power source point of view, conventional rechargeable batteries (represented by lithium-ion batteries) with fixed shapes and dimensions are generally fabricated by winding (or stacking) cell components (such as anodes, cathodes and separator membranes) and then packaging them with (cylindrical-/rectangular-shaped) metallic canisters or pouch films, finally followed by injection of liquid electrolytes. In particular, the use of liquid electrolytes gives rise to serious concerns in cell assembly, because they require strict packaging materials to avoid leakage problems and also separator membranes to prevent electrical contact between electrodes. For these reasons, the conventional cell assembly and materials have pushed the batteries to lack of variety in form factors, thus imposing formidable challenges on their integration into versatile-shaped electronic devices. Here, as a facile and efficient strategy to address the aforementioned longstanding challenge, we demonstrate a new class of printed solid-state Li-ion batteries and also all-inkjet-printed solid-state supercapacitors with exceptional shape conformability and aesthetic versatility which lie far beyond those achievable with conventional battery technologies.

Metal-air cell with performance enhancing additive

DOEpatents

Friesen, Cody A; Buttry, Daniel

2015-11-10

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

Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.

Guided cracking of electrodes by stretching prism-patterned membrane electrode assemblies for high-performance fuel cells.

PubMed

Ahn, Chi-Yeong; Jang, Segeun; Cho, Yong-Hun; Choi, Jiwoo; Kim, Sungjun; Kim, Sang Moon; Sung, Yung-Eun; Choi, Mansoo

2018-01-19

Guided cracks were successfully generated in an electrode using the concentrated surface stress of a prism-patterned Nafion membrane. An electrode with guided cracks was formed by stretching the catalyst-coated Nafion membrane. The morphological features of the stretched membrane electrode assembly (MEA) were investigated with respect to variation in the prism pattern dimension (prism pitches of 20 μm and 50 μm) and applied strain (S ≈ 0.5 and 1.0). The behaviour of water on the surface of the cracked electrode was examined using environmental scanning electron microscopy. Guided cracks in the electrode layer were shown to be efficient water reservoirs and liquid water passages. The MEAs with and without guided cracks were incorporated into fuel cells, and electrochemical measurements were conducted. As expected, all MEAs with guided cracks exhibited better performance than conventional MEAs, mainly because of the improved water transport.

Apical membrane permeability and kinetic properties of the sodium pump in rabbit urinary bladder.

PubMed

Lewis, S A; Wills, N K

1983-08-01

Previous studies have shown that aldosterone stimulates the rate of Na+ transport across the rabbit urinary bladder epithelium by increasing the apical membrane permeability to Na+. Paradoxically, ion-sensitive and conventional micro-electrode measurements demonstrated that intracellular Na+ activity aiNa+ was essentially unchanged by aldosterone, i.e. aiNa+ was constant regardless of the rate of Na+ transport. The present study was designed to resolve this apparent contradiction. The effects of elevated, endogenous aldosterone levels produced by low-Na+ diet (Lewis & Diamond, 1976) on urinary bladder Na+ transport were investigated in vitro using Ussing-type chambers and intracellular conventional and ion-sensitive microelectrodes. Apical membrane selectivity and kinetics of the Na+ pump were assessed as a function of hormone stimulation. The aldosterone-stimulated increase in Na+ transport was accounted for by increases in both the relative selective permeability of the apical membrane to Na+ and an increase in its absolute Na+ permeability. The kinetics of the Na+ pump were evaluated electrically by loading the cells with Na+ (monitored with Na+-sensitive micro-electrodes) or alternatively by manipulating serosal solution K+ concentration and measuring changes in the basolateral membrane electromotive forces and resistance. From these measurements the current generated by the pump was calculated as a function of intracellular Na+ or extracellular K+. The kinetics of the pump were not altered by aldosterone. A model of highly co-operative binding estimated Km for Na+ as 14.2 mM and 2.3 mM for K+. Hill coefficients for these ions were 2.8 and 1.8, respectively, consistent with a pump stoichiometry of 3 Na+ to 2 K+. The kinetic properties of the Na-K pump indicate that physiological levels of aiNa+ are poised at the foot of a step kinetic curve which energetically favours Na+ extrusion.

Method of removing and detoxifying a phosphorus-based substance

DOEpatents

Vandegrift, George F.; Steindler, Martin J.

1989-01-01

A method of removing organic phosphorus-based poisonous substances from water contaminated therewith and of subsequently destroying the toxicity of the substance is disclosed. Initially, a water-immiscible organic is immobilized on a supported liquid membrane. Thereafter, the contaminated water is contacted with one side of the supported liquid membrane to selectively dissolve the phosphorus-based substance in the organic extractant. At the same time, the other side of the supported liquid membrane is contacted with a hydroxy-affording strong base to react the phosphorus-based substance dissolved by the organic extractant with a hydroxy ion. This forms a non-toxic reaction product in the base. The organic extractant can be a water-insoluble trialkyl amine, such as trilauryl amine. The phosphorus-based substance can be phosphoryl or a thiophosphoryl.

The importance of ion size and electrode curvature on electrical double layers in ionic liquids.

PubMed

Feng, Guang; Qiao, Rui; Huang, Jingsong; Dai, Sheng; Sumpter, Bobby G; Meunier, Vincent

2011-01-21

Room-temperature ionic liquids (ILs) are an emerging class of electrolytes for supercapacitors. We investigate the effects of ion size and electrode curvature on the electrical double layers (EDLs) in two ILs 1-butyl-3-methylimidazolium chloride [BMIM][Cl] and 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF(6)], using a combination of molecular dynamics (MD) and quantum density functional theory (DFT) simulations. The sizes of the counter-ion and co-ion affect the ion distribution and orientational structure of EDLs. The EDL capacitances near both planar and cylindrical electrodes were found to follow the order: [BMIM][Cl] (near the positive electrode) > [BMIM][PF(6)] (near the positive electrode) ≈ [BMIM][Cl] (near the negative electrode) ≈ [BMIM][PF(6)] (near the negative electrode). The EDL capacitance was also found to increase as the electrode curvature increases. These capacitance data can be fit to the Helmholtz model and the recently proposed exohedral electrical double-cylinder capacitor (xEDCC) model when the EDL thickness is properly parameterized, even though key features of the EDLs in ILs are not accounted for in these models. To remedy the shortcomings of existing models, we propose a "Multiple Ion Layers with Overscreening" (MILO) model for the EDLs in ILs that takes into account two critical features of such EDLs, i.e., alternating layering of counter-ions and co-ions and charge overscreening. The capacitance computed from the MILO model agrees well with the MD prediction. Although some input parameters of the MILO model must be obtained from MD simulations, the MILO model may provide a new framework for understanding many important aspects of EDLs in ILs (e.g., the variation of EDL capacitance with the electrode potential) that are difficult to interpret using classical EDL models and experiments.

Dense ceramic membranes for converting methane to syngas

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

Balachandran, U.; Dusek, J.T.; Picciolo, J.J.

1995-07-01

Dense mixed-oxide ceramics capable of conducting both electrons and oxygen ions are promising materials for partial oxygenation of methane to syngas. We are particularly interested in an oxide based on the Sr-Fe-Co-O system. Dense ceramic membrane tubes have been fabricated by a plastic extrusion technique. The sintered tubes were then used to selectively transport oxygen from air through the membrane to make syngas without the use of external electrodes. The sintered tubes have operated for >1000 h, and methane conversion efficiencies of >98% have been observed. Mechanical properties, structural integrity of the tubes during reactor operation, results of methane conversion,more » selectivity of methane conversion products, oxygen permeation, and fabrication of multichannel configurations for large-scale production of syngas will be presented.« less

Kinetic Studies with Ion Selective Electrodes: Determination of Creatinine in Urine with a Picrate Ion Selective Electrode: A Laboratory Experiment.

ERIC Educational Resources Information Center

Diamandis, E. P.; And Others

1983-01-01

The kinetic of the Jaffe reaction with picrate ion selective electrode (ISE) and a kinetic method for determining creatinine in urine is presented. The experiment could be used to familarize students with the application of ISE in kinetic studies and chemical analysis. (Author/JN)

Ion-Selective Electrodes for Basic Drugs.

DTIC Science & Technology

1981-01-01

coated wire ion selective electrodes for methadone , methylamphetamine, J cocaine, protriptyline i 20. ABSTRACT (Continue on reverse side If neeeeary...end Identify by block number) Coated-wire ion-selective electrodes based on dinonylnaphthalene u-i sulfonic acid (DNNS) are prepared for methadone ...range from 10- 5.5M for cocaine and methylamphetamine electrodes to 10Ś.0M for methadone , and 10-6.5M for DD I 󈨍 1473 EDITION OF I NOV 5 IS OBSOLETE

Dynamic Charge Storage in Ionic Liquids-Filled Nanopores: Insight from a Computational Cyclic Voltammetry Study.

PubMed

He, Yadong; Huang, Jingsong; Sumpter, Bobby G; Kornyshev, Alexei A; Qiao, Rui

2015-01-02

Understanding the dynamic charge storage in nanoporous electrodes with room-temperature ionic liquid electrolytes is essential for optimizing them to achieve supercapacitors with high energy and power densities. Herein, we report coarse-grained molecular dynamics simulations of the cyclic voltammetry of supercapacitors featuring subnanometer pores and model ionic liquids. We show that the cyclic charging and discharging of nanopores are governed by the interplay between the external field-driven ion transport and the sloshing dynamics of ions inside of the pore. The ion occupancy along the pore length depends strongly on the scan rate and varies cyclically during charging/discharging. Unlike that at equilibrium conditions or low scan rates, charge storage at high scan rates is dominated by counterions while the contribution by co-ions is marginal or negative. These observations help explain the perm-selective charge storage observed experimentally. We clarify the mechanisms underlying these dynamic phenomena and quantify their effects on the efficiency of the dynamic charge storage in nanopores.

Simultaneous Analysis of Monovalent Anions and Cations with a Sub-Microliter Dead-Volume Flow-Through Potentiometric Detector for Ion Chromatography

PubMed Central

Dumanli, Rukiye; Attar, Azade; Erci, Vildan; Isildak, Ibrahim

2016-01-01

A microliter dead-volume flow-through cell as a potentiometric detector is described in this article for sensitive, selective and simultaneous detection of common monovalent anions and cations in single column ion chromatography for the first time. The detection cell consisted of less selective anion- and cation-selective composite membrane electrodes together with a solid-state composite matrix reference electrode. The simultaneous separation and sensitive detection of sodium (Na+), potassium (K+), ammonium (NH4+), chloride (Cl−) and nitrate (NO3−) in a single run was achieved by using 98% 1.5 mM MgSO4 and 2% acetonitrile eluent with a mixed-bed ion-exchange separation column without suppressor column system. The separation and simultaneous detection of the anions and cations were completed in 6 min at the eluent flow-rate of 0.8 mL/min. Detection limits, at S/N = 3, were ranged from 0.2 to 1.0 µM for the anions and 0.3 to 3.0 µM for the cations, respectively. The developed method was successfully applied to the simultaneous determination of monovalent anions and cations in several environmental and biological samples. PMID:26786906

Ion thrusting system

NASA Technical Reports Server (NTRS)

Hartley, Frank T. (Inventor)

2007-01-01

An ion thrusting system is disclosed comprising an ionization membrane having at least one area through which a gas is passed, and which ionizes the gas molecules passing therethrough to form ions and electrons, and an accelerator element which accelerates the ions to form thrust. In some variations, a potential is applied to the ionization membrane may be reversed to thrust ions in an opposite direction. The ionization membrane may also include an opening with electrodes that are located closer than a mean free path of the gas being ionized. Methods of manufacture and use are also provided.

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

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

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

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

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

DOE PAGES

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

2017-12-05

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

Microelectrodes in microbial ecology

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

Boots, S.

1989-03-15

Understanding the microenvironment of bacteria has presented many challenges for the microbial ecologist. Simple intracellular capillary electrodes have been used in neurophysiology since the 1950s to measure action potentials in ion transport over biological membranes, and ion-selective electrodes were developed soon thereafter for the determination of H{sup +}, Na{sup +}, K{sup +}, and Ca{sup 2+}. However, these analytical techniques did not receive much attention until 1978, when Niels Peter Revsbech and Bo Barker Joergensen at the Institute of Ecology and Genetics, University of Aarhus, Denmark, began using oxygen microelectrodes in their studies of the ecology and biogeochemistry of marine sedimentsmore » and other microbial environments. Today, Revsbech and Joergensen use five types of microelectrodes, two types of oxygen microelectrodes, a combined microelectrode for nitrous oxide and oxygen, a sulfide microelectrode, and a pH microelectrode. The first three microelectrodes have diameters of about 10 {mu}m and the last two of about 50 {mu}m. Some of the electrodes actually contain two or three cathodes plus a reference electrode, all situated behind a polymer membrane. In situ experiments have been done for several years at a water depth of several meters, where the micromanipulator is operated by a diver. Recently measurements were obtained in the deep sea with the microelectrodes mounted on a free-falling vehicle or operated from a submersible vessel.« less

Lipid bilayers suspended on microfabricated supports

NASA Astrophysics Data System (ADS)

Ogier, Simon D.; Bushby, Richard J.; Cheng, Yaling; Cox, Tim I.; Evans, Stephen D.; Knowles, Peter F.; Miles, Robert E.; Pattison, Ian

2001-03-01

The plasma membrane, that exists as part of many animal and plant cells, is a regulator for the transport of ions and small molecules across cell boundaries. Two main components involved are the phospholipid bilayer and the transport proteins. This paper details the construction of a micromachined support for bilayers (MSB) as a first step towards the development of highly selective and highly sensitive ion-channel based biosensors. The device consists of a ~100 micrometer hole in a polymeric support above a cavity that can hold ~25 nL of electrolyte. Electrodes attached to the structure allow the resistance of the membranes to be measured using d.c. conductivity. The MSB is made in two halves, using SU8 ultra-thick resist, which are subsequently bonded together to make the final structure. A layer of gold, surrounding the aperture, enables self-assembled monolayers of alkanethiols to be used to make the polymeric structure biocompatible. Lipid membranes have been formed over these holes with resistances comparable with those of natural membranes >10 MOhmcm^2. The ion-channel gramicidin has successfully been incorporated into the bilayer and its activity monitored. It is proposed that this type of device could be used not only for studying membrane transport phenomena but also as part of an ion-channel based biosensor.

Determination of arsenate and organic arsenic via potentiometric titration of its heteropoly anions.

PubMed

Metelka, R; Slavíková, S; Vytras, K

2002-08-16

Determination of arsenate based on its conversion to molybdoarsenate heteropoly anions followed by potentiometric titration is described. The titration is realized on the ion-pairing principle using cetylpyridinium chloride (or an analogous titrant containing a lipophilic cation), and is monitored by a carbon paste electrode, although other liquid-polymeric membrane-based electrodes can also be used. Calibration plots of the titrant end-point consumption versus concentration of arsenic were constructed and used to evaluate the content of arsenic in aqueous samples. The method could be applied in the analyses of samples with quite low arsenic content (amounts approximately 10 mug As in 50 cm(3) could be titrated). Organic arsenic was determined analogously after the Schöniger combustion of the sample and conversion of its arsenic to arsenate.

Thermally conductive lithium ion electrodes and batteries

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

Shevchenko, Elena; Sumant, Anirudha V.; Balandin, Alexander

A thermally conductive electrochemical cell comprises a lithium ion-containing liquid electrolyte contacting a cathode and anode. The cathode and anode are in the form of electroactive sheets separated from each other by a membrane that is permeable to the electrolyte. One or more of the cathode and anode comprises two or more layers of carbon nanotubes, one of which layers includes electrochemically active nanoparticles and/or microparticles disposed therein or deposited on the nanotubes thereof. The majority of the carbon nanotubes in each of the layers are oriented generally parallel to the layers. Optionally, one or more of the layers includesmore » an additional carbon material such as graphene, nanoparticulate diamond, microparticulate diamond, and a combination thereof.« less

Nano-level monitoring of Mn(2+) ion by fabrication of coated pyrolytic graphite electrode based on isonicotinohydrazide derivatives.

PubMed

Sahani, Manoj Kumar; Singh, A K; Jain, A K

2015-05-01

The two ionophores N'(N',N‴E,N',N‴E)-N',N‴-((((oxybis(ethane-2,1-diyl))bis(oxy)) bis(2,1-phenylene))bis(methanylylidene))di(isonicotinohydrazide) (I1) and (N',N‴E,N',N‴E)-N',N‴-(((propane-1,3-diylbis(oxy))bis(2,1-phenylene))bis(methanylylidene))di(isonicotinohydrazide) (I2) were synthesised and investigated as neutral carrier in the fabrication of Mn(2+) ion selective sensor. Several membranes were prepared by incorporating different plasticizers and anionic excluders and their effect on potentiometric response was studied. The best analytical performance was obtained with the electrode having a membrane of composition of I2: PVC: o-NPOE: NaTPB in the ratio of 6:34:58:2 (w/w, mg). Comparative studies of coated graphite electrode (CGE) and coated pyrolytic graphite electrode (CPGE) based on I2 reveal the superiority of CPGE. The CPGE exhibits wide working concentration range of 1.23×10(-8)-1.0×10(-1) mol L(-1) and a detection limit down to 4.78×10(-9) mol L(-1) with a Nernstian slope of 29.5±0.4 mV decade(-1) of activity. The sensor performs satisfactorily over a wide pH range (3.5-9.0) and exhibited a quick response time (9s). The sensor can work satisfactorily in water-acetonitrile and water-methanol mixtures. It can tolerate 30% acetonitrile and 20% methanol content in the mixtures. The sensor could be used for a period of four months without any significant divergence in performance. The sensor reflects its utility in the quantification of Mn(2+) ion in real samples and has been successfully employed as an indicator electrode in the potentiometric titration of Mn(2+) ion with ethylenediaminetetraacetic acid (EDTA). Copyright © 2015 Elsevier B.V. All rights reserved.

Time-resolved determination of the potential of zero charge at polycrystalline Au/ionic liquid interfaces

NASA Astrophysics Data System (ADS)

Vargas-Barbosa, Nella M.; Roling, Bernhard

2018-05-01

The potential of zero charge (PZC) is a fundamental property that describes the electrode/electrolyte interface. The determination of the PZC at electrode/ionic liquid interfaces has been challenging due to the lack of models that fully describe these complex interfaces as well as the non-standardized approaches used to characterize them. In this work, we present a method that combines electrode immersion transient and impedance measurements for the determination of the PZC. This combined approach allows the distinction of the potential of zero free charge (pzfc), related to fast double layer charging on a millisecond timescale, from a potential of zero charge on a timescale of tens of seconds related to slower ion transport processes at the interface. Our method highlights the complementarity of these electrochemical techniques and the importance of selecting the correct timescale to execute experiments and interpret the results.

In situ nanostructure formation of (micro-hydroxo)bis(micro-carboxylato) diruthenium units in nafion membrane and its utilization for selective reduction of nitrosonium ion in aqueous medium.

PubMed

Kumar, Annamalai Senthil; Tanase, Tomoaki; Iida, Masayasu

2007-01-16

Nanostructured molecular film containing the (micro-hydroxo)bis(micro-carboxylato) diruthenium(III) units, [RuIII2(micro-OH)(micro-CH3COO)2(HBpz3)2]+ ({RuIII2(micro-OH)}), was prepared by an in situ conversion of its micro-oxo precursor, [RuIII2(micro-O)(micro-CH3COO)2(HBpz3)2] ({RuIII2(micro-O)}), in a Nafion membrane matrix, where HBpz3 is hydrotris(1-pyrazolyl)borate. The conversion procedure results in fine nanoparticle aggregates of the {RuIII2(micro-OH)} units in the Nafion membrane (Nf-{RuIII2(micro-OH)}), where an average particle size (4.1 +/- 2.3 nm) is close to the Nafion's cluster dimension of approximately 4 nm. Chemically modified electrodes by using the Nafion molecular membrane films (Nf-{RuIII2(micro-OH)}-MMFEs) were further developed on ITO/glass and glassy carbon electrode (GCE) surfaces, and a selective reduction of nitrosonium ion (NO+), presumably through reaction of a {RuIIRuIII(micro-OH)} mixed-valence state with HNO2, was demonstrated without interference by molecular oxygen in an acidic aqueous solution. The Nf-{RuIII2(micro-OH)}-MMFEs are stable even in a physiological condition (pH 7), where the naked {RuIII2(-OH)} complex is readily transformed into its deprotonated {RuIII2(micro-O)} form, demonstrating an unusual stabilizing effects for the {RuIII2(micro-OH)} unit by the Nafion cluster environment.

A novel electrochemical ion exchange system and its application in water treatment.

PubMed

Li, Yansheng; Li, Yongbin; Liu, Zhigang; Wu, Tao; Tian, Ying

2011-06-01

A novel electrochemical ion exchange system with porous cylinder electrodes is proposed for treatment of wastewater. This system can be used for desalination without the costly ion-exchange membrane and extra chemical reagents. Since the electrodes are completely uniform and no ion-exchange membrane was used in this system, it can be operated by switching anodes and cathodes flexibly for eliminating the scaling on the surface of electrodes. The strong base ion-exchange resin grains placed among the anode and cathode have played as supporting electrolyte, which is capable for the treatment of wastewater with low conductivity. The concentrated and neutralized anolyte containing chlorine is effective for disinfection and contaminants removal. Under the experimental conditions, the removal percentage of total dissolved salts was 83% and the removal percentage of chemical oxygen demand was 92% without consumption of extra chemical reagents. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

A simple, fast and accurate in-situ method to measure the rate of transport of redox species through membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Meddings, Nina; Owen, John R.; Garcia-Araez, Nuria

2017-10-01

Lithium ion conducting membranes are important to protect the lithium metal electrode and act as a barrier to crossover species such as polysulphides in Li-S systems, redox mediators in Li-O2 cells or dissolved cathode species or electrolyte oxidation products in high voltage Li-ion batteries. We present an in-situ method for measuring permeability of membranes to crossover redox species. The method employs a 'Swagelok' cell design equipped with a glassy carbon working electrode, in which redox species are placed initially in the counter electrode compartment only. Permeability through the membrane, which separates working and counter electrodes, is determined using a square wave voltammetry technique that allows the concentration of crossover redox species to be evaluated over time with very high precision. We test the method using a model and well-behaved electrochemical system to demonstrate its sensitivity, reproducibility and reliability relative to alternative approaches. This new method offers advantages in terms of small electrolyte volume, and simple, fast, quantitative and in-situ measurement.

Cytosine substituted calix[4]pyrroles: Neutral receptors for 5′-guanosine monophosphate

PubMed Central

Sessler, Jonathan L.; Král, Vladimír; Shishkanova, Tatiana V.; Gale, Philip A.

2002-01-01

The synthesis and characterization of two cytosine-substituted calix[4]pyrrole conjugates, bearing the appended cytosine attached at either a β- or meso-pyrrolic position, is described. These systems were tested as nucleotide-selective carriers and as active components of nucleotide-sensing ion-selective electrodes at pH 6.6. Studies of carrier selectivity were made using a Pressman-type model membrane system consisting of an initial pH 6.0 aqueous phase, an intervening dichloromethane barrier containing the calix[4]pyrrole conjugate, and a receiving basic aqueous phase. Good selectivity for the Watson–Crick complementary nucleotide, 5′-guanosine monophosphate (5′-GMP), was seen in the case of the meso-linked conjugate with the relative rates of through-membrane transport being 7.7:4.1:1 for 5′-GMP, 5′-AMP, and 5′-CMP, respectively. By contrast, the β-substituted conjugate, while showing a selectivity for 5′-GMP that was enhanced relative to unsubstituted calix[4]pyrrole, was found to transport 5′-CMP roughly 4.5 times more quickly than 5′-GMP. Higher selectivities were also found for 5′-CMP when both the β- and meso-substituted conjugates were incorporated into polyvinyl chloride membranes and tested as ion selective electrodes at pH 6.6, whereas near-equal selectivities were observed for 5′-CMP and 5′-GMP in the case of unsubstituted calix[4]pyrroles. These seemingly disparate results are consistent with a picture wherein the meso-substituted cytosine calix[4]pyrrole conjugate, but not its β-linked congener, is capable of acting as a ditopic receptor, binding concurrently both the phosphate anion and nucleobase portions of 5′-GMP to the calixpyrrole core and cytosine “tails” of the molecule, respectively, with the effect of this binding being most apparent under the conditions of the transport experiments. PMID:11929967

Parasitic Currents Caused by Different Ionic and Electronic Conductivities in Fuel Cell Anodes.

PubMed

Schalenbach, Maximilian; Zillgitt, Marcel; Maier, Wiebke; Stolten, Detlef

2015-07-29

The electrodes in fuel cells simultaneously realize electric and ionic conductivity. In the case of acidic polymer electrolytes, the electrodes are typically made of composites of carbon-supported catalyst and Nafion polymer electrolyte binder. In this study, the interaction of the proton conduction, the electron conduction, and the electrochemical hydrogen conversion in such composite electrode materials was examined. Exposed to a hydrogen atmosphere, these composites displayed up to 10-fold smaller resistivities for the proton conduction than that of Nafion membranes. This effect was ascribed to the simultaneously occurring electrochemical hydrogen oxidation and evolution inside the composite samples, which are driven by different proton and electron resistivities. The parasitic electrochemical currents resulting were postulated to occur in the anode of fuel cells with polymer, solid oxide, or liquid alkaline electrolytes, when the ohmic drop of the ion conduction in the anode is higher with the anodic kinetic overvoltage (as illustrated in the graphical abstract). In this case, the parasitic electrochemical currents increase the anodic kinetic overpotential and the ohmic drop in the anode. Thinner fuel cell anodes with smaller ohmic drops for the ion conduction may reduce the parasitic electrochemical currents.

Inexpensive and Disposable pH Electrodes

ERIC Educational Resources Information Center

Goldcamp, Michael J.; Conklin, Alfred; Nelson, Kimberly; Marchetti, Jessica; Brashear, Ryan; Epure, Emily

2010-01-01

Inexpensive electrodes for the measurement of pH have been constructed using the ionophore tribenzylamine for sensing H[superscript +] concentrations. Both traditional liquid-membrane electrodes and coated-wire electrodes have been constructed and studied, and both exhibit linear, nearly Nernstian responses to changes in pH. Measurements of pH…

Method of making MEA for PEM/SPE fuel cell

DOEpatents

Hulett, Jay S.

2000-01-01

A method of making a membrane-electrode-assembly (MEA) for a PEM/SPE fuel cell comprising applying a slurry of electrode-forming material directly onto a membrane-electrolyte film. The slurry comprises a liquid vehicle carrying catalyst particles and a binder for the catalyst particles. The membrane-electrolyte is preswollen by contact with the vehicle before the electrode-forming slurry is applied to the membrane-electrolyte. The swollen membrane-electrolyte is constrained against shrinking in the "x" and "y" directions during drying. Following assembly of the fuel cell, the MEA is rehydrated inside the fuel cell such that it swells in the "z" direction for enhanced electrical contact with contiguous electrically conductive components of the fuel cell.

Compact high-sensitivity potentiometer for detection of low ion concentrations in liquids

NASA Astrophysics Data System (ADS)

Balevicius, Z.; Lescinskas, R.; Celiesiute, R.; Stirke, A.; Balevicius, S.; Kersulis, S.; Bleizgys, V.; Maciuleviciene, R.; Ramanavicius, A.; Zurauskiene, N.

2018-04-01

The compact potentiometer, based on an electronic circuit protected from electrostatic and electromagnetic interference, was developed for the measurement of low ion concentrations in liquids. The electronic circuit of the potentiometer, consisting of analogous and digital parts, enables the measurement of fA currents. This makes it possible to perform reliable measurements of ion concentrations in liquids that are as small as 10-8-10-7M. The instrument was tested using electrodes that were selective for tetraphenylphosphonium (TPP+) ions. It was demonstrated that the characteristic response time of the potentiometer electronic circuit to changes in the concentration of these ions in a liquid was in the order of 10 s. An investigation of TPP+ absorption by baker yeast has shown that this device can be successfully used for long term (several hours) measurements with zero signal drift, which was about 1 μV/s. Finally, due to the small dimensions of the electronic circuit (7.5 × 2 × 1.5 cm), this potentiometer can be easily installed at a large apparatus in the laboratory condition (≈25 °C), such as high pulsed electrical generators of magnetic fields that are used in electroporation studies of biological cells.

Oxygen-producing inert anodes for SOM process

DOEpatents

Pal, Uday B

2014-02-25

An electrolysis system for generating a metal and molecular oxygen includes a container for receiving a metal oxide containing a metallic species to be extracted, a cathode positioned to contact a metal oxide housed within the container; an oxygen-ion-conducting membrane positioned to contact a metal oxide housed within the container; an anode in contact with the oxygen-ion-conducting membrane and spaced apart from a metal oxide housed within the container, said anode selected from the group consisting of liquid metal silver, oxygen stable electronic oxides, oxygen stable crucible cermets, and stabilized zirconia composites with oxygen stable electronic oxides.

Determination of trace mercury in water based on N-octylpyridinium ionic liquids preconcentration and stripping voltammetry.

PubMed

Li, Zhenhan; Xia, Shanhong; Wang, Jinfen; Bian, Chao; Tong, Jianhua

2016-01-15

A novel method for determination of trace mercury in water is developed. The method is performed by extracting mercury firstly with ionic liquids (ILs) and then detecting the concentration of mercury in organic media with anodic stripping voltammetry. Liquid-liquid extraction of mercury(II) ions by four ionic liquids with N-octylpyridinium cations ([OPy](+)) was studied. N-octylpyridinium tetrafluoroborate and N-octylpyridinium trifluoromethylsulfonate were found to be efficient and selective extractant for mercury. Temperature controlled dispersive liquid phase microextraction (TC-DLPME) technique was utilized to improve the performance of preconcentration. After extraction, precipitated IL was diluted by acetonitrile buffer and mercury was detected by differential pulse stripping voltammetry (DPSV) with gold disc electrode. Mercury was enriched by 17 times while interfering ions were reduced by two orders of magnitude in the organic media under optimum condition. Sensitivity and selectivity for electrochemical determination of mercury were improved by using the proposed method. Tap, pond and waste water samples were analyzed with recoveries ranging from 81% to 107% and detection limit of 0.05 μg/L. Copyright © 2015 Elsevier B.V. All rights reserved.

Capillary electrophoresis with contactless conductivity detection for the quantification of fluoride in lithium ion battery electrolytes and in ionic liquids-A comparison to the results gained with a fluoride ion-selective electrode.

PubMed

Pyschik, Marcelina; Klein-Hitpaß, Marcel; Girod, Sabrina; Winter, Martin; Nowak, Sascha

2017-02-01

In this study, an optimized method using capillary electrophoresis (CE) with a direct contactless conductivity detector (C 4 D) for a new application field is presented for the quantification of fluoride in common used lithium ion battery (LIB) electrolyte using LiPF 6 in organic carbonate solvents and in ionic liquids (ILs) after contacted to Li metal. The method development for finding the right buffer and the suitable CE conditions for the quantification of fluoride was investigated. The results of the concentration of fluoride in different LIB electrolyte samples were compared to the results from the ion-selective electrode (ISE). The relative standard deviations (RSDs) and recovery rates for fluoride were obtained with a very high accuracy in both methods. The results of the fluoride concentration in the LIB electrolytes were in very good agreement for both methods. In addition, the limit of detection (LOD) and limit of quantification (LOQ) values were determined for the CE method. The CE method has been applied also for the quantification of fluoride in ILs. In the fresh IL sample, the concentration of fluoride was under the LOD. Another sample of the IL mixed with Li metal has been investigated as well. It was possible to quantify the fluoride concentration in this sample. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion-selective gold-thiol film on integrated screen-printed electrodes for analysis of Cu(II) ions.

PubMed

Li, Meng; Zhou, Hao; Shi, Lei; Li, Da-Wei; Long, Yi-Tao

2014-02-07

A novel type of ion-selective electrode (ISE) was manufactured for detecting trace amounts of Cu(II) ions. The basic substrates of ISE were fabricated using screen-printing technology, which could produce disposable electrodes on a large-scale with good repeatability. Moreover, the printed integrated three-electrode system of ISE could be directly used to read out the open-circuit potentials by a handheld device through a USB port. The ion-selective film was composed of gold nanorods (GNRs) and 6-(bis(pyridin-2-ylmethyl)amino)hexane-1-thiol (compound ), which were layer-by-layer modified on the electrode through an easily controlled self-assembly method. Compound contained the 2,2'-dipyridylamine (dpa) group that could coordinate with Cu(II) ions to form a 2 : 1 complex, therefore the screen-printed ISEs exhibited Nernstian potentiometric responses to Cu(II) ions with a detection limit of 6.3 × 10(-7) mol L(-1) over the range of 1.0 × 10(-6) to 1.0 × 10(-2) mol L(-1). The easily prepared screen-printed ion-selective electrode reported here was appropriate for in field analysis and pollutant detection in remote environments.

Evaluation of molecular dynamics simulation methods for ionic liquid electric double layers.

PubMed

Haskins, Justin B; Lawson, John W

2016-05-14

We investigate how systematically increasing the accuracy of various molecular dynamics modeling techniques influences the structure and capacitance of ionic liquid electric double layers (EDLs). The techniques probed concern long-range electrostatic interactions, electrode charging (constant charge versus constant potential conditions), and electrolyte polarizability. Our simulations are performed on a quasi-two-dimensional, or slab-like, model capacitor, which is composed of a polarizable ionic liquid electrolyte, [EMIM][BF4], interfaced between two graphite electrodes. To ensure an accurate representation of EDL differential capacitance, we derive new fluctuation formulas that resolve the differential capacitance as a function of electrode charge or electrode potential. The magnitude of differential capacitance shows sensitivity to different long-range electrostatic summation techniques, while the shape of differential capacitance is affected by charging technique and the polarizability of the electrolyte. For long-range summation techniques, errors in magnitude can be mitigated by employing two-dimensional or corrected three dimensional electrostatic summations, which led to electric fields that conform to those of a classical electrostatic parallel plate capacitor. With respect to charging, the changes in shape are a result of ions in the Stern layer (i.e., ions at the electrode surface) having a higher electrostatic affinity to constant potential electrodes than to constant charge electrodes. For electrolyte polarizability, shape changes originate from induced dipoles that soften the interaction of Stern layer ions with the electrode. The softening is traced to ion correlations vertical to the electrode surface that induce dipoles that oppose double layer formation. In general, our analysis indicates an accuracy dependent differential capacitance profile that transitions from the characteristic camel shape with coarser representations to a more diffuse profile with finer representations.

Double-barreled and Concentric Microelectrodes for Measurement of Extracellular Ion Signals in Brain Tissue

PubMed Central

Haack, Nicole; Durry, Simone; Kafitz, Karl W.; Chesler, Mitchell; Rose, Christine R.

2015-01-01

Electrical activity in the brain is accompanied by significant ion fluxes across membranes, resulting in complex changes in the extracellular concentration of all major ions. As these ion shifts bear significant functional consequences, their quantitative determination is often required to understand the function and dysfunction of neural networks under physiological and pathophysiological conditions. In the present study, we demonstrate the fabrication and calibration of double-barreled ion-selective microelectrodes, which have proven to be excellent tools for such measurements in brain tissue. Moreover, so-called “concentric” ion-selective microelectrodes are also described, which, based on their different design, offer a far better temporal resolution of fast ion changes. We then show how these electrodes can be employed in acute brain slice preparations of the mouse hippocampus. Using double-barreled, potassium-selective microelectrodes, changes in the extracellular potassium concentration ([K+]o) in response to exogenous application of glutamate receptor agonists or during epileptiform activity are demonstrated. Furthermore, we illustrate the response characteristics of sodium-sensitive, double-barreled and concentric electrodes and compare their detection of changes in the extracellular sodium concentration ([Na+]o) evoked by bath or pressure application of drugs. These measurements show that while response amplitudes are similar, the concentric sodium microelectrodes display a superior signal-to-noise ratio and response time as compared to the double-barreled design. Generally, the demonstrated procedures will be easily transferable to measurement of other ions species, including pH or calcium, and will also be applicable to other preparations. PMID:26381747

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.

Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus

DOEpatents

Zaromb, S.

1994-06-21

Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity [>=]10[sup [minus]4] (ohm-cm)[sup [minus]1], and preferably [>=]0.01 (ohm-cm)[sup [minus]1]. The conductivity may be due predominantly to Ag[sup +] ions, as in Ag[sub 2]WO[sub 4], or to F[sup [minus

A single-walled carbon nanotube thin film-based pH-sensing microfluidic chip.

PubMed

Li, Cheng Ai; Han, Kwi Nam; Pham, Xuan-Hung; Seong, Gi Hun

2014-04-21

A novel microfluidic pH-sensing chip was developed based on pH-sensitive single-walled carbon nanotubes (SWCNTs). In this study, the SWCNT thin film acted both as an electrode and a pH-sensitive membrane. The potentiometric pH response was observed by electronic structure changes in the semiconducting SWCNTs in response to the pH level. In a microfluidic chip consisting of a SWCNT pH-sensing working electrode and an Ag/AgCl reference electrode, the calibration plot exhibited promising pH-sensing performance with an ideal Nernstian response of 59.71 mV pH(-1) between pH 3 and 11 (standard deviation of the sensitivity is 1.5 mV pH(-1), R(2) = 0.985). Moreover, the SWCNT electrode in the microfluidic device showed no significant variation at any pH value in the range of the flow rate between 0.1 and 15 μl min(-1). The selectivity coefficients of the SWCNT electrode revealed good selectivity against common interfering ions.

Plasma processes in the preparation of lithium-ion battery electrodes and separators

NASA Astrophysics Data System (ADS)

Nava-Avendaño, J.; Veilleux, J.

2017-04-01

Lithium-ion batteries (LIBs) are the energy storage devices that dominate the portable electronic market. They are now also considered and used for electric vehicles and are foreseen to enable the smart grid. Preparing batteries with high energy and power densities, elevated cycleability and improved safety could be achieved by controlling the microstructure of the electrode materials and the interaction they have with the electrolyte over the working potential window. Selecting appropriate precursors, reducing the preparation steps and selecting more efficient synthesis methods could also significantly reduce the costs of LIB components. Implementing plasma technologies can represent a high capital investment, but the versatility of the technologies allows the preparation of powdered nanoparticles with different morphologies, as well as with carbon and metal oxide coatings. Plasma technologies can also enable the preparation of binder-free thin films and coatings for LIB electrodes, and the treatment of polymeric membranes to be used as separators. This review paper aims at highlighting the different thermal and non-thermal plasma technologies recently used to synthesize coated and non-coated active materials for LIB cathodes and anodes, and to modify the surface of separators.

Membraneless laminar flow cell for electrocatalytic CO2 reduction with liquid product separation

NASA Astrophysics Data System (ADS)

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei; Ager, Joel W.

2017-04-01

The production of liquid fuel products via electrochemical reduction of CO2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O2) from reaching the cathode. Ion-conducting membranes have been applied in CO2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flow cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.

MOF-Based Membrane Encapsulated ZnO Nanowires for Enhanced Gas Sensor Selectivity.

PubMed

Drobek, Martin; Kim, Jae-Hun; Bechelany, Mikhael; Vallicari, Cyril; Julbe, Anne; Kim, Sang Sub

2016-04-06

Gas sensors are of a great interest for applications including toxic or explosive gases detection in both in-house and industrial environments, air quality monitoring, medical diagnostics, or control of food/cosmetic properties. In the area of semiconductor metal oxides (SMOs)-based sensors, a lot of effort has been devoted to improve the sensing characteristics. In this work, we report on a general methodology for improving the selectivity of SMOx nanowires sensors, based on the coverage of ZnO nanowires with a thin ZIF-8 molecular sieve membrane. The optimized ZnO@ZIF-8-based nanocomposite sensor shows markedly selective response to H2 in comparison with the pristine ZnO nanowires sensor, while showing the negligible sensing response to C7H8 and C6H6. This original MOF-membrane encapsulation strategy applied to nanowires sensor architecture pave the way for other complex 3D architectures and various types of applications requiring either gas or ion selectivity, such as biosensors, photo(catalysts), and electrodes.

Electrochemical forces for chloride transport in the proximal tubules of the rat kidney.

PubMed

Sohtell, M

1978-08-01

The electrochemical forces for chloride transport in the proximal tubule of the rat kidney were studied using micropuncture techniques. Electrical transmembrane potentials were recorded in randomly punctured tubules with Ling-Gerhard electrodes. Chloride activities in the luminal, cellular and interstitial compartments were measured with ion selective micro-electrodes. Electrical potential measurements between cell to interstitium and lumen to interstitium were -72.1 +/- 2.6 mV and +0.5 +/- 1.4 mV (mean +/- S.D.) respectively. The calculated chloride concentrations for lumen, cell and interstitium were 133.0 +/- 10.3 mM, 8.5 +/- 1.0 mM and 99.1 +/- 3.2 mM (mean +/- S.D.) respectively. The net electrochemical forces, qualitatively, offer a passive chloride ion pathway through the tubular wall and a chloride equilibrium over the luminal membrane seems to exist.

Developments in the Field of Conducting and Non-conducting Polymer Based Potentiometric Membrane Sensors for Ions Over the Past Decade

PubMed Central

Faridbod, Farnoush; Ganjali, Mohammad Reza; Dinarvand, Rassoul; Norouzi, Parviz

2008-01-01

Many research studies have been conducted on the use of conjugated polymers in the construction of chemical sensors including potentiometric, conductometric and amperometric sensors or biosensors over the last decade. The induction of conductivity on conjugated polymers by treating them with suitable oxidizing agents won Heeger, MacDiarmid and Shirakawa the 2000 Nobel Prize in Chemistry. Common conjugated polymers are poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(terthiophene)s, poly(aniline)s, poly(fluorine)s, poly(3-alkylthiophene)s, polytetrathiafulvalenes, poly-napthalenes, poly(p-phenylene sulfide), poly(p-phenylenevinylene)s, poly(3,4-ethylene-dioxythiophene), polyparaphenylene, polyazulene, polyparaphenylene sulfide, poly-carbazole and polydiaminonaphthalene. More than 60 sensors for inorganic cations and anions with different characteristics based on conducting polymers have been reported. There have also been reports on the application of non-conducting polymers (nCPs), i.e. PVC, in the construction of potentiometric membrane sensors for determination of more than 60 inorganic cations and anions. However, the leakage of ionophores from the membranes based on these polymers leads to relatively lower life times. In this article, we try to give an overview of Solid-Contact ISE (SCISE), Single-Piece ISE (SPISE), Conducting Polymer (CP)-Based, and also non-conducting polymer PVC-based ISEs for various ions which their difference is in the way of the polymer used with selective\\ membrane. In SCISEs and SPISEs, the plasticized PVC containing the ionophore and ionic additives govern the selectivity behavior of the electrode and the conducting polymer is responsible of ion-to-electron transducer. However, in CPISEs, the conducting polymer layer is doped with a suitable ionophore which enhances the ion selectivity of the CP while its redox response has to be suppressed. PMID:27879825

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

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

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

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

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

DOE PAGES

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

2018-04-19

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

Supercapacitors based on modified graphene electrodes with poly(ionic liquid)

NASA Astrophysics Data System (ADS)

Trigueiro, João Paulo C.; Lavall, Rodrigo L.; Silva, Glaura G.

2014-06-01

The improved accessibility of the electrolyte to the surface of carbon nanomaterials is a challenge to be overcome in supercapacitors based on ionic liquid electrolytes. In this study, we report the preparation of supercapacitors based on reduced graphene oxide (RGO) electrodes and ionic liquid as the electrolyte (specifically, 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide or [MPPy][TFSI]). Two types of electrodes were compared: the RGO-based electrode and a poly(ionic liquid)-modified RGO electrode (PIL:RGO). The supercapacitor produced with the PIL:RGO electrode and [MPPy][TFSI] showed an electrochemical stability of 3 V and provided a capacitance of 71.5 F g-1 at room temperature; this capacitance is 130% higher with respect to the RGO-based supercapacitor. The decrease of the specific capacitance after 2000 cycles is only 10% for the PIL:RGO-based device. The results revealed the potential of the PIL:RGO material as an electrode for supercapacitors. This composite electrode increases the compatibility with the ionic liquid electrolyte compared to an RGO electrode, promoting an increase in the effective surface area of the electrode accessible to the electrolyte ions.

Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane

NASA Astrophysics Data System (ADS)

He, Ruixuan; Echeverri, Mauricio; Kyu, Thein

2014-03-01

With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

Ion trapping by the graphene electrode in a graphene-ITO hybrid liquid crystal cell

NASA Astrophysics Data System (ADS)

Basu, Rajratan; Lee, Andrew

2017-10-01

A monolayer graphene coated glass slide and an indium tin oxide (ITO) coated glass slide with a planar-aligning polyimide layer were placed together to make a planar hybrid liquid crystal (LC) cell. The free-ion concentration in the LC was found to be significantly reduced in the graphene-ITO hybrid cell compared to that in a conventional ITO-ITO cell. The free-ion concentration was suppressed in the hybrid cell due to the graphene-electrode's ion trapping process. The dielectric anisotropy of the LC was found to increase in the hybrid cell, indicating an increase in the nematic order parameter of the LC due to the reduction of ionic impurities.

Understanding and improving lithium ion batteries through mathematical modeling and experiments

NASA Astrophysics Data System (ADS)

Deshpande, Rutooj D.

There is an intense, worldwide effort to develop durable lithium ion batteries with high energy and power densities for a wide range of applications, including electric and hybrid electric vehicles. For improvement of battery technology understanding the capacity fading mechanism in batteries is of utmost importance. Novel electrode material and improved electrode designs are needed for high energy- high power batteries with less capacity fading. Furthermore, for applications such as automotive applications, precise cycle-life prediction of batteries is necessary. One of the critical challenges in advancing lithium ion battery technologies is fracture and decrepitation of the electrodes as a result of lithium diffusion during charging and discharging operations. When lithium is inserted in either the positive or negative electrode, there is a volume change associated with insertion or de-insertion. Diffusion-induced stresses (DISs) can therefore cause the nucleation and growth of cracks, leading to mechanical degradation of the batteries. With different mathematical models we studied the behavior of diffusion induces stresses and effects of electrode shape, size, concentration dependent material properties, pre-existing cracks, phase transformations, operating conditions etc. on the diffusion induced stresses. Thus we develop tools to guide the design of the electrode material with better mechanical stability for durable batteries. Along with mechanical degradation, chemical degradation of batteries also plays an important role in deciding battery cycle life. The instability of commonly employed electrolytes results in solid electrolyte interphase (SEI) formation. Although SEI formation contributes to irreversible capacity loss, the SEI layer is necessary, as it passivates the electrode-electrolyte interface from further solvent decomposition. SEI layer and diffusion induced stresses are inter-dependent and affect each-other. We study coupled chemical-mechanical degradation of electrode materials to understand the capacity fading of the battery with cycling. With the understanding of chemical and mechanical degradation, we develop a simple phenomenological model to predict battery life. On the experimental part we come up with a novel concept of using liquid metal alloy as a self-healing battery electrode. We develop a method to prepare thin film liquid gallium electrode on a conductive substrate. This enabled us to perform a series of electrochemical and characterization experiments which certify that liquid electrode undergo liquid-solid-liquid transition and thus self-heals the cracks formed during de-insertion. Thus the mechanical degradation can be avoided. We also perform ab-initio calculations to understand the equilibrium potential of various lithium-gallium phases. KEYWORDS: Lithium ion batteries, diffusion induced stresses, self-healing electrode, coupled chemical and mechanical degradation, life-prediction model.

Recovery of [CO2]T from Aqueous Bicarbonate using a Gas Permeable Membrane

DTIC Science & Technology

2008-06-25

pores as a function of differential partial gas pressures. Therefore it has been assumed for gas/ liquid systems that only the dissolved carbon dioxide...and pressure [10]. Gas permeable membranes are available commercially for the removal or addition of gases to liquids . Most of these applications...measurements were conducted with a standardized Fisher combination glass electrode. A microporous polypropylene membrane commercially designated as 2400

A selective potentiometric copper (II) ion sensor based on the functionalized ZnO nanorods.

PubMed

Khun, K; Ibupoto, Z H; Liu, X; Nur, O; Willander, M; Danielsson, B

2014-09-01

In this work, ZnO nanorods were hydrothermally grown on the gold-coated glass substrate and characterized by field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) techniques. The ZnO nanorods were functionalized by two different approaches and performance of the sensor electrode was monitored. Fourier transform infrared spectroscopy (FTIR) was carried out for the confirmation of interaction between the ionophore molecules and ZnO nanorods. In addition to this, the surface of the electrode was characterized by X-ray photoelectron spectroscopy (XPS) showing the chemical and electronic state of the ionophore and ZnO nanorod components. The ionophore solution was prepared in the stabilizer, poly vinyl chloride (PVC) and additives, and then functionalized on the ZnO nanorods that have shown the Nernstian response with the slope of 31 mV/decade. However, the Cu2+ ion sensor was fabricated only by immobilizing the selective copper ion ionophore membrane without the use of PVC, plasticizers, additives and stabilizers and the sensor electrode showed a linear potentiometric response with a slope of 56.4 mV/decade within a large dynamic concentration range (from 1.0 x 10(-6) to 1.0 x 10(-1) M) of copper (II) nitrate solutions. The sensor showed excellent repeatability and reproducibility with response time of less than 10 s. The negligible response to potentially interfering metal ions such as calcium (Ca2+), magnesium (Mg2+), potassium (K+), iron (Fe3+), zinc (Zn2+), and sodium (Na+) allows this sensor to be used in biological studies. It may also be used as an indicator electrode in the potentiometric titration.

A liquid hydrocarbon deuteron source for neutron generators

NASA Astrophysics Data System (ADS)

Schwoebel, P. R.

2017-06-01

Experimental studies of a deuteron spark source for neutron generators using hydrogen isotope fusion reactions are reported. The ion source uses a spark discharge between electrodes coated with a deuterated hydrocarbon liquid, here Santovac 5, to inhibit permanent electrode erosion and extend the lifetime of high-output neutron generator spark ion sources. Thompson parabola mass spectra show that principally hydrogen and deuterium ions are extracted from the ion source. Hydrogen is the chief residual gas phase species produced due to source operation in a stainless-steel vacuum chamber. The prominent features of the optical emission spectra of the discharge are C+ lines, the hydrogen Balmer Hα-line, and the C2 Swan bands. Operation of the ion source was studied in a conventional laboratory neutron generator. The source delivered an average deuteron current of ˜0.5 A nominal to the target in a 5 μs duration pulse at 1 Hz with target voltages of -80 to -100 kV. The thickness of the hydrocarbon liquid in the spark gap and the consistency thereof from spark to spark influences the deuteron yield and plays a role in determining the beam-focusing characteristics through the applied voltage necessary to break down the spark gap. Higher breakdown voltages result in larger ion beam spots on the target and vice-versa. Because the liquid self-heals and thereby inhibits permanent electrode erosion, the liquid-based source provides long life, with 104 pulses to date, and without clear evidence that, in principle, the lifetime could not be much longer. Initial experiments suggest that an alternative cylindrical target-type generator design can extract approximately 10 times the deuteron current from the source. Preliminary data using the deuterated source liquid as a neutron-producing target are also presented.

Poly(ionic liquid)/Ionic Liquid Ion-Gels with High "Free" Ionic Liquid Content: Platform Membrane Materials for CO2/Light Gas Separations.

PubMed

Cowan, Matthew G; Gin, Douglas L; Noble, Richard D

2016-04-19

The recycling or sequestration of carbon dioxide (CO2) from the waste gas of fossil-fuel power plants is widely acknowledged as one of the most realistic strategies for delaying or avoiding the severest environmental, economic, political, and social consequences that will result from global climate change and ocean acidification. For context, in 2013 coal and natural gas power plants accounted for roughly 31% of total U.S. CO2 emissions. Recycling or sequestering this CO2 would reduce U.S. emissions by ca. 1800 million metric tons-easily meeting the U.S.'s currently stated CO2 reduction targets of ca. 17% relative to 2005 levels by 2020. This situation is similar for many developed and developing nations, many of which officially target a 20% reduction relative to 1990 baseline levels by 2020. To make CO2 recycling or sequestration processes technologically and economically viable, the CO2 must first be separated from the rest of the waste gas mixture-which is comprised mostly of nitrogen gas and water (ca. 85%). Of the many potential separation technologies available, membrane technology is particularly attractive due to its low energy operating cost, low maintenance, smaller equipment footprint, and relatively facile retrofit integration with existing power plant designs. From a techno-economic standpoint, the separation of CO2 from flue gas requires membranes that can process extremely high amounts of CO2 over a short time period, a property defined as the membrane "permeance". In contrast, the membrane's CO2/N2 selectivity has only a minor effect on the overall cost of some separation processes once a threshold permeability selectivity of ca. 20 is reached. Given the above criteria, the critical properties when developing membrane materials for postcombustion CO2 separation are CO2 permeability (i.e., the rate of CO2 transport normalized to the material thickness), a reasonable CO2/N2 selectivity (≥20), and the ability to be processed into defect-free thin-films (ca. 100-nm-thick active layer). Traditional polymeric membrane materials are limited by a trade-off between permeability and selectivity empirically described by the "Robeson upper bound"-placing the desired membrane properties beyond reach. Therefore, the investigation of advanced and composite materials that can overcome the limitations of traditional polymeric materials is the focus of significant academic and industrial research. In particular, there has been substantial work on ionic-liquid (IL)-based materials due to their gas transport properties. This review provides an overview of our collaborative work on developing poly(ionic liquid)/ionic liquid (PIL/IL) ion-gel membrane technology. We detail developmental work on the preparation of PIL/IL composites and describe how this chemical technology was adapted to allow the roll-to-roll processing and preparation of membranes with defect-free active layers ca. 100 nm thick, CO2 permeances of over 6000 GPU, and CO2/N2 selectivity of ≥20-properties with the potential to reduce the cost of CO2 removal from coal-fired power plant flue gas to ca. $15 per ton of CO2 captured. Additionally, we examine the materials developments that have produced advanced PIL/IL composite membranes. These advancements include cross-linked PIL/IL blends, step-growth PIL/IL networks with facilitated transport groups, and PIL/IL composites with microporous additives for CO2/CH4 separations.

A four-diode full-wave ionic current rectifier based on bipolar membranes: overcoming the limit of electrode capacity.

PubMed

Gabrielsson, Erik O; Janson, Per; Tybrandt, Klas; Simon, Daniel T; Berggren, Magnus

2014-08-13

Full-wave rectification of ionic currents is obtained by constructing the typical four-diode bridge out of ion conducting bipolar membranes. Together with conjugated polymer electrodes addressed with alternating current, the bridge allows for generation of a controlled ionic direct current for extended periods of time without the production of toxic species or gas typically arising from electrode side-reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Construction and evaluation of ion selective electrodes for nitrate with a summing operational amplifier. Application to tobacco analysis.

PubMed

Pérez-Olmos, R; Rios, A; Fernández, J R; Lapa, R A; Lima, J L

2001-01-05

In this paper, the construction and evaluation of an electrode selective to nitrate with improved sensitivity, constructed like a conventional electrode (ISE) but using an operational amplifier to sum the potentials supplied by four membranes (ESOA) is described. The two types of electrodes, without an inner reference solution, were constructed using tetraoctylammonium bromide as sensor, dibutylphthalate as solvent mediator and PVC as plastic matrix, the membranes obtained directly applied onto a conductive epoxy resin support. After the comparative evaluation of their working characteristics they were used in the determination of nitrate in different types of tobacco. The limit of detection of the direct potentiometric method developed was found to be 0.18 g kg(-1) and the precision and accuracy of the method, when applied to eight different samples of tobacco, expressed in terms of mean R.S.D. and average percentage of spike recovery was 0.6 and 100.3%, respectively. The comparison of variances showed, on all ocassions, that the results obtained by the ESOA were similar to those obtained by the conventional ISE, but with higher precision. Linear regression analysis showed good agreement (r=0.9994) between the results obtained by the developed potentiometric method and those of a spectrophotometric method based on brucine, adopted as reference method, when applied simultaneously to 32 samples of different types of tobacco.

Biparametric potentiometric analytical microsystem for nitrate and potassium monitoring in water recycling processes for manned space missions.

PubMed

Calvo-López, Antonio; Arasa-Puig, Eva; Puyol, Mar; Casalta, Joan Manel; Alonso-Chamarro, Julián

2013-12-04

The construction and evaluation of a Low Temperature Co-fired Ceramics (LTCC)-based continuous flow potentiometric microanalyzer prototype to simultaneously monitor the presence of two ions (potassium and nitrate) in samples from the water recycling process for future manned space missions is presented. The microsystem integrates microfluidics and the detection system in a single substrate and it is smaller than a credit card. The detection system is based on two ion-selective electrodes (ISEs), which are built using all-solid state nitrate and potassium polymeric membranes, and a screen-printed Ag/AgCl reference electrode. The obtained analytical features after the optimization of the microfluidic design and hydrodynamics are a linear range from 10 to 1000 mg L(-1) and from 1.9 to 155 mg L(-1) and a detection limit of 9.56 mg L(-1) and 0.81 mg L(-1) for nitrate and potassium ions respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Controlled Synthesis and Functionalization of Vertically-Aligned Carbon Nanotubes for Multifunctional Applications

DTIC Science & Technology

2015-05-07

6 1.6 Lithium - Ion Batteries Based on Vertically-Aligned Carbon Nanotube Electrodes and Ionic...Cl, Br, or I) Prepared by Ball-Milling and Used as Anode Materials for Lithium - Ion Batteries ……………....................23 3.4 Well-Defined Two...9 1.6 Lithium - Ion Batteries Based on Vertically-Aligned Carbon Nanotube Electrodes and Ionic Liquid Electrolytes

Fabrication of an Inexpensive Ion-Selective Electrode.

ERIC Educational Resources Information Center

Palanivel, A.; Riyazuddin, P.

1984-01-01

The preparation and performance of a graphite (silver/copper sulfide) electrode is described. This rod, extracted from a used dry cell, is an acceptable substitute for ion-selective electrodes after it has been cleaned by abrasion followed by an overnight treatment with hydrochloric acid. (JN)

Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon

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

Soto, Fernando A.; Yan, Pengfei; Engelhard, Mark H.

Solid-electrolyte interphase (SEI) with controllable properties are highly desirable to improve battery performance. In this paper, we use a combined experimental and simulation approach to study the SEI formation on hard carbon in Li and Na-ion batteries. We show that with proper additives, stable SEI can be formed on hard carbon by pre-cycling the electrode materials in Li or Na-ion electrolyte. Detailed mechanistic studies suggest that the ion transport in the SEI layer is kinetically controlled and can be tuned by the applied voltage. Selective Na and Li-ion SEI membranes are produced using the Na or Li-ion based electrolytes respectively.more » The large Na ion SEI allows easy transport of Li ions, while the small Li ion SEI shuts off the Na-ion transport. Na-ion storage can be manipulated by tuning the SEI with film-forming electrolyte additives or preforming a SEI on the electrodes’ surface. The Na specific capacity can be controlled to <25 mAh/g, ~1/10 of the normal capacity (250 mAh/g). Unusual selective/preferential transport of Li-ion is demonstrated by preforming a SEI on the electrode’s surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion selective conductors using electrochemical approaches in the future.« less

Hydrogen-based electrochemical energy storage

DOEpatents

Simpson, Lin Jay

2013-08-06

An energy storage device (100) providing high storage densities via hydrogen storage. The device (100) includes a counter electrode (110), a storage electrode (130), and an ion conducting membrane (120) positioned between the counter electrode (110) and the storage electrode (130). The counter electrode (110) is formed of one or more materials with an affinity for hydrogen and includes an exchange matrix for elements/materials selected from the non-noble materials that have an affinity for hydrogen. The storage electrode (130) is loaded with hydrogen such as atomic or mono-hydrogen that is adsorbed by a hydrogen storage material such that the hydrogen (132, 134) may be stored with low chemical bonding. The hydrogen storage material is typically formed of a lightweight material such as carbon or boron with a network of passage-ways or intercalants for storing and conducting mono-hydrogen, protons, or the like. The hydrogen storage material may store at least ten percent by weight hydrogen (132, 134) at ambient temperature and pressure.

Improved lifetime high voltage switch electrode

NASA Astrophysics Data System (ADS)

Halverson, W.

1985-06-01

In this Phase 1 Small Business Innovation Research (SBIR) program, preliminary tests of ion implantation to increase the lifetime of spark switch electrodes have indicated that a 185 keV carbon ion implant into a tungsten-copper composite has reduced electrode erosion by a factor of two to four. Apparently, the thin layer of tungsten carbide (WC) has better thermal properties than pure tungsten; the WC may have penetrated into the unimplanted body of the electrode by liquid and/or solid phase diffusion during erosion testing. These encouraging results should provide the basis for a Phase 2 SBIR program to investigate further the physical and chemical effects of ion implantation on spark gap electrodes and to optimize the technique for applications.

A New Electrochemical Sensor Based on Task-Specific Ionic Liquids-Modified Palm Shell Activated Carbon for the Determination of Mercury in Water Samples

PubMed Central

Ismaiel, Ahmed Abu; Aroua, Mohamed Kheireddine; Yusoff, Rozita

2014-01-01

In this study, a potentiometric sensor composed of palm shell activated carbon modified with trioctylmethylammonium thiosalicylate (TOMATS) was used for the potentiometric determination of mercury ions in water samples. The proposed potentiometric sensor has good operating characteristics towards Hg (II), including a relatively high selectivity; a Nernstian response to Hg (II) ions in a concentration range of 1.0 × 10−9 to 1.0 × 10−2 M, with a detection limit of 1 × 10−10 M and a slope of 44.08 ± 1.0 mV/decade; and a fast response time (∼5 s). No significant changes in electrode potential were observed when the pH was varied over the range of 3–9. Additionally, the proposed electrode was characterized by good selectivity towards Hg (II) and no significant interferences from other cationic or anionic species. PMID:25051034

Potentiometric determination of trypsin using a polymeric membrane polycation-sensitive electrode based on current-controlled reagent delivery.

PubMed

Chen, Yan; Ding, Jiawang; Qin, Wei

2012-12-01

A potentiometric biosensor for the determination of trypsin is described based on current-controlled reagent delivery. A polymeric membrane protamine-sensitive electrode with dinonylnaphthalene sulfonate as cation exchanger is used for in situ generation of protamine. Diffusion of protamine across the polymeric membrane can be controlled precisely by applying an external current. The hydrolysis catalyzed with trypsin in sample solution decreases the concentration of free protamine released at the sample-membrane interface and facilitates the stripping of protamine out of the membrane surface via the ion-exchange process with sodium ions from the sample solution, thus decreasing the membrane potential, by which the protease can be sensed potentiometrically. The influences of anodic current amplitude, current pulse duration and protamine concentration in the inner filling solution on the membrane potential response have been studied. Under optimum conditions, the proposed protamine-sensitive electrode is useful for continuous and reversible detection of trypsin over the concentration range of 0.5-5UmL(-1) with a detection limit of 0.3UmL(-1). The proposed detection strategy provides a rapid and reagentless way for the detection of protease activities and offers great potential in the homogeneous immunoassays using proteases as labels. Copyright © 2012 Elsevier B.V. All rights reserved.

AC impedance investigations of proton conduction in Nafion(sup TM)

NASA Astrophysics Data System (ADS)

Cahan, B. D.; Wainright, J. S.

1993-12-01

AC impedance spectroscopy has been employed to study the conduction of protons in Nafion 117 polymer electrolyte membrane. Both two- and four-electrode geometries have been used to uniquely distinguish between the membrane impedance and the interfacial impedances. The results show that the impedance of Nafion for frequencies up to 100 kHz is characterized by a pure resistance, similar to conventional liquid electrolytes. The frequency dependent features observed using a two-electrode geometry are shown to be consistent will well-characterized interfacial impedances and do not arise from ionic conduction in the membrane. These results show that previous two-electrode studies reported in the literature have misinterpreted the impedance of the electrode interfaces as belonging to the conduction process in the electrolyte.

Characterization of home-made silver sulphide based iodide selective electrode.

PubMed

Rajbhandari Nyachhyon, A; Yadav, A P; Manandhar, K; Pradhananga, R R

2010-09-15

Polycrystalline silver sulphide/silver iodide ion selective electrodes (ISEs) with four different compositions, 9:1, 2:1, 1:1, 1:9 Ag(2)S-AgI mole ratios, have been fabricated in the laboratory and characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). X-ray diffraction studies show the presence of Ag(3)SI, Ag(2)S and AgI crystalline phases in the electrode material. The electrode surfaces have been found to become smoother and lustrous with increasing percentage of silver sulphide in silver iodide. ISE 1:1, ISE 2:1 and ISE 9:1 all responded in Nernstian manner with slopes of about 60 mV/decade change in iodide ion concentration in the linear range of 1 x 10(-1) to 1 x 10(-6)M while ISE 1:9 showed sub-Nernstian behavior with slope of about 45 mV up to the concentration 1 x 10(-5)M. Two capacitive loops, one corresponding to the charge transfer process at metal electrode and the back contact and a second loop corresponding to the charge transfer process at membrane-electrolyte interface have been observed at high and low frequency ranges, respectively. Mott-Schottky analysis shows that the materials are n-type semiconductors with donor defect concentrations in the range of 5.1 x 10(14) to 2.4 x 10(19)/cm(3). Copyright (c) 2010 Elsevier B.V. All rights reserved.

Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture

DOEpatents

Roelofs, Mark Gerrit; Yang, Zhen-Yu; Han, Amy Qi

2010-06-15

A fluorinated ion exchange polymer is prepared by grafting at least one grafting monomer derived from trifluorostyrene on to at least one base polymer in a organic solvent/water mixture. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores

PubMed Central

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D.; Hill, Anita J.; Wang, Huanting

2018-01-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future. PMID:29487910

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores.

PubMed

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D; Hill, Anita J; Wang, Huanting

2018-02-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future.

Indirect Determination of Mercury Ion by Inhibition of a Glucose Biosensor Based on ZnO Nanorods

PubMed Central

Chey, Chan Oeurn; Ibupoto, Zafar Hussain; Khun, Kimleang; Nur, Omer; Willander, Magnus

2012-01-01

A potentiometric glucose biosensor based on immobilization of glucose oxidase (GOD) on ZnO nanorods (ZnO-NRs) has been developed for the indirect determination of environmental mercury ions. The ZnO-NRs were grown on a gold coated glass substrate by using the low temperature aqueous chemical growth (ACG) approach. Glucose oxidase in conjunction with a chitosan membrane and a glutaraldehyde (GA) were immobilized on the surface of the ZnO-NRs using a simple physical adsorption method and then used as a potentiometric working electrode. The potential response of the biosensor between the working electrode and an Ag/AgCl reference electrode was measured in a 1mM phosphate buffer solution (PBS). The detection limit of the mercury ion sensor was found to be 0.5 nM. The experimental results provide two linear ranges of the inhibition from 0.5 × 10−6 mM to 0.5 × 10−4 mM, and from 0.5 × 10−4 mM to 20 mM of mercury ion for fixed 1 mM of glucose concentration in the solution. The linear range of the inhibition from 10−3 mM to 6 mM of mercury ion was also acquired for a fixed 10 mM of glucose concentration. The working electrode can be reactivated by more than 70% after inhibition by simply dipping the used electrode in a 10 mM PBS solution for 7 min. The electrodes retained their original enzyme activity by about 90% for more than three weeks. The response to mercury ions was highly sensitive, selective, stable, reproducible, and interference resistant, and exhibits a fast response time. The developed glucose biosensor has a great potential for detection of mercury with several advantages such as being inexpensive, requiring minimum hardware and being suitable for unskilled users. PMID:23202200

Indirect determination of mercury ion by inhibition of a glucose biosensor based on ZnO nanorods.

PubMed

Chey, Chan Oeurn; Ibupoto, Zafar Hussain; Khun, Kimleang; Nur, Omer; Willander, Magnus

2012-11-06

A potentiometric glucose biosensor based on immobilization of glucose oxidase (GOD) on ZnO nanorods (ZnO-NRs) has been developed for the indirect determination of environmental mercury ions. The ZnO-NRs were grown on a gold coated glass substrate by using the low temperature aqueous chemical growth (ACG) approach. Glucose oxidase in conjunction with a chitosan membrane and a glutaraldehyde (GA) were immobilized on the surface of the ZnO-NRs using a simple physical adsorption method and then used as a potentiometric working electrode. The potential response of the biosensor between the working electrode and an Ag/AgCl reference electrode was measured in a 1mM phosphate buffer solution (PBS). The detection limit of the mercury ion sensor was found to be 0.5 nM. The experimental results provide two linear ranges of the inhibition from 0.5 × 10(-6) mM to 0.5 × 10(-4) mM, and from 0.5 × 10(-4) mM to 20 mM of mercury ion for fixed 1 mM of glucose concentration in the solution. The linear range of the inhibition from 10(-3) mM to 6 mM of mercury ion was also acquired for a fixed 10 mM of glucose concentration. The working electrode can be reactivated by more than 70% after inhibition by simply dipping the used electrode in a 10 mM PBS solution for 7 min. The electrodes retained their original enzyme activity by about 90% for more than three weeks. The response to mercury ions was highly sensitive, selective, stable, reproducible, and interference resistant, and exhibits a fast response time. The developed glucose biosensor has a great potential for detection of mercury with several advantages such as being inexpensive, requiring minimum hardware and being suitable for unskilled users.

Anion recognition using newly synthesized hydrogen bonding disubstituted phenylhydrazone-based receptors: poly(vinyl chloride)-based sensor for acetate.

PubMed

Gupta, Vinod K; Goyal, Rajendra N; Sharma, Ram A

2008-08-15

A potentiometric acetate-selective sensor, based on the use of butane-2,3-dione,bis[(2,4-dinitrophenyl)hydrazone] (BDH) as a neutral carrier in poly(vinyl chloride) (PVC) matrix, is reported. Effect of various plasticizers and cation excluder, cetryaltrimethylammonium bromide (CTAB) was studied. The best performance was obtained with a membrane composition of PVC:BDH:CTAB ratio (w/w; mg) of 160:8:8. The sensor exhibits significantly enhanced selectivity toward acetate ions over a wide concentration range 5.0 x 10(-6) to 1.0 x 10(-1)M with a lower detection limit of 1.2 x 10(-6)M within pH range 6.5-7.5 with a response time of <15s and a Nernstian slope of 60.3+/-0.3 mV decade(-1) of activity. Influences of the membrane composition, and possible interfering anions were investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability are demonstrated. The sensor has a response time of 15s and can be used for at least 65 days without any considerable divergence in their potential response. Selectivity coefficients determined with the separate solution method (SSM) and fixed interference method (FIM) indicate that high selectivity for acetate ion. The proposed electrode shows fairly good discrimination of acetate from several inorganic and organic anions. It was successfully applied to direct determination of acetate within food preservatives. Total concentration of acetic acid in vinegar samples were determined by direct potentiometry and the values agreed with those mentioned by the manufacturers.

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

PubMed

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

2012-04-17

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

Membrane electrode gasket assembly (MEGA) technology for polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Pozio, A.; Giorgi, L.; De Francesco, M.; Silva, R. F.; Lo Presti, R.; Danzi, A.

A new technology for the production of a membrane electrode gasket assembly (MEGA) for polymer electrolyte fuel cells (PEFCs) is defined. The MEGA system was prepared by sealing a previously prepared membrane electrode assembly (MEA) in a moulded gasket. For this aim, a proprietary silicone based liquid mixture was injected directly into the MEA borders. Gaskets obtained in different shapes and hardness grades are stable in a wide temperature range. The MEGA technology shows several advantages with respect to traditional PEFCs stack assembling systems: effective membrane saving, reduced fabrication time, possibility of quality control and failed elements substitution. This technology was successfully tested at the ENEA laboratories and the results were acquired in laboratory scale, but industrial production appears to be simple and cheap.

Ultra-Thin Solid-State Nanopores: Fabrication and Applications

NASA Astrophysics Data System (ADS)

Kuan, Aaron Tzeyang

Solid-state nanopores are a nanofluidic platform with unique advantages for single-molecule analysis and filtration applications. However, significant improvements in device performance and scalable fabrication methods are needed to make nanopore devices competitive with existing technologies. This dissertation investigates the potential advantages of ultra-thin nanopores in which the thickness of the membrane is significantly smaller than the nanopore diameter. Novel, scalable fabrication methods were first developed and then utilized to examine device performance for water filtration and single molecule sensing applications. Fabrication of nanometer-thin pores in silicon nitride membranes was achieved using a feedback-controlled ion beam method in which ion sputtering is arrested upon detection of the first few ions that drill through the membrane. Performing fabrication at liquid nitrogen temperatures prevents surface atom rearrangements that have previously complicated similar processes. A novel cross-sectional imaging method was also developed to allow careful examination of the full nanopore geometry. Atomically-thin graphene nanopores were fabricated via an electrical pulse method in which sub-microsecond electrical pulses applied across a graphene membrane in electrolyte solution are used to create a defect in the membrane and controllably enlarge it into a nanopore. This method dramatically increases the accuracy and reliability of graphene nanopore production, allowing consistent production of single nanopores down to subnanometer sizes. In filtration applications in which nanopores are used to selectively restrict the passage of dissolved contaminants, ultra-thin nanopores minimize the flow resistance, increasing throughput and energy-efficiency. The ability of graphene nanopores to separate different ions was characterized via ionic conductance and reversal potential measurements. Graphene nanopores were observed to conduct cations preferentially over anions with selectivity ratios of 100 or higher for pores as large as 20 nm in diameter, suggesting that porous graphene membranes can be used to create highly effective cation exchange membranes for electrodialysis filtration. These surprisingly high selectivities cannot be explained by current models of ionic conduction in graphene nanopores, motivating the development of a new model in which elevated concentrations of mobile cations near the graphene surface generate additional ion selectivity.

Method of removing oxides of sulfur and oxides of nitrogen from exhaust gases

DOEpatents

Walker, Richard J.

1986-01-01

A continuous method is presented for removing both oxides of sulfur and oxides of nitrogen from combustion or exhaust gases with the regeneration of the absorbent. Exhaust gas is cleaned of particulates and HCl by a water scrub prior to contact with a liquid absorbent that includes an aqueous solution of bisulfite and sulfite ions along with a metal chelate, such as, an iron or zinc aminopolycarboxylic acid. Following contact with the combustion gases the spent absorbent is subjected to electrodialysis to transfer bisulfite ions into a sulfuric acid solution while splitting water with hydroxide and hydrogen ion migration to equalize electrical charge. The electrodialysis stack includes alternate layers of anion selective and bipolar membranes. Oxides of nitrogen are removed from the liquid absorbent by air stripping at an elevated temperature and the regenerated liquid absorbent is returned to contact with exhaust gases for removal of sulfur oxides and nitrogen oxides.

Titanium (III) cation selective electrode based on synthesized tris(2pyridyl) methylamine ionophore and its application in water samples

NASA Astrophysics Data System (ADS)

Rezayi, Majid; Karazhian, Reza; Abdollahi, Yadollah; Narimani, Leila; Sany, Seyedeh Belin Tavakoly; Ahmadzadeh, Saeid; Alias, Yatimah

2014-04-01

The introduction of low detection limit ion selective electrodes (ISEs) may well pave the way for the determination of trace targets of cationic compounds. This research focuses on the detection of titanium (III) cation using a new PVC-membrane sensor based on synthesized tris(2pyridyl) methylamine (tpm) ionophore. The application and validation of the proposed sensor was done using potentiometric titration, inductively coupled plasma atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). The membrane sensor exhibited a Nernstian response to the titanium (III) cation over a concentration range of 1.0 × 10-6-1.0 × 10-2 M and pH range from 1-2.5. The Nernstian slope, the lower of detection (LOD), and the response time (t95%) of the proposed sensor were 29.17 +/- 0.24 mV/dec, 7.9 × 10-7 M, and 20 s, respectively. The direct determination of 4-39 μg/ml of titanium (III) standard solution showed an average recovery of 94.60 and a mean relative standard deviation of 1.8 at 100.0 μg/ml. Finally, the utilization of the electrodes as end-point indicators for potentiometric titration with EDTA solutions for titanium (III) sensor was successfully carried out.

High-capacity FeTiO3/C negative electrode for sodium-ion batteries with ultralong cycle life

NASA Astrophysics Data System (ADS)

Ding, Changsheng; Nohira, Toshiyuki; Hagiwara, Rika

2018-06-01

The development of electrode materials which improve both the energy density and cycle life is one of the most challenging issues facing the practical application of sodium-ion batteries today. In this work, FeTiO3/C nanoparticles are synthesized as negative electrode materials for sodium-ion batteries. The electrochemical performance and charge-discharge mechanism of the FeTiO3/C negative electrode are investigated in an ionic liquid electrolyte at 90 °C. The FeTiO3/C negative electrode delivers a high reversible capacity of 403 mAh g-1 at a current rate of 10 mA g-1, and exhibits high rate capability and excellent cycling stability for up to 2000 cycles. The results indicate that FeTiO3/C is a promising negative electrode material for sodium-ion batteries.

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

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

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

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

Functionalized β-cyclodextrin based potentiometric sensor for naproxen determination.

PubMed

Lenik, Joanna; Łyszczek, Renata

2016-04-01

Potentiometric sensors based on neutral β-cyclodextrins: (2-hydroxypropyl)-β-cyclodextrin, heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin, heptakis(2,3,6-tri-O-benzoyl)-β-cyclodextrin and anionic β-cyclodextrin: (2-hydroxy-3-N,N,N-trimethylamino)propyl-β-cyclodextrin chloride for naproxen are described. Inclusion complexes of naproxen with the above-mentioned cyclodextrins were studied using IR spectroscopy. The electrode surface was made from PVC membranes doped with the appropriate β-cyclodextrin as ionophores and quaternary ammonium chlorides as positive charge additives that were dispersed in plasticizers. The optimum membrane contains heptakis(2,3,6-tri-O-benzoyl)-β-cyclodextrin, o-nitrophenyloctyl ether and tetraoctyl ammonium chloride as a lipophilic salt. The electrode is characterized by a Nernstian response slope of -59.0 ± 0.5 mV decade(-1) over the linear range of 5.0 × 10(-5)-1.0 × 10(-2) mol L(-1) and the detection limit 1.0 × 10(-5) mol L(-1), as well as the response time 10s. It can be used in the pH range 6.2-8.5 for 10 months without any considerable deterioration. Incorporation of β-cyclodextrins improved the electrode selectivity towards naproxen ions from several inorganic and organic interferents and some common drug excipients due to concovalent interactions (host molecule-guest molecule). The notable advantages of the naproxen-selective electrode include its high sensitivity, high selectivity, cost-effectiveness as well as accurate and comfortable application in drug analysis and milk samples. Copyright © 2015. Published by Elsevier B.V.

Aqueous liquid feed organic fuel cell using solid polymer electrolyte membrane

NASA Technical Reports Server (NTRS)

Olah, George A. (Inventor); Surampudi, Subbarao (Inventor); Vamos, Eugene (Inventor); Halpert, Gerald (Inventor); Narayanan, Sekharipuram R. (Inventor); Frank, Harvey A. (Inventor); Prakash, G. K. Surya (Inventor)

1997-01-01

A liquid organic fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion.TM.. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon.TM.-binder structure is immersed within a Nafion.TM./methanol bath to impregnate the electrode with Nafion.TM.. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.

Polymethacrylate Polymers with Appended Aluminum(III)-Tetraphenylporphyrins: Synthesis, Characterization and Evaluation as Macromolecular Ionophores for Electrochemical and Optical Fluoride Sensors

PubMed Central

Wang, Lin; Meyerhoff, Mark E.

2008-01-01

The synthesis and characterization of a novel polymethacylate polymer with covalently linked Al(III)-tetraphenylporphyrin (Al(III)-TPP) groups is reported. The new polymer is examined as a potential macromolecular ionophore for the preparation of polymeric membrane-based potentiometric and optical fluoride selective sensors. To prepare the polymer, an Al(III) porphyrin monomer modified with a methacrylate functionality is synthesized, allowing insertion into a polymethacrylate block copolymer (methyl methacrylate and decyl methacrylate) backbone. The resulting polymer can then be incorporated, along with appropriate additives, into conventional plasticized poly(vinyl chloride) films for testing electrochemical and optical fluoride response properties. The covalent attachment of the Al(III)-TPP ionophore to the copolymer matrix provides potentiometric sensors that exhibit significant selectivity for fluoride ion with extended lifetimes (compared to ion-selective membrane electrodes formulated with conventional free Al(III)-TPP structure). However, quite surprisingly, the attachment of the ionophore to the polymer does not eliminate the interaction of Al(III)-TPP structures to form dimeric species within the membrane phase in the presence of fluoride ion. Such interactions are confirmed by UV/visible spectroscopy of the blended polymeric films. Use of the new polymer-Al(III)-TPP conjugates to prepare optical fluoride sensors by co-incorporating a lipophilic pH indicator (4’,5’-dibromofluorescein octadecyl ester; ETH7075) is also examined and the resulting optical sensing films are shown to exhibit excellent selectivity for fluoride, with the potential for prolonged operational lifetime. PMID:18298973

Membrane interactions of ionic liquids and imidazolium salts.

PubMed

Wang, Da; Galla, Hans-Joachim; Drücker, Patrick

2018-06-01

Room-temperature ionic liquids (RTILs) have attracted considerable attention in recent years due to their versatile properties such as negligible volatility, inflammability, high extractive selectivity and thermal stability. In general, RTILs are organic salts with a melting point below ~100 °C determined by the asymmetry of at least one of their ions. Due to their amphiphilic character, strong interactions with biological materials can be expected. However, rising attention has appeared towards their similarity and interaction with biomolecules. By employing structural modifications, the biochemical properties of RTILs can be designed to mimic lipid structures and to tune their hydrophobicity towards a lipophilic behavior. This is evident for the interaction with lipid-membranes where some of these compounds present membrane-disturbing effects or cellular toxicity. Moreover, they can form micelles or lipid-like bilayer structures by themselves. Both aspects, cellular effects and membrane-forming capacities, of a novel class of lipophilic imidazolium salts will be discussed.

Production of an ion-exchange membrane-catalytic electrode bonded material for electrolytic cells

NASA Technical Reports Server (NTRS)

Takenaka, H.; Torikai, E.

1986-01-01

A good bond is achieved by placing a metal salt in solution on one side of a membrane and a reducing agent on the other side so that the reducing agent penetrates the membrane and reduces the metal. Thus, a solution containing Pt, Rh, etc., is placed on one side of the membrane and a reducing agent such as NaBH, is placed on the other side. The bonded metal layer obtained is superior in catalytic activity and is suitable as an electrode in a cell such as for solid polymer electrolyte water electrolysis.

System and method for liquid extraction electrospray-assisted sample transfer to solution for chemical analysis

DOEpatents

Kertesz, Vilmos; Van Berkel, Gary J.

2016-07-12

A system for sampling a surface includes a surface sampling probe comprising a solvent liquid supply conduit and a distal end, and a sample collector for suspending a sample collection liquid adjacent to the distal end of the probe. A first electrode provides a first voltage to solvent liquid at the distal end of the probe. The first voltage produces a field sufficient to generate electrospray plume at the distal end of the probe. A second electrode provides a second voltage and is positioned to produce a plume-directing field sufficient to direct the electrospray droplets and ions to the suspended sample collection liquid. The second voltage is less than the first voltage in absolute value. A voltage supply system supplies the voltages to the first electrode and the second electrode. The first electrode can apply the first voltage directly to the solvent liquid. A method for sampling for a surface is also disclosed.

Soft X-ray emission spectroscopy of liquids and lithium batterymaterials

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

Augustsson, Andreas

2004-01-01

Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed tomore » view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools. In this thesis examples of studies of lithium battery electrodes and liquid systems using soft x-ray emission spectroscopy will be presented. Monochromatized synchrotron radiation has been used to accomplish selective excitation, in terms of energy and polarization. The electronic structure of graphite electrodes has been studied, before and after lithium intercalation. Changes in the electronic structure upon lithiation due to transfer of electrons into the graphite π-bands have been observed. Transfer of electrons in to the 3d states of transition metal oxides upon lithiation have been studied, through low energy excitations as dd- and charge transfer-excitations. A SEI was detected on cycled graphite electrodes. By the use of selective excitation different carbon sites were probed in the SEI. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell, to separate the liquid from the vacuum in the experimental chamber. Results from the study of liquid water showed a strong influence on the 3a1 molecular orbital and orbital mixing between water molecules upon hydrogen bonding. Apart from the four-hydrogen-bonding structure in water, a structure where one hydrogen bond is broken could be separated and identified. The soft x-ray emission study of methanol showed the existence of ring and chain formations in the liquid phase and the dominating structures are formed of 6 and 8 molecules. Upon mixing of the two liquids, a segregation at the molecular level was found and the formation of new structures, which could explain the unexpected low increase of the entropy.« less

Bio-inspired spider-web-like membranes with a hierarchical structure for high performance lithium/sodium ion battery electrodes: the case of 3D freestanding and binder-free bismuth/CNF anodes.

PubMed

Jin, Yuqiang; Yuan, Haocheng; Lan, Jin-Le; Yu, Yunhua; Lin, Yuan-Hua; Yang, Xiaoping

2017-09-14

High gravimetric energy density and volumetric energy density energy storage devices are highly desirable due to the rapid development of electric vehicles, and portable and wearable electronic equipment. Electrospinning is a promising technology for preparing freestanding electrodes with high gravimetric and volumetric energy density. However, the energy density of the traditional electrospun electrodes is restricted by the low mass loading of active materials (e.g. 20%-30 wt%). Herein, a biomimetic strategy inspired by the phenomenon of the sticky spider web is demonstrated as a high performance anode, which simultaneously improves the gravimetric and volumetric energy density. Freestanding carbon nanofiber (CNF) membranes containing over 50 wt% of bismuth were prepared by electrospinning and subsequent thermal treatment. Membranes consisting of CNF network structures bonded tightly with active Bi cluster materials, resulting in excellent mechanical protection and a fast charge transport path, which are difficult to achieve simultaneously. The composite membrane delivers high reversible capacity (483 mA h g -1 at 100 mA g -1 after 200 cycles) and high rate performance (242 mA h g -1 at 1 A g -1 ) as a lithium-ion battery anode. For use as a sodium ion battery, the composite membrane also shows a high reversible specific capacity of 346 mA h g -1 and outstanding cycling performance (186 mA h g -1 at 50 mA g -1 after 100 cycles). This work offers a simple, low cost and eco-friendly method for fabricating free-standing and binder-free composite electrodes with high loading used in LIBs and SIBs.

Field ionizing elements and applications thereof

NASA Technical Reports Server (NTRS)

Hartley, Frank T. (Inventor)

2003-01-01

A field ionizing element formed of a membrane that houses electrodes therein that are located closer to one another than the mean free path of the gas being ionized. The membrane includes a supporting portion, and a non supporting portion where the ions are formed. The membrane may be used as the front end for a number of different applications including a mass spectrometer, a thruster, an ion mobility element, or an electrochemical device such as a fuel cell.

A Membrane-Free Ferrocene-Based High-Rate Semiliquid Battery.

PubMed

Ding, Yu; Zhao, Yu; Yu, Guihua

2015-06-10

We report here a ferrocene-based membrane-free, high-rate semiliquid battery that takes advantage of a highly soluble ferrocene/ferrocenium redox couple in nonaqueous phase. The designed battery exhibits stable capacity retention up to 94% of theoretical capacity of ferrocene (145 mAh g(-1)) at a broad current rate up to 60 C owing to rapid mass transport in a liquid phase and fast redox kinetics. The diffusion coefficient and the standard reaction constant are determined to be in the order of 10(-6) cm(2) s(-1) and 10(-1) cm s(-1), respectively, orders of magnitude greater than those in a solid-phase electrode and those in conventional redox flow batteries. Additionally, the battery demonstrates power density and energy density exceeding 1400 W L(-1) and 40 Wh L(-1), respectively, and stable cyclability with capacity retention of ∼80% for 500 cycles. Compared with state-of-the-art energy storage technologies such as Li-ion batteries or conventional redox flow batteries, the proposed liquid battery shows the potential to be an efficient energy storage system with exceptionally high power and reasonable energy density.

Interfaces and Materials in Lithium Ion Batteries: Challenges for Theoretical Electrochemistry.

PubMed

Kasnatscheew, Johannes; Wagner, Ralf; Winter, Martin; Cekic-Laskovic, Isidora

2018-04-18

Energy storage is considered a key technology for successful realization of renewable energies and electrification of the powertrain. This review discusses the lithium ion battery as the leading electrochemical storage technology, focusing on its main components, namely electrode(s) as active and electrolyte as inactive materials. State-of-the-art (SOTA) cathode and anode materials are reviewed, emphasizing viable approaches towards advancement of the overall performance and reliability of lithium ion batteries; however, existing challenges are not neglected. Liquid aprotic electrolytes for lithium ion batteries comprise a lithium ion conducting salt, a mixture of solvents and various additives. Due to its complexity and its role in a given cell chemistry, electrolyte, besides the cathode materials, is identified as most susceptible, as well as the most promising, component for further improvement of lithium ion batteries. The working principle of the most important commercial electrolyte additives is also discussed. With regard to new applications and new cell chemistries, e.g., operation at high temperature and high voltage, further improvements of both active and inactive materials are inevitable. In this regard, theoretical support by means of modeling, calculation and simulation approaches can be very helpful to ex ante pre-select and identify the aforementioned components suitable for a given cell chemistry as well as to understand degradation phenomena at the electrolyte/electrode interface. This overview highlights the advantages and limitations of SOTA lithium battery systems, aiming to encourage researchers to carry forward and strengthen the research towards advanced lithium ion batteries, tailored for specific applications.

Membraneless laminar flow cell for electrocatalytic CO 2 reduction with liquid product separation

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

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei

The production of liquid fuel products via electrochemical reduction of CO 2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O 2) from reaching the cathode. Ion-conducting membranes have been applied in CO 2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flowmore » cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO 2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.« less

Membraneless laminar flow cell for electrocatalytic CO 2 reduction with liquid product separation

DOE PAGES

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei; ...

2017-03-16

The production of liquid fuel products via electrochemical reduction of CO 2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O 2) from reaching the cathode. Ion-conducting membranes have been applied in CO 2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flowmore » cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO 2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.« less

Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

PubMed

Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

2016-01-14

In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested.

Carbon/PTFE Electrode for Lithium/Air-Water Batteries

DTIC Science & Technology

2007-03-01

non-electronically conducting ceramic membrane impervious to water but with a high ionic conductivity for lithium-ions. LiTixAly(PO4)3 is one such...example of a ceramic composition that has been used in this manner. The lithium ion can be thought of as being solvated by the ceramic membrane as it...through 5) provides current. To balance the overall charge in the reaction, positive lithium ions flow 1 through an ionically conducting ceramic

NASA Redox Storage System Development Project

NASA Technical Reports Server (NTRS)

Hagedorn, N. H.

1984-01-01

The Redox Storage System Technology Project was jointly supported by the U.S. Department of Energy and NASA. The objectives of the project were to develop the Redox flow battery concept and to probe its technical and economic viability. The iron and chromium redox couples were selected as the reactants. Membranes and electrodes were developed for the original mode of operating at 25 C with the reactants separated by an ion-exchange membrane. Analytical capabilities and system-level operating concepts were developed and verified in a 1-kW, 13-kWh preprototype system. A subsequent change was made in operating mode, going to 65 C and using mixed reactants. New membranes and a new electrode catalyst were developed, resulting in single cell operation as high as 80 mA/sq cm with energy efficiencies greater than 80 percent. Studies indicate a likely system cost of about $75/kWh. Standard Oil of Ohio (Sohio) has undertaken further development of the Redox system. An exclusive patent license was obtained from NASA by Sohio. Transfer of Redox technology to Sohio is supported by the NASA Technology Utilization Office.

Formulated plastic separators for soluble electrode cells. [rubber-ion transport membranes

NASA Technical Reports Server (NTRS)

Sheibley, D. W. (Inventor)

1979-01-01

The fabrication and milling of membranes comprising a hydrochloric acid-insoluble sheet of a mixture of a rubber and a powdered ion transport material are described. The sheet can be present as a coating upon a flexible and porous substrate. These membranes can be used in oxidation-reduction electrical accumulator cells wherein the reduction of one member of a couple is accompanied by the by the oxidation of the other member of the couple on the other side of the cell and this must be accompanied by a change in chloride ion concentration in both sides.

Diels Alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

DOE PAGES

Small, Leo J.; Pratt, III, Harry D.; Fujimoto, Cy H.; ...

2015-10-23

Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3–10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediatemore » ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. As a result, improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.« less

Numerical analysis of field-modulated electroosmotic flows in microchannels with arbitrary numbers and configurations of discrete electrodes.

PubMed

Chao, Kan; Chen, Bo; Wu, Jiankang

2010-12-01

The formation of an electric double layer and electroosmosis are important theoretic foundations associated with microfluidic systems. Field-modulated electroosmotic flows in microchannels can be obtained by applying modulating electric fields in a direction perpendicular to a channel wall. This paper presents a systematic numerical analysis of modulated electroosmotic flows in a microchannel with discrete electrodes on the basis of the Poisson equation of electric fields in a liquid-solid coupled domain, the Navier-Stokes equation of liquid flow, and the Nernst-Planck equation of ion transport. These equations are nonlinearly coupled and are simultaneously solved numerically for the electroosmotic flow velocity, electric potential, and ion concentrations in the microchannel. A number of numerical examples of modulated electroosmotic flows in microchannels with discrete electrodes are presented, including single electrodes, symmetric/asymmetric double electrodes, and triple electrodes. Numerical results indicate that chaotic circulation flows, micro-vortices, and effective fluid mixing can be realized in microchannels by applying modulating electric fields with various electrode configurations. The interaction of a modulating field with an applied field along the channel is also discussed.

Electrochemical ion transfer across liquid/liquid interfaces confined within solid-state micropore arrays--simulations and experiments.

PubMed

Strutwolf, Jörg; Scanlon, Micheál D; Arrigan, Damien W M

2009-01-01

Miniaturised liquid/liquid interfaces provide benefits for bioanalytical detection with electrochemical methods. In this work, microporous silicon membranes which can be used for interface miniaturisation were characterized by simulations and experiments. The microporous membranes possessed hexagonal arrays of pores with radii between 10 and 25 microm, a pore depth of 100 microm and pore centre-to-centre separations between 99 and 986 microm. Cyclic voltammetry was used to monitor ion transfer across arrays of micro-interfaces between two immiscible electrolyte solutions (microITIES) formed at these membranes, with the organic phase present as an organogel. The results were compared to computational simulations taking into account mass transport by diffusion and encompassing diffusion to recessed interfaces and overlapped diffusion zones. The simulation and experimental data were both consistent with the situation where the location of the liquid/liquid (l/l) interface was on the aqueous side of the silicon membrane and the pores were filled with the organic phase. While the current for the forward potential scan (transfer of the ion from the aqueous phase to the organic phase) was strongly dependent on the location of the l/l interface, the current peak during the reverse scan (transfer of the ion from the organic phase to the aqueous phase) was influenced by the ratio of the transferring ion's diffusion coefficients in both phases. The diffusion coefficient of the transferring ion in the gelified organic phase was ca. nine times smaller than in the aqueous phase. Asymmetric cyclic voltammogram shapes were caused by the combined effect of non-symmetrical diffusion (spherical and linear) and by the inequality of the diffusion coefficient in both phases. Overlapping diffusion zones were responsible for the observation of current peaks instead of steady-state currents during the forward scan. The characterisation of the diffusion behaviour is an important requirement for application of these silicon membranes in electroanalytical chemistry.

High-performance supercapacitors based on poly(ionic liquid)-modified graphene electrodes.

PubMed

Kim, Tae Young; Lee, Hyun Wook; Stoller, Meryl; Dreyer, Daniel R; Bielawski, Christopher W; Ruoff, Rodney S; Suh, Kwang S

2011-01-25

We report a high-performance supercapacitor incorporating a poly(ionic liquid)-modified reduced graphene oxide (PIL:RG-O) electrode and an ionic liquid (IL) electrolyte (specifically, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide or EMIM-NTf(2)). PIL:RG-O provides enhanced compatibility with the IL electrolyte, thereby increasing the effective electrode surface area accessible to electrolyte ions. The supercapacitor assembled with PIL:RG-O electrode and EMIM-NTf(2) electrolyte showed a stable electrochemical response up to 3.5 V operating voltage and was capable of yielding a maximum energy density of 6.5 W·h/kg with a power density of 2.4 kW/kg. These results demonstrate the potential of the PIL:RG-O material as an electrode in high-performance supercapacitors.

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.

Promising applications of graphene and graphene-based nanostructures

NASA Astrophysics Data System (ADS)

Nguyen, Bich Ha; Hieu Nguyen, Van

2016-06-01

The present article is a review of research works on promising applications of graphene and graphene-based nanostructures. It contains five main scientific subjects. The first one is the research on graphene-based transparent and flexible conductive films for displays and electrodes: efficient method ensuring uniform and controllable deposition of reduced graphene oxide thin films over large areas, large-scale pattern growth of graphene films for stretchble transparent electrodes, utilization of graphene-based transparent conducting films and graphene oxide-based ones in many photonic and optoelectronic devices and equipments such as the window electrodes of inorganic, organic and dye-sensitized solar cells, organic light-emitting diodes, light-emitting electrochemical cells, touch screens, flexible smart windows, graphene-based saturated absorbers in laser cavities for ultrafast generations, graphene-based flexible, transparent heaters in automobile defogging/deicing systems, heatable smart windows, graphene electrodes for high-performance organic field-effect transistors, flexible and transparent acoustic actuators and nanogenerators etc. The second scientific subject is the research on conductive inks for printed electronics to revolutionize the electronic industry by producing cost-effective electronic circuits and sensors in very large quantities: preparing high mobility printable semiconductors, low sintering temperature conducting inks, graphene-based ink by liquid phase exfoliation of graphite in organic solutions, and developing inkjet printing technique for mass production of high-quality graphene patterns with high resolution and for fabricating a variety of good-performance electronic devices, including transparent conductors, embedded resistors, thin-film transistors and micro supercapacitors. The third scientific subject is the research on graphene-based separation membranes: molecular dynamics simulation study on the mechanisms of the transport of molecules, vapors and gases through nanopores in graphene membranes, experimental works investigating selective transport of different molecules through nanopores in single-layer graphene and graphene-based membranes toward the water desalination, chemical mixture separation and gas control. Various applications of graphene in bio-medicine are the contents of the fourth scientific subject of the review. They include the DNA translocations through nanopores in graphene membranes toward the fabrication of devices for genomic screening, in particular DNA sequencing; subnanometre trans-electrode membranes with potential applications to the fabrication of very high resolution, high throughput nanopore-based single-molecule detectors; antibacterial activity of graphene, graphite oxide, graphene oxide and reduced graphene oxide; nanopore sensors for nucleic acid analysis; utilization of graphene multilayers as the gates for sequential release of proteins from surface; utilization of graphene-based electroresponsive scaffolds as implants for on-demand drug delivery etc. The fifth scientific subject of the review is the research on the utilization of graphene in energy storage devices: ternary self-assembly of ordered metal oxide-graphene nanocomposites for electrochemical energy storage; self-assembled graphene/carbon nanotube hybrid films for supercapacitors; carbon-based supercapacitors fabricated by activation of graphene; functionalized graphene sheet-sulfure nanocomposite for using as cathode material in rechargeable lithium batteries; tunable three-dimensional pillared carbon nanotube-graphene networks for high-performance capacitance; fabrications of electrochemical micro-capacitors using thin films of carbon nanotubes and chemically reduced graphenes; laser scribing of high-performance and flexible graphene-based electrochemical capacitors; emergence of next-generation safe batteries featuring graphene-supported Li metal anode with exceptionally high energy or power densities; fabrication of anodes for lithium ion batteries from crumpled graphene-encapsulated Si nanoparticles; liquid-mediated dense integration of graphene materials for compact capacitive energy storage; scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage; superior micro-supercapacitors based on graphene quantum dots; all-graphene core-sheat microfibres for all-solid-state, stretchable fibriform supercapacitors and wearable electronic textiles; micro-supercapacitors with high electrochemical performance based on three-dimensional graphene-carbon nanotube carpets; macroscopic nitrogen-doped graphene hydrogels for ultrafast capacitors; manufacture of scalable ultra-thin and high power density graphene electrochemical capacitor electrodes by aqueous exfoliation and spray deposition; scalable synthesis of hierarchically structured carbon nanotube-graphene fibers for capacitive energy storage; phosphorene-graphene hybrid material as a high-capacity anode material for sodium-ion batteries. Beside above-presented promising applications of graphene and graphene-based nanostructures, other less widespread, but perhaps not less important, applications of graphene and graphene-based nanomaterials, are also briefly discussed.

Method and apparatus for selective filtering of ions

DOEpatents

Page, Jason S [Kennewick, WA; Tang, Keqi [Richland, WA; Smith, Richard D [Richland, WA

2009-04-07

An adjustable, low mass-to-charge (m/z) filter is disclosed employing electrospray ionization to block ions associated with unwanted low m/z species from entering the mass spectrometer and contributing their space charge to down-stream ion accumulation steps. The low-mass filter is made by using an adjustable potential energy barrier from the conductance limiting terminal electrode of an electrodynamic ion funnel, which prohibits species with higher ion mobilities from being transmitted. The filter provides a linear voltage adjustment of low-mass filtering from m/z values from about 50 to about 500. Mass filtering above m/z 500 can also be performed; however, higher m/z species are attenuated. The mass filter was evaluated with a liquid chromatography-mass spectrometry analysis of an albumin tryptic digest and resulted in the ability to block low-mass, "background" ions which account for 40-70% of the total ion current from the ESI source during peak elution.

Imidazolium-organic solvent mixtures as electrolytes for lithium batteries

NASA Astrophysics Data System (ADS)

Chagnes, A.; Diaw, M.; Carré, B.; Willmann, P.; Lemordant, D.

γ-Butyrolactone (BL) has been mixed to the room temperature ionic liquid (RTIL) 1-butyl 3-methyl-imidazolium tetrafluoroborate (BMIBF 4) (ratio: 3/2, v/v) in the presence of lithium tetrafluoroborate (LiBF 4) for use as electrolyte in lithium-ion batteries. This mixture exhibits a larger thermal stability than the reference electrolyte EC/DEC/DMC (2/2/1) + LiPF 6 (1 M) and can be considered as a new RTIL as no free BL molecules are present in the liquid phase. The cycling ability of this electrolyte has been investigated at a graphite, a titanate oxide (Li 4Ti 5O 12) and a cobalt oxide (Li xCoO 2) electrodes. The ionic liquid is strongly reduced at the graphite electrode near 1 V and leads to the formation of a blocking film, which prevents any further cycling. The titanate oxide electrode can be cycled with a high capacity without any significant fading. Cycling of the positive cobalt oxide electrode was unsuccessfully owing to an oxidation reaction at the electrode surface, which prevents the intercalation or de-intercalation of Li ions in and from the host material. Less reactive cathode material than cobalt oxide must be employed with this RTIL.

Metal-air cell comprising an electrolyte with a room temperature ionic liquid and hygroscopic additive

DOEpatents

Friesen, Cody A.; Krishnan, Ramkumar; Tang, Toni; Wolfe, Derek

2014-08-19

An electrochemical cell comprising an electrolyte comprising water and a hydrophobic ionic liquid comprising positive ions and negative ions. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. A hydrophilic or hygroscopic additive modulates the hydrophobicity of the ionic liquid to maintain a concentration of the water in the electrolyte is between 0.001 mol % and 25 mol %.

Fuel Cell Performance Implications of Membrane Electrode Assembly Fabrication with Platinum-Nickel Nanowire Catalysts

DOE PAGES

Mauger, Scott A.; Neyerlin, K. C.; Alia, Shaun M.; ...

2018-03-13

Platinum-nickel nanowire (PtNiNW) catalysts have shown exceptionally high oxygen reduction mass activity in rotating disk electrode measurements. However, the ability to successfully incorporate PtNiNWs into high performance membrane electrode assemblies (MEAs) has been challenging due to their size, shape, density, dispersion characteristics, and corrosion-susceptible nickel core. We have investigated the impact of specific processing steps and electrode composition on observed fuel cell performance and electrochemical properties in order to optimize performance. We have found that nickel ion contamination is a major concern for PtNiNWs that can be addressed through ion exchange in fabricated/tested MEAs or by acid leaching of catalystmore » materials prior to MEA incorporation, with the latter being the more successful method. Additionally, decreased ionomer incorporation has led to the highest performance demonstrating 238 mA/mg Pt (0.9 V IR-free) for PtNiNWs (pre-leached to 80 wt% Pt) with 9 wt% ionomer incorporation.« less

Fuel Cell Performance Implications of Membrane Electrode Assembly Fabrication with Platinum-Nickel Nanowire Catalysts

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

Mauger, Scott A.; Neyerlin, K. C.; Alia, Shaun M.

Platinum-nickel nanowire (PtNiNW) catalysts have shown exceptionally high oxygen reduction mass activity in rotating disk electrode measurements. However, the ability to successfully incorporate PtNiNWs into high performance membrane electrode assemblies (MEAs) has been challenging due to their size, shape, density, dispersion characteristics, and corrosion-susceptible nickel core. We have investigated the impact of specific processing steps and electrode composition on observed fuel cell performance and electrochemical properties in order to optimize performance. We have found that nickel ion contamination is a major concern for PtNiNWs that can be addressed through ion exchange in fabricated/tested MEAs or by acid leaching of catalystmore » materials prior to MEA incorporation, with the latter being the more successful method. Additionally, decreased ionomer incorporation has led to the highest performance demonstrating 238 mA/mg Pt (0.9 V IR-free) for PtNiNWs (pre-leached to 80 wt% Pt) with 9 wt% ionomer incorporation.« less

Selective passive adsorption of nitrate with surfactant treated porous electrode and electrostatic regeneration

NASA Astrophysics Data System (ADS)

Oyarzun, Diego I.; Hemmatifar, Ali; Palko, James W.; Stadermann, Michael; Santiago, Juan G.; Stanford microfluidics lab Team; Lawrence Livermore National Lab Team

2017-11-01

Nitrate is an important pollutant in drinking water worldwide, and a number of methods exist for the removal of nitrate from water including ion exchange and reverse osmosis. However, these approaches suffer from a variety of disadvantages including the need for a regenerating brine supply and disposal of used brine for ion exchange and low water recovery ratio for reverse osmosis. We are researching and developing a form of capacitive deionization (CDI) for energy efficient desalination and selective removal of ionic toxins from water. In CDI an electrode is used to electrostatically trap ions in a pair of porous electrodes. Here, we demonstrate the use of high surface area activated carbon electrodes functionalized with ion exchange moieties for adsorption of nitrate from aqueous solution. Unlike a traditional ion exchanger, the functionalized surfaces can be repeatedly regenerated by the application of an electrostatic potential which displaces the bound NO3- while leaving an excess of electronic charge on the electrode. Trimethylammonium has an intrinsic selectivity, we are using this moiety to selectively remove nitrate over chloride. We performed adsorption/desorption cycles under several desorption voltages and ratios of concentrations.

Oxygen-selective immobilized liquid membranes for operation of lithium-air batteries in ambient air

NASA Astrophysics Data System (ADS)

Zhang, Jian; Xu, Wu; Liu, Wei

In this work, nonaqueous electrolyte-based Li-air batteries with an O 2-selective membrane have been developed for operation in ambient air of 20-30% relative humidity (RH). The O 2 gas is continuously supplied through a membrane barrier layer at the interface of the cathode and ambient air. The membrane allows O 2 to permeate through while blocking moisture. Such membranes can be prepared by loading O 2-selective silicone oils into porous supports such as porous metal sheets and Teflon (PTFE) films. It was found that the silicone oil of high viscosity shows better performance. The immobilized silicone oil membrane in the porous PTFE film enabled the Li-air batteries with carbon black air electrodes to operate in ambient air (at 20% RH) for 16.3 days with a specific capacity of 789 mAh g -1 carbon and a specific energy of 2182 Wh kg -1 carbon. Its performance is much better than a reference battery assembled with a commercial, porous PTFE diffusion membranes as the moisture barrier layer on the cathode, which only had a discharge time of 5.5 days corresponding to a specific capacity of 267 mAh g -1 carbon and a specific energy of 704 Wh kg -1 carbon. The Li-air battery with the present selective membrane barrier layer even showed better performance in ambient air operation (20% RH) than the reference battery tested in the dry air box (<1% RH).

Ion-selective electrodes in organic elemental and functional group analysis: a review

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

Selig, W.

1977-11-08

The literature on the use of ion-selective electrodes in organic elemental and functional group analysis is surveyed in some detail. The survey is complete through Chemical Abstracts, Vol. 83 (1975). 40 figures, 52 tables, 236 references.

Electroactive nanostructured polymer actuators fabricated using sulfonated styrenic pentablock copolymer/montmorillonite/ionic liquid nanocomposite membranes

NASA Astrophysics Data System (ADS)

Lee, Jang-Woo; Hong, Soon Man; Koo, Chong Min

2014-08-01

High-bendable, air-operable ionic polymer-metal composite (IPMC) actuators composed of electroactive nanostructured middle-block sulfonated styrenic pentablock copolymer (SSPB)/sulfonated montmorillonite (s-MMT) nanocomposite electrolyte membranes with bulky imidazolium ionic liquids (ILs) incorporated were fabricated and their bending actuation performances were evaluated. The SSPB-based IPMC actuators showed larger air-operable bending displacements, higher displacement rates, and higher energy efficiency of actuations without conventional IPMC bottlenecks, including back relaxation and actuation instability during actuation in air, than the Nafion counterpart. Incorporation of s-MMT into the SSPB matrix further enhanced the actuation performance of the IPMC actuators in terms of displacement, displacement rate, and energy efficiency. The remarkably high performance of the SSPB/s-MMT/IL IPMCs was considered to be due to the microphase-separated large ionic domains of the SSPB (the average diameter of the ionic domain: ca. 20 nm) and the role of s-MMT as an ionic bridge between the ionic domains, and the ion pumping effect of the bulky imidazolium cations of the ILs as well. The microphase-separated nanostructure of the composite membranes caused a high dimensional stability upon swelling in the presence of ILs, which effectively preserved the original electrode resistance against swelling, leading to a high actuation performance of IPMC.

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

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

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

Application of nonflammable electrolyte with room temperature ionic liquids (RTILs) for lithium-ion cells

NASA Astrophysics Data System (ADS)

Nakagawa, Hiroe; Fujino, Yukiko; Kozono, Suguru; Katayama, Yoshihiro; Nukuda, Toshiyuki; Sakaebe, Hikari; Matsumoto, Hajime; Tatsumi, Kuniaki

A mixture of flammable organic solvent and nonflammable room temperature ionic liquid (RTIL) has been investigated as a new concept electrolyte to improve the safety of lithium-ion cells. This study focused on the use of N-methyl- N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13-TFSI) as the RTIL for the flame-retardant additive. It was found that a carbon negative electrode, both graphite and hard carbon, could be used with the mixed electrolyte. A 383562-size lithium-ion trial cell made with the mixed electrolyte showed good discharge capacity, which was equivalent to a cell with conventional organic electrolyte up to a discharge current rate of complete discharge in 1 h. Moreover, the mixed electrolyte was observed to be nonflammable at ionic liquid contents of 40 mass% or more. Thus the mixed electrolyte was found to realize both nonflammability and the good discharge performance of lithium-ion cells with carbon negative electrodes. These results indicate that RTILs have potential as a flame-retardant additive for the organic electrolytes used in lithium-ion cells.

Manual and Flow-Injection Detection/Quantification of Polyquaterniums via Fully Reversible Polyion-Sensitive Polymeric Membrane-Based Ion-Selective Electrodes.

PubMed

Ferguson, Stephen A; Meyerhoff, Mark E

2017-10-27

The detection of four different polyquaterniums (PQs) using a fully reversible potentiometric polyion sensor in three different detection modes is described. The polyion sensing "pulstrodes" serve as the detector for direct dose-response experiments, beaker titrations, and in a flow-injection analysis (FIA) system. Direct polycation response toward PQ-2, PQ-6, PQ-10, and poly(2-methacryloxyethyltrimethylammonium) chloride (PMETAC) yields characteristic information about each PQ species (e.g., relative charge densities, etc.) via syringe pump addition of each PQ species to a background electrolyte solution. Quantitative titrations are performed using a syringe pump to deliver heparin as the polyanion titrant to quantify all four PQs at μg/mL levels. Both the direct and indirect methods incorporate the use of a three-electrode system including counter, double junction reference, and working electrodes. The working electrode possesses a plasticized poly(vinyl chloride) (PVC) membrane containing the neutral lipophilic salt of dinonylnaphthalenesulfonate (DNNS - ) tridodecylmethylammonium (TDMA + ). Further, the titration method is shown to be useful to quantify PQ-6 levels in recreational swimming pool water collected in Ann Arbor, MI. Finally, a FIA system equipped with a pulstrode detector is used to demonstrate the ability to potentially quantify PQ levels via a more streamlined and semiautomated testing platform.

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

Towards understanding the effects of van der Waals strengths on the electric double-layer structures and capacitive behaviors

NASA Astrophysics Data System (ADS)

Yang, Huachao; Bo, Zheng; Yang, Jinyuan; Yan, Jianhua; Cen, Kefa

2017-10-01

Solid-liquid interactions are considered to play a crucial role in charge storage capability of electric double-layer capacitors (EDLCs). In this work, effects of van der Waals (VDW) strengths on the EDL structures and capacitive performances within two representative electrolytes of solvated aqueous solutions and solvent-free ionic liquids are illuminated by molecular dynamics simulations. Single crystalline metals with similar lattice constant but diverse VDW potentials are employed as electrodes. Upon enhancing VDW strengths, capacitance of aqueous electrolytes first increases conspicuously by ∼34.0% and then descends, manifesting a non-monotonic trend, which goes beyond traditional perspectives. Such unusual observation is interpreted by the excluded-volume effects stemmed from ion-solvent competitions. Stimulated by predominant coulombic interactions, more ions are aggregated at the interface despite of the increasing VDW potentials, facilitating superior screening efficiency and capacitance. However, further enhancing strengths preferentially attracts more solvents instead of ions to the electrified surface, which in turn strikingly repels ions from Helmholtz layers, deteriorating electrode capacitance. An essentially similar feather is also recognized for ionic liquids, while the corresponding mechanisms are prominently ascribed to the suppressed ionic separations issued from cation-anion competitions. We highlight that constructing electrode materials with a moderate-hydrophilicity could further advance the performances of EDLCs.

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.

Environmental Technology Verification Report for Instrumentation Northwest, Inc., Aquistar® TempHion Smart Sensor and Datalogger Nitrate-specific Ion-selective Electrode for Groundwater Remediation Monitoring

EPA Science Inventory

Environmental Technology Verification Report for Instrumentation Northwest, Inc., Aquistar® TempHion Smart Sensor and Datalogger Nitrate-specific Ion-selective Electrode for Groundwater Remediation Monitoring

A liquid-phase microextraction method, combining a dual gauge microsyringe with a hollow fiber membrane, for the determination of organochlorine pesticides in aqueous solution by gas chromatography/ion trap mass spectrometry.

PubMed

Yan, Chih-Hao; Wu, Hui-Fen

2004-01-01

A liquid-phase microextraction (LPME) method has been demonstrated for the extraction and determination of organochlorine pesticides (OCPs) in aqueous solution. The method combines a dual gauge microsyringe with a hollow fiber membrane (LPME/DGM-HF) followed by detection by gas chromatography/ion trap mass spectrometry (GC/ITMS). The advantages include speed, low solvent and sample consumption, simplicity and ease of use. The extraction time, solvent selection, salt concentration and sample stirring rate have been investigated in order to optimize extraction efficiency. The viability is evaluated by measuring the linearity and detection limit of the five OCPs in aqueous solution. Detection linearity for the OCPs has been achieved over a range of concentrations between 1 and 500 microg/L (r2 > 0.930), with a detection limit of 0.1 microg/L for each OCP. Copyright 2004 John Wiley & Sons, Ltd.

Recovery of cesium

DOEpatents

Izatt, Reed M.; Christensen, James J.; Hawkins, Richard T.

1984-01-01

A process of recovering cesium ions from mixtures of ions containing them and other ions, e.g., a solution of nuclear waste materials, which comprises establishing a separate source phase containing such a mixture of ions, establishing a separate recipient phase, establishing a liquid membrane phase in interfacial contact with said source and recipient phases, said membrane phase containing a ligand, preferably a selected calixarene as depicted in the drawing, maintaining said interfacial contact for a period of time long enough to transport by said ligand a substantial portion of the cesium ion from the source phase to the recipient phase, and recovering the cesium ion from the recipient phase. The separation of the source and recipient phases may be by the membrane phase only, e.g., where these aqueous phases are emulsified as dispersed phases in a continuous membrane phase, or may include a physical barrier as well, e.g., an open-top outer container with an inner open-ended container of smaller cross-section mounted in the outer container with its open bottom end spaced from and above the closed bottom of the outer container so that the membrane phase may fill the outer container to a level above the bottom of the inner container and have floating on its upper surface a source phase and a recipient phase separated by the wall of the inner container as a physical barrier. A preferred solvent for the ligand is a mixture of methylene chloride and carbon tetrachloride.

Calixarene-Mediated Liquid-Membrane Transport of Choline Conjugates.

PubMed

Adhikari, Birendra Babu; Fujii, Ayu; Schramm, Michael P

2014-05-01

A series of supramolecular calixarenes efficiently transport distinct molecular species through a liquid membrane when attached to a receptor-complementary choline handle. Calix-[6]arene hexacarboxylic acid was highly effective at transporting different target molecules against a pH gradient. Both carboxylic- and phosphonic-acid-functionalized calix[4]arenes effect transport without requiring a pH or ion gradient. NMR binding studies, two-phase solvent extraction, and three-phase transport experiments reveal the necessary and subtle parameters to effect the transport of molecules attached to a choline "handle". On the other hand, rescorin[4]arene cavitands, which have similar guest recognition profiles, did not transport guest molecules. These developments reveal new approaches towards attempting synthetic-receptor-mediated selective small-molecule transport in vesicular and cellular systems.

Ion trap device

DOEpatents

Ibrahim, Yehia M.; Smith, Richard D.

2016-01-26

An ion trap device is disclosed. The device includes a series of electrodes that define an ion flow path. A radio frequency (RF) field is applied to the series of electrodes such that each electrode is phase shifted approximately 180 degrees from an adjacent electrode. A DC voltage is superimposed with the RF field to create a DC gradient to drive ions in the direction of the gradient. A second RF field or DC voltage is applied to selectively trap and release the ions from the device. Further, the device may be gridless and utilized at high pressure.

A review on lithium-ion power battery thermal management technologies and thermal safety

NASA Astrophysics Data System (ADS)

An, Zhoujian; Jia, Li; Ding, Yong; Dang, Chao; Li, Xuejiao

2017-10-01

Lithium-ion power battery has become one of the main power sources for electric vehicles and hybrid electric vehicles because of superior performance compared with other power sources. In order to ensure the safety and improve the performance, the maximum operating temperature and local temperature difference of batteries must be maintained in an appropriate range. The effect of temperature on the capacity fade and aging are simply investigated. The electrode structure, including electrode thickness, particle size and porosity, are analyzed. It is found that all of them have significant influences on the heat generation of battery. Details of various thermal management technologies, namely air based, phase change material based, heat pipe based and liquid based, are discussed and compared from the perspective of improving the external heat dissipation. The selection of different battery thermal management (BTM) technologies should be based on the cooling demand and applications, and liquid cooling is suggested being the most suitable method for large-scale battery pack charged/discharged at higher C-rate and in high-temperature environment. The thermal safety in the respect of propagation and suppression of thermal runaway is analyzed.

Nanoscale potentiometry.

PubMed

Bakker, Eric; Pretsch, Ernö

2008-01-01

Potentiometric sensors share unique characteristics that set them apart from other electrochemical sensors. Potentiometric nanoelectrodes have been reported and successfully used for many decades, and we review these developments. Current research chiefly focuses on nanoscale films at the outer or the inner side of the membrane, with outer layers for increasing biocompatibility, expanding the sensor response, or improving the limit of detection (LOD). Inner layers are mainly used for stabilizing the response and eliminating inner aqueous contacts or undesired nanoscale layers of water. We also discuss the ultimate detectability of ions with such sensors and the power of coupling the ultra-low LODs of ion-selective electrodes with nanoparticle labels to give attractive bioassays that can compete with state-of-the-art electrochemical detection.

Titanium (III) cation selective electrode based on synthesized tris(2pyridyl) methylamine ionophore and its application in water samples

PubMed Central

Rezayi, Majid; Karazhian, Reza; Abdollahi, Yadollah; Narimani, Leila; Sany, Seyedeh Belin Tavakoly; Ahmadzadeh, Saeid; Alias, Yatimah

2014-01-01

The introduction of low detection limit ion selective electrodes (ISEs) may well pave the way for the determination of trace targets of cationic compounds. This research focuses on the detection of titanium (III) cation using a new PVC-membrane sensor based on synthesized tris(2pyridyl) methylamine (tpm) ionophore. The application and validation of the proposed sensor was done using potentiometric titration, inductively coupled plasma atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). The membrane sensor exhibited a Nernstian response to the titanium (III) cation over a concentration range of 1.0 × 10−6–1.0 × 10−2 M and pH range from 1–2.5. The Nernstian slope, the lower of detection (LOD), and the response time (t95%) of the proposed sensor were 29.17 ± 0.24 mV/dec, 7.9 × 10−7 M, and 20 s, respectively. The direct determination of 4–39 μg/ml of titanium (III) standard solution showed an average recovery of 94.60 and a mean relative standard deviation of 1.8 at 100.0 μg/ml. Finally, the utilization of the electrodes as end-point indicators for potentiometric titration with EDTA solutions for titanium (III) sensor was successfully carried out. PMID:24722576

[Construction and characterization of a selective membrane electrode for tenoxicam determination].

PubMed

Murăraşu, Andreea Elena; Mândrescu, Mariana; Spac, A F; Dorneanu, V

2010-01-01

This paper describes the construction and characterization of a selective membrane electrode which can be used for determination of tenoxicam. The electroactive compound is a precipitate obtained in 2 N hydrocloric acid solution containing tenoxicam in which a solution of iodine is added. The membrane is made by mixing the electroactive compound with polyethylene using tetrahydrofurane as solvent. The solution is evaporated in order to obtain a thick membrane, which is attached at one end of a PVC tube and is fixed with the same polymeric solution. In this tube an internal Ag/AgCl reference electrode is inserted. The assembly is filled with an internal solution containing tenoxicam. The electrode was characterized (electrode slope, selectivity, optimal pH range, response time, life time). The developed method was validated. The method showed a good liniarity in the range of 10(-6)-10(-1) M (the correlation coefficient r = 0.9999). The detection limit (LD) was 7.347 x 10(-7) M and the quantification limit (LQ) was 1.017 x 10(-6) M. There were established the precision (RSD = 1.79%) and the accuracy (mean recovery is 100.17%) The experimental results demonstrated a good sensibility.

Thin membrane sensor with biochemical switch

NASA Technical Reports Server (NTRS)

Worley, III, Jennings F. (Inventor); Case, George D. (Inventor)

1994-01-01

A modular biosensor system for chemical or biological agent detection utilizes electrochemical measurement of an ion current across a gate membrane triggered by the reaction of the target agent with a recognition protein conjugated to a channel blocker. The sensor system includes a bioresponse simulator or biochemical switch module which contains the recognition protein-channel blocker conjugate, and in which the detection reactions occur, and a transducer module which contains a gate membrane and a measuring electrode, and in which the presence of agent is sensed electrically. In the poised state, ion channels in the gate membrane are blocked by the recognition protein-channel blocker conjugate. Detection reactions remove the recognition protein-channel blocker conjugate from the ion channels, thus eliciting an ion current surge in the gate membrane which subsequently triggers an output alarm. Sufficiently large currents are generated that simple direct current electronics are adequate for the measurements. The biosensor has applications for environmental, medical, and industrial use.

Composite fuel cell membranes

DOEpatents

Plowman, K.R.; Rehg, T.J.; Davis, L.W.; Carl, W.P.; Cisar, A.J.; Eastland, C.S.

1997-08-05

A bilayer or trilayer composite ion exchange membrane is described suitable for use in a fuel cell. The composite membrane has a high equivalent weight thick layer in order to provide sufficient strength and low equivalent weight surface layers for improved electrical performance in a fuel cell. In use, the composite membrane is provided with electrode surface layers. The composite membrane can be composed of a sulfonic fluoropolymer in both core and surface layers.

Composite fuel cell membranes

DOEpatents

Plowman, Keith R.; Rehg, Timothy J.; Davis, Larry W.; Carl, William P.; Cisar, Alan J.; Eastland, Charles S.

1997-01-01

A bilayer or trilayer composite ion exchange membrane suitable for use in a fuel cell. The composite membrane has a high equivalent weight thick layer in order to provide sufficient strength and low equivalent weight surface layers for improved electrical performance in a fuel cell. In use, the composite membrane is provided with electrode surface layers. The composite membrane can be composed of a sulfonic fluoropolymer in both core and surface layers.

Growth of Ionic Selectivity Prussian Blue Modified Celgard Separator for High Performance Lithium Sulfur Battery.

PubMed

Wu, Xian; Fan, Lishuang; Qiu, Yue; Wang, Maoxu; Cheng, Junhan; Guan, Bin; Guo, Zhikun; Zhang, Naiqing; Sun, Kening

2018-06-26

Lithium sulfur batteries have been restricted on their major technical problem of shuttling soluble polysulfides between electrodes, resulting in serious capacity fading. For purpose of develop a high-performance lithium-sulfur battery, we first time utilize a simple growth method to introduce a Prussian blue modified Celgard separator as an ion selective membrane in lithium sulfur batteries. The unique structure of Prussian blue could effectively suppress the shuttle of polysulfides but scarcely affect the transfer ability of lithium ions, which is beneficial to achieve high sulfur conversion efficiency and capacity retention. The lithium sulfur battery with Prussian blue modified Celgard separator reveals an average capacity decaying of only 0.03% per cycle at 1C after 1000 cycles. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of a Highly Fluorophilic Phosphonium Salt and its Use in a Fluorous Anion-Exchanger Membrane with High Selectivity for Perfluorinated Acids

PubMed Central

Boswell, Paul G.; Anfang, Alyce C.; Bühlmann, Philippe

2008-01-01

Fluorous solvents are the most nonpolar, nonpolarizable phases known, whereas ions are inherently polar. This makes it difficult to create salts that are soluble in a fluorous solvent. Here we present the synthesis and characterization of a new fluorophilic phosphonium salt, tris{3,5-bis[(perfluorooctyl)propyl]phenyl}methylphosphonium methyl sulfate. The salt has a solubility of at least 14 mM in perfluoro(perhydrophenanthrene), perfluoro(methylcyclohexane), and perfluorohexanes. It also shows immediate potential for use as a phase-transfer catalyst in fluorous biphasic catalysis, but in this work it is used as an anion exchanger site in the first potentiometric fluorous-membrane anion-selective electrode. The membrane sensor exhibited the exceptional selectivity of 3.9 × 1010 to 1 for perfluorooctanesulfonate over chloride, and of 2.5 × 107 to 1 for perfluorooctanoate over chloride. With improvements to the sensor’s detection limit and lifetime, it has the potential to be an attractive alternative to the expensive, time-consuming methods currently employed for measurement of perfluorinated acids. PMID:22072222

The Li-ion rechargeable battery: a perspective.

PubMed

Goodenough, John B; Park, Kyu-Sung

2013-01-30

Each cell of a battery stores electrical energy as chemical energy in two electrodes, a reductant (anode) and an oxidant (cathode), separated by an electrolyte that transfers the ionic component of the chemical reaction inside the cell and forces the electronic component outside the battery. The output on discharge is an external electronic current I at a voltage V for a time Δt. The chemical reaction of a rechargeable battery must be reversible on the application of a charging I and V. Critical parameters of a rechargeable battery are safety, density of energy that can be stored at a specific power input and retrieved at a specific power output, cycle and shelf life, storage efficiency, and cost of fabrication. Conventional ambient-temperature rechargeable batteries have solid electrodes and a liquid electrolyte. The positive electrode (cathode) consists of a host framework into which the mobile (working) cation is inserted reversibly over a finite solid-solution range. The solid-solution range, which is reduced at higher current by the rate of transfer of the working ion across electrode/electrolyte interfaces and within a host, limits the amount of charge per electrode formula unit that can be transferred over the time Δt = Δt(I). Moreover, the difference between energies of the LUMO and the HOMO of the electrolyte, i.e., electrolyte window, determines the maximum voltage for a long shelf and cycle life. The maximum stable voltage with an aqueous electrolyte is 1.5 V; the Li-ion rechargeable battery uses an organic electrolyte with a larger window, which increase the density of stored energy for a given Δt. Anode or cathode electrochemical potentials outside the electrolyte window can increase V, but they require formation of a passivating surface layer that must be permeable to Li(+) and capable of adapting rapidly to the changing electrode surface area as the electrode changes volume during cycling. A passivating surface layer adds to the impedance of the Li(+) transfer across the electrode/electrolyte interface and lowers the cycle life of a battery cell. Moreover, formation of a passivation layer on the anode robs Li from the cathode irreversibly on an initial charge, further lowering the reversible Δt. These problems plus the cost of quality control of manufacturing plague development of Li-ion rechargeable batteries that can compete with the internal combustion engine for powering electric cars and that can provide the needed low-cost storage of electrical energy generated by renewable wind and/or solar energy. Chemists are contributing to incremental improvements of the conventional strategy by investigating and controlling electrode passivation layers, improving the rate of Li(+) transfer across electrode/electrolyte interfaces, identifying electrolytes with larger windows while retaining a Li(+) conductivity σ(Li) > 10(-3) S cm(-1), synthesizing electrode morphologies that reduce the size of the active particles while pinning them on current collectors of large surface area accessible by the electrolyte, lowering the cost of cell fabrication, designing displacement-reaction anodes of higher capacity that allow a safe, fast charge, and designing alternative cathode hosts. However, new strategies are needed for batteries that go beyond powering hand-held devices, such as using electrode hosts with two-electron redox centers; replacing the cathode hosts by materials that undergo displacement reactions (e.g. sulfur) by liquid cathodes that may contain flow-through redox molecules, or by catalysts for air cathodes; and developing a Li(+) solid electrolyte separator membrane that allows an organic and aqueous liquid electrolyte on the anode and cathode sides, respectively. Opportunities exist for the chemist to bring together oxide and polymer or graphene chemistry in imaginative morphologies.

Selective crystallization with preferred lithium-ion storage capability of inorganic materials

PubMed Central

2012-01-01

Lithium-ion batteries are supposed to be a key method to make a more efficient use of energy. In the past decade, nanostructured electrode materials have been extensively studied and have presented the opportunity to achieve superior performance for the next-generation batteries which require higher energy and power densities and longer cycle life. In this article, we reviewed recent research activities on selective crystallization of inorganic materials into nanostructured electrodes for lithium-ion batteries and discuss how selective crystallization can improve the electrode performance of materials; for example, selective exposure of surfaces normal to the ionic diffusion paths can greatly enhance the ion conductivity of insertion-type materials; crystallization of alloying-type materials into nanowire arrays has proven to be a good solution to the electrode pulverization problem; and constructing conversion-type materials into hollow structures is an effective approach to buffer the volume variation during cycling. The major goal of this review is to demonstrate the importance of crystallization in energy storage applications. PMID:22353373

High-energy metal air batteries

DOEpatents

Zhang, Ji-Guang; Xiao, Jie; Xu, Wu; Wang, Deyu; Williford, Ralph E.; Liu, Jun

2014-07-01

Disclosed herein are embodiments of lithium/air batteries and methods of making and using the same. Certain embodiments are pouch-cell batteries encased within an oxygen-permeable membrane packaging material that is less than 2% of the total battery weight. Some embodiments include a hybrid air electrode comprising carbon and an ion insertion material, wherein the mass ratio of ion insertion material to carbon is 0.2 to 0.8. The air electrode may include hydrophobic, porous fibers. In particular embodiments, the air electrode is soaked with an electrolyte comprising one or more solvents including dimethyl ether, and the dimethyl ether subsequently is evacuated from the soaked electrode. In other embodiments, the electrolyte comprises 10-20% crown ether by weight.

High-energy metal air batteries

DOEpatents

Zhang, Ji-Guang; Xiao, Jie; Xu, Wu; Wang, Deyu; Williford, Ralph E.; Liu, Jun

2013-07-09

Disclosed herein are embodiments of lithium/air batteries and methods of making and using the same. Certain embodiments are pouch-cell batteries encased within an oxygen-permeable membrane packaging material that is less than 2% of the total battery weight. Some embodiments include a hybrid air electrode comprising carbon and an ion insertion material, wherein the mass ratio of ion insertion material to carbon is 0.2 to 0.8. The air electrode may include hydrophobic, porous fibers. In particular embodiments, the air electrode is soaked with an electrolyte comprising one or more solvents including dimethyl ether, and the dimethyl ether subsequently is evacuated from the soaked electrode. In other embodiments, the electrolyte comprises 10-20% crown ether by weight.

Electrokinetic migration across artificial liquid membranes Tuning the membrane chemistry to different types of drug substances.

PubMed

Gjelstad, Astrid; Rasmussen, Knut Einar; Pedersen-Bjergaard, Stig

2006-08-18

Twenty different basic drugs were electrokinetically extracted across a thin artificial organic liquid membrane with a 300 V d.c. electrical potential difference as the driving force. From a 300 microl aqueous sample (acidified corresponding to 10mM HCl), the drugs were extracted for 5 min through a 200 microm artificial liquid membrane of a water immiscible organic solvent immobilized in the pores of a polypropylene hollow fiber, and into a 30 microl aqueous acceptor solution of 10mM HCl inside the lumen of the hollow fiber. Hydrophobic basic drugs (logP>1.7) were effectively isolated utilizing 2-nitrophenyl octyl ether (NPOE) as the artificial liquid membrane, with recoveries up to 83%. For more hydrophilic basic drugs (logP<1.0), a mixture of NPOE and 25% (w/w) di-(2-ethylhexyl) phosphate (DEHP) was required to ensure efficient extraction, resulting in recoveries up to 75%. DEHP was expected to act as an ion-pair reagent ion-pairing the protonated hydrophilic drugs at the interface between the sample and the membrane, resulting in permeation of the interface.

Electrically driven ion separations and nanofiltration through membranes coated with polyelectrolyte multilayers

NASA Astrophysics Data System (ADS)

White, Nicholas

Polyelectrolyte multilayer (PEM) films deposited using the layer-by-layer (LBL) method are attractive for their simple deposition, tailorable nature, scalability, and charge or size-based selectivity for solutes. This dissertation explores ion separations in electrodialysis (ED) and solute removal through nanofiltration with PEMs deposited on polymer membranes. ED membranes typically exhibit modest selectivities between monovalent and divalent ions. In contrast, this work shows that K+/Mg 2+ ED selectivities reach values >1000 when using Nafion 115 cation-exchange membranes coated with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For comparison, the corresponding K+ /Mg2+ selectivity of bare Nafion 115 is <2. However, water-splitting at strongly overlimiting current densities may lead to a local pH increase close to the membrane surface and alter film permeability or allow passage of Mg(OH)x species to decrease selectivity. When the source phase contains high salt concentrations, the K+ transference number approaches unity and the K+/Mg2+ selectivity is >20,000, presumably because the applied current is below the limiting value for K+ and H+ transport is negligible at this high K+ concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions. The high ED selectivities of (PAH/PSS)5PAH-coated Nafion membranes translate to separations with Li+/Co2+ and K +/La3+. Even with adsorption of only 3 polyelectrolyte layers, Nafion membranes exhibit a Li+/Co2+ selectivity >23. However, the resistance to monovalent-ion passage does not decrease significantly with fewer polyelectrolyte layers. At overlimiting currents, hydroxides from water splitting form insoluble metal hydroxides to foul the membrane. With 0.1 M source-phase salt concentrations, transference numbers for monovalent cations approach unity and selectivities are >5000 because the diffusion-limited K+ or Li+ currents exceed the applied current. However, ED selectivities gradually decline with time. Thus, future research should aim to increase membrane stability and limiting currents to fully exploit the remarkable selectivity of these membranes. PEMs deposited on commercial ultrafiltration (UF) membranes also show high rejections of organic dyes. Coating the surface of polyethersulfone (PES) membranes imparts a selective barrier to dye molecules used in textile production. These films achieve dye rejections >98% and may be useful for wastewater treatment and dye recovery. Other studies in microfluidic channels exploit ion transport phenomena in the vicinity of ion-selective junctions, such as cation-exchange membranes. These studies suggest that ion concentration polarization (ICP) could remove charged species from feed streams.

Self-assembled asymmetric membrane containing micron-size germanium for high capacity lithium ion batteries

DOE PAGES

Byrd, Ian; Chen, Hao; Webber, Theron; ...

2015-10-23

We report the formation of novel asymmetric membrane electrode containing micron-size (~5 μm) germanium powders through a self-assembly phase inversion method for high capacity lithium ion battery anode. 850 mA h g -1 capacity (70%) can be retained at a current density of 600 mA g -1 after 100 cycles with excellent rate performance. Such a high retention rate has rarely been seen for pristine micron-size germanium anodes. Moreover, scanning electron microscope studies reveal that germanium powders are uniformly embedded in a networking porous structure consisting of both nanopores and macropores. It is believed that such a unique porous structuremore » can efficiently accommodate the ~260% volume change during germanium alloying and de-alloying process, resulting in an enhanced cycling performance. Finally, these porous membrane electrodes can be manufactured in large scale using a roll-to-roll processing method.« less

The Effect of Platinum Electrocatalyst on Membrane Degradation in Polymer Electrolyte Fuel Cells.

PubMed

Bodner, Merit; Cermenek, Bernd; Rami, Mija; Hacker, Viktor

2015-12-08

Membrane degradation is a severe factor limiting the lifetime of polymer electrolyte fuel cells. Therefore, obtaining a deeper knowledge is fundamental in order to establish fuel cells as competitive product. A segmented single cell was operated under open circuit voltage with alternating relative humidity. The influence of the catalyst layer on membrane degradation was evaluated by measuring a membrane without electrodes and a membrane-electrode-assembly under identical conditions. After 100 h of accelerated stress testing the proton conductivity of membrane samples near the anode and cathode was investigated by means of ex situ electrochemical impedance spectroscopy. The membrane sample near the cathode inlet exhibited twofold lower membrane resistance and a resulting twofold higher proton conductivity than the membrane sample near the anode inlet. The results from the fluoride ion analysis have shown that the presence of platinum reduces the fluoride emission rate; which supports conclusions drawn from the literature.

The Effect of Platinum Electrocatalyst on Membrane Degradation in Polymer Electrolyte Fuel Cells

PubMed Central

Bodner, Merit; Cermenek, Bernd; Rami, Mija; Hacker, Viktor

2015-01-01

Membrane degradation is a severe factor limiting the lifetime of polymer electrolyte fuel cells. Therefore, obtaining a deeper knowledge is fundamental in order to establish fuel cells as competitive product. A segmented single cell was operated under open circuit voltage with alternating relative humidity. The influence of the catalyst layer on membrane degradation was evaluated by measuring a membrane without electrodes and a membrane-electrode-assembly under identical conditions. After 100 h of accelerated stress testing the proton conductivity of membrane samples near the anode and cathode was investigated by means of ex situ electrochemical impedance spectroscopy. The membrane sample near the cathode inlet exhibited twofold lower membrane resistance and a resulting twofold higher proton conductivity than the membrane sample near the anode inlet. The results from the fluoride ion analysis have shown that the presence of platinum reduces the fluoride emission rate; which supports conclusions drawn from the literature. PMID:26670258

Intracellular recording of action potentials by nanopillar electroporation.

PubMed

Xie, Chong; Lin, Ziliang; Hanson, Lindsey; Cui, Yi; Cui, Bianxiao

2012-02-12

Action potentials have a central role in the nervous system and in many cellular processes, notably those involving ion channels. The accurate measurement of action potentials requires efficient coupling between the cell membrane and the measuring electrodes. Intracellular recording methods such as patch clamping involve measuring the voltage or current across the cell membrane by accessing the cell interior with an electrode, allowing both the amplitude and shape of the action potentials to be recorded faithfully with high signal-to-noise ratios. However, the invasive nature of intracellular methods usually limits the recording time to a few hours, and their complexity makes it difficult to simultaneously record more than a few cells. Extracellular recording methods, such as multielectrode arrays and multitransistor arrays, are non-invasive and allow long-term and multiplexed measurements. However, extracellular recording sacrifices the one-to-one correspondence between the cells and electrodes, and also suffers from significantly reduced signal strength and quality. Extracellular techniques are not, therefore, able to record action potentials with the accuracy needed to explore the properties of ion channels. As a result, the pharmacological screening of ion-channel drugs is usually performed by low-throughput intracellular recording methods. The use of nanowire transistors, nanotube-coupled transistors and micro gold-spine and related electrodes can significantly improve the signal strength of recorded action potentials. Here, we show that vertical nanopillar electrodes can record both the extracellular and intracellular action potentials of cultured cardiomyocytes over a long period of time with excellent signal strength and quality. Moreover, it is possible to repeatedly switch between extracellular and intracellular recording by nanoscale electroporation and resealing processes. Furthermore, vertical nanopillar electrodes can detect subtle changes in action potentials induced by drugs that target ion channels.

Intracellular recording of action potentials by nanopillar electroporation

NASA Astrophysics Data System (ADS)

Xie, Chong; Lin, Ziliang; Hanson, Lindsey; Cui, Yi; Cui, Bianxiao

2012-03-01

Action potentials have a central role in the nervous system and in many cellular processes, notably those involving ion channels. The accurate measurement of action potentials requires efficient coupling between the cell membrane and the measuring electrodes. Intracellular recording methods such as patch clamping involve measuring the voltage or current across the cell membrane by accessing the cell interior with an electrode, allowing both the amplitude and shape of the action potentials to be recorded faithfully with high signal-to-noise ratios. However, the invasive nature of intracellular methods usually limits the recording time to a few hours, and their complexity makes it difficult to simultaneously record more than a few cells. Extracellular recording methods, such as multielectrode arrays and multitransistor arrays, are non-invasive and allow long-term and multiplexed measurements. However, extracellular recording sacrifices the one-to-one correspondence between the cells and electrodes, and also suffers from significantly reduced signal strength and quality. Extracellular techniques are not, therefore, able to record action potentials with the accuracy needed to explore the properties of ion channels. As a result, the pharmacological screening of ion-channel drugs is usually performed by low-throughput intracellular recording methods. The use of nanowire transistors, nanotube-coupled transistors and micro gold-spine and related electrodes can significantly improve the signal strength of recorded action potentials. Here, we show that vertical nanopillar electrodes can record both the extracellular and intracellular action potentials of cultured cardiomyocytes over a long period of time with excellent signal strength and quality. Moreover, it is possible to repeatedly switch between extracellular and intracellular recording by nanoscale electroporation and resealing processes. Furthermore, vertical nanopillar electrodes can detect subtle changes in action potentials induced by drugs that target ion channels.

Investigation of Ion Channel Activities of Gramicidin A in the Presence of Ionic Liquids Using Model Cell Membranes

PubMed Central

Ryu, Hyunil; Lee, Hwankyu; Iwata, Seigo; Choi, Sangbaek; Ki Kim, Moon; Kim, Young-Rok; Maruta, Shinsaku; Min Kim, Sun; Jeon, Tae-Joon

2015-01-01

Ionic liquids (ILs) are considered to be green solvents because of their non-volatility. Although ILs are relatively safe in the atmospheric environment, they may be toxic in other environments. Our previous research showed that the cytotoxicity of ILs to biological organisms is attributable to interference with cell membranes by IL insertion. However, the effects of ILs on ion channels, which play important roles in cell homeostasis, have not been comprehensively studied to date. In this work, we studied the interactions between ILs and lipid bilayer membranes with gramicidin A ion channels. We used two methods, namely electrical and fluorescence measurements of ions that permeate the membrane. The lifetimes of channels were increased by all the ILs tested in this work via stabilizing the compressed structure of the lipid bilayer and the rate of ion flux through gA channels was decreased by changing the membrane surface charge. The former effect, which increased the rate of ion flux, was dominant at high salt concentrations, whereas the latter, which decreased the rate of ion flux, was dominant at low salt concentrations. The effects of ILs increased with increasing concentration and alkyl chain length. The experimental results were further studied using molecular dynamics simulations. PMID:26189604

Adsorbent for metal ions and method of making and using

DOEpatents

White, Lloyd R.; Lundquist, Susan H.

1999-01-01

A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions.

Adsorbent for metal ions and method of making and using

DOEpatents

White, L.R.; Lundquist, S.H.

1999-08-10

A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions. 2 figs.

Adsorbent for metal ions and method of making and using

DOEpatents

White, Lloyd R.; Lundquist, Susan H.

2000-01-01

A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions.

High performance red phosphorus electrode in ionic liquid-based electrolyte for Na-ion batteries

NASA Astrophysics Data System (ADS)

Dahbi, Mouad; Fukunishi, Mika; Horiba, Tatsuo; Yabuuchi, Naoaki; Yasuno, Satoshi; Komaba, Shinichi

2017-09-01

Electrochemical performance of the red phosphorus electrode was examined in ionic-liquid electrolyte, 0.25 mol dm-3 sodium bisfluorosulfonylamide (NaFSA) dissolved N-methyl-N-propylpyridinium-bisfluorosulfonylamide (MPPFSA), at room temperature. We compared its electrochemical performance to conventional EC/PC/DEC, EC/DEC, and PC solutions containing 1 mol dm-3 NaPF6. The electrode in NaFSA/MPPFSA demonstrated a reversible capacity of 1480 mAh g-1 and excellent capacity retention of 93% over 80 cycles, which is much better than those in the conventional electrolytes. The difference in capacity retention for the electrolytes correlates to the different solid electrolyte interphase (SEI) layer formed on the phosphorus electrode. To understand the SEI formation in NaFSA/MPPFSA and its evolution during cycling, we investigate the surface layer of the red phosphorus electrodes with hard X-ray photoelectron spectroscopy (HAXPES) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). A detailed analysis of HAXPES spectra demonstrates that SEI layer consists of major inorganic and minor organic species, originating from decomposition of MPP+ and FSA-. Homogenous surface layer is formed during the first cycle in NaFSA/MPPFSA while in alkyl carbonate ester electrolytes, continuous growth of surface film up to the 20th cycle is observed. Possibility of red phosphorous electrode for battery applications with pure ionic liquid is discussed.

Engineering the Membrane/Electrode Interface To Improve the Performance of Solid-State Supercapacitors.

PubMed

Huang, Chun; Zhang, Jin; Snaith, Henry J; Grant, Patrick S

2016-08-17

This paper investigates the effect of adding a 450 nm layer based on porous TiO2 at the interface between a 4.5 μm carbon/TiO2 nanoparticle-based electrode and a polymer electrolyte membrane as a route to improve energy storage performance in solid-state supercapacitors. Electrochemical characterization showed that adding the interface layer reduced charge transfer resistance, promoted more efficient ion transfer across the interface, and significantly improved charge/discharge dynamics in a solid-state supercapacitor, resulting in an increased areal capacitance from 45.3 to 111.1 mF cm(-2) per electrode at 0.4 mA cm(-2).

Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy

DOE PAGES

Leenheer, Andrew J.; Jungjohann, Katherine L.; Zavadil, Kevin R.; ...

2016-05-31

Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. In this study, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge–discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed formore » the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Lastly, our results show that electrochemically induced solid–solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.« less

Fuel cell with ionization membrane

NASA Technical Reports Server (NTRS)

Hartley, Frank T. (Inventor)

2007-01-01

A fuel cell is disclosed comprising an ionization membrane having at least one area through which gas is passed, and which ionizes the gas passing therethrough, and a cathode for receiving the ions generated by the ionization membrane. The ionization membrane may include one or more openings in the membrane with electrodes that are located closer than a mean free path of molecules within the gas to be ionized. Methods of manufacture are also provided.

Reliability of high-strain ionomeric polymer transducers fabricated using the novel direct assembly process

NASA Astrophysics Data System (ADS)

Akle, Barbar; Nawshin, Saila; Leo, Donald

2006-03-01

Ionomeric polymer transducers have received considerable attention in the past several years. These actuators, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typically, ionic polymer actuators are composed of Nafion-117 membranes with platinum electrodes and are saturated with water diluents. Recently the authors have developed a novel fabrication technique named the Direct Assembly Process (DAP), which allowed good control on electrode morphology and composition. The DAP consists of spraying two high surface area metal-ionomer electrodes on a Nafion membrane. A single- walled carbon nanotubes (SWNT) and ruthenium dioxide (RuO II) hybrid electrode was sprayed on a Formamide hydrated Nafion-117 membrane using the DAP method. This transducer was shown to generate 9.4% peak-peak strain under the application of +/-2V at a strain rate of 1%/sec. Furthermore using the DAP one is capable of incorporating several types of diluents in ionomeric polymer transducers. Transducers with ionic liquid diluents are demonstrated to operate in air for long periods of time. In this work we will present a reliability study of transducers fabricated using the DAP. Each transducer is tested under a frequency range of 0.2Hz to 1Hz, and a potential of +/-1V to +/-3V. Water hydrated transducers dehydrates and stop moving within 5 minutes while operating in air under +/-2V. Transducers with Formamide diluents operate for 20,000 cycles under +/-1.5V and 0.5Hz (around 11hrs), while they degrade in less than 3000 cycles under +/-2V and 0.5Hz. Ionic liquid based transducers are demonstrated to operate in air for over 400,000 with little loss in performance, and over 1 million cycle with a loss of only 43%. Actuators with several electrode compositions are fabricated and a correlation between the reliability of ionic liquid-ionic polymer transducers and maximum strain will be presented. This correlation will be used to assess the adhesion between the high surface area electrodes and the Nafion membrane. SEM images of tested transducers will be presented.

Ion sensing method

DOEpatents

Smith, Richard Harding; Martin, Glenn Brian

2004-05-18

The present invention allows the determination of trace levels of ionic substances in a sample solution (ions, metal ions, and other electrically charged molecules) by coupling a separation method, such as liquid chromatography, with ion selective electrodes (ISE) prepared so as to allow detection at activities below 10.sup.-6 M. The separation method distributes constituent molecules into fractions due to unique chemical and physical properties, such as charge, hydrophobicity, specific binding interactions, or movement in an electrical field. The separated fractions are detected by means of the ISE(s). These ISEs can be used singly or in an array. Accordingly, modifications in the ISEs are used to permit detection of low activities, specifically, below 10.sup.-6 M, by using low activities of the primary analyte (the molecular species which is specifically detected) in the inner filling solution of the ISE. Arrays constructed in various ways allow flow-through sensing for multiple ions.

Soft ionization device with characterization systems and methods of manufacture

NASA Technical Reports Server (NTRS)

Hartley, Frank T. (Inventor)

2004-01-01

Various configurations of characterization systems such as ion mobility spectrometers and mass spectrometers are disclosed that are coupled to an ionization device. The ionization device is formed of a membrane that houses electrodes therein that are located closer to one another than the mean free path of the gas being ionized. Small voltages across the electrodes generate large electric fields which act to ionize substantially all molecules passing therethrough without fracture. Methods to manufacture the mass spectrometer and ion mobility spectrometer systems are also described.

Construction of a new Cu2+ coated wire ion selective electrode based on 2-((2-(2-(2-(2-hydroxy-5-methoxybenzylidene amino)phenyl)disufanyl)phenylimino)methyl)-4-methoxyphenol Schiff base.

PubMed

Shokrollahi, A; Abbaspour, A; Ghaedi, M; Haghighi, A Naghashian; Kianfar, A H; Ranjbar, M

2011-03-15

In this article a new coated platinum Cu(2+) ion selective electrode based on 2-((2-(2-(2-(2-hydroxy-5-methoxybenzylideneamino)phenyl)disufanyl)phenylimino) methyl)-4-methoxyphenol Schiff base (L(1)) as a new ionophore is described. This sensor has a wide linear range of concentration (1.2 × 10(-7)-1.0 × 10(-1) mol L(-1)) and a low detection limit of 9.8 × 10(-8) mol L(-1)of Cu(NO(3))(2). It has a Nernstian response with slope of 29.54 ± 1.62 mV decade(-1) and it is applicable in the pH range of 4.0-6.0 without any divergence in potential. The coated electrode has a short response time of approximately 9s and is stable at least for 3.5 months. The electrode shows a good selectivity for Cu(2+) ion toward a wide variety of metal ions. The proposed sensor was successfully applied for the determination of Cu(2+) ion in different real and environmental samples and as indicator electrode for potentiometric titration of Cu(2+) ion with EDTA. Copyright © 2010 Elsevier B.V. All rights reserved.

Understanding of ammonia transport in PEM fuel cells

NASA Astrophysics Data System (ADS)

Jung, Myunghee

This dissertation investigates ammonia (NH3) as a fuel contaminant to the anode in Proton Exchange Membrane Fuel Cells (PEMFCs). Since NH 3 is fed to the anode in a gas phase and transferred to the cathode, the effect of a contaminant is distributed through MEA and quite complicated. This study is focused on the investigation of mechanism of NH3 transport and the isolation of multiple effects to degrade the performance of fuel cell. An External Reference Electrode (ERE) was employed to decouple the effect of individual electrode and explain the mechanism of NH3 contamination. A mechanism of NH3 transport is proposed and supported by data for various inlet conditions in a N2/N2 laboratory-scale fuel cell at Open Circuit Conditions (OCC). With a commercialized GORE(TM) PRIMEA RTM 5631 MEAs at 70°C, data were obtained utilizing a material balance technique, which uses an ion selective electrode (ISE) to determine the concentration of ammonium ion in the process streams. The results indicate that ammonia is not transported across the membrane when the feeds to both electrodes are dry. However, with humidified feeds ammonia was transported from the anode to the cathode. The data also indicate the water content of in the MEA is the critical factor that causes NH3 crossover in the MEA. Diffusion coefficients of NH3 in MEA are also calculated at different relative humilities. An ERE was developed for PEM fuel cell by using a NafionRTM strip which was used to understand contamination mechanism. The voltage of anode electrode relative to ERE was measured during a polarization curve. The data showed the measurement of individual electrode potential was extremely affected by the misalignment between two electrodes. We compare the overpotential measured from the reference electrode and the calculated overpotential from subtracting the cell voltages between neat hydrogen and a 25 ppm CO in H 2 stream at same current. The studies indicated that the overpotentials obtained from two different methods were same and the location of a Nafion RTM strip on MEA did not affect the measured overpotentials. When NH3 was introduced as a contaminant to the cell at OCC, the thermodynamic potential of the anode electrode was measured for GORETM PRIMEARTM 57 series MEA at 80°C. High Frequency Resistance (HFR) and material balance were also analyzed during the change of thermodynamic potential. The results show that the injected NH3 was absorbed in the MEA until the ion exchange capacity was fully saturated and then NH 3 reaction occurred on the electrode. Finally, we studied how NH 3 contamination process occurs from transient voltage changes of the cell and an individual electrode.

Semi-solid electrodes having high rate capability

DOEpatents

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

2016-06-07

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode and a semi-solid cathode. The semi-solid cathode includes a suspension of an active material of about 35% to about 75% by volume of an active material and about 0.5% to about 8% by volume of a conductive material in a non-aqueous liquid electrolyte. An ion-permeable membrane is disposed between the anode and the semi-solid cathode. The semi-solid cathode has a thickness of about 250 .mu.m to about 2,000 .mu.m, and the electrochemical cell has an area specific capacity of at least about 7 mAh/cm.sup.2 at a C-rate of C/4. In some embodiments, the semi-solid cathode slurry has a mixing index of at least about 0.9.

Graphene-based supercapacitors in the parallel-plate electrode configuration: ionic liquids versus organic electrolytes.

PubMed

Shim, Youngseon; Kim, Hyung J; Jung, Younjoon

2012-01-01

Supercapacitors with two single-sheet graphene electrodes in the parallel plate geometry are studied via molecular dynamics (MD) computer simulations. Pure 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI+BF4-) and a 1.1 M solution of EMI+BF4- in acetonitrile are considered as prototypes of room-temperature ionic liquids (RTILs) and organic electrolytes. Electrolyte structure, charge density and associated electric potential are investigated by varying the charges and separation of the two electrodes. Multiple charge layers formed in the electrolytes in the vicinity of the electrodes are found to screen the electrode surface charge almost completely. As a result, the supercapacitors show nearly an ideal electric double layer behavior, i.e., the electric potential exhibits essentially a plateau behavior in the entire electrolyte region except for sharp changes in screening zones very close to the electrodes. Due to its small size and large charge separation, BF4- is considerably more efficient in shielding electrode charges than EMI+. In the case of the acetonitrile solution, acetonitrile also plays an important role by aligning its dipoles near the electrodes; however, the overall screening mainly arises from ions. Because of the disparity of shielding efficiency between cations and anions, the capacitance of the positively-charged anode is significantly larger than that of the negatively-charged cathode. Therefore, the total cell capacitance in the parallel plate configuration is primarily governed by the cathode. Ion conductivity obtained via the Green-Kubo (GK) method is found to be largely independent of the electrode surface charge. Interestingly, EMI+BF4- shows higher GK ion conductivity than the 1.1 M acetonitrile solution between two parallel plate electrodes.

Ion dynamics in porous carbon electrodes in supercapacitors using in situ infrared spectroelectrochemistry.

PubMed

Richey, Francis W; Dyatkin, Boris; Gogotsi, Yury; Elabd, Yossef A

2013-08-28

Electrochemical double layer capacitors (EDLCs), or supercapacitors, rely on electrosorption of ions by porous carbon electrodes and offer a higher power and a longer cyclic lifetime compared to batteries. Ionic liquid (IL) electrolytes can broaden the operating voltage window and increase the energy density of EDLCs. Herein, we present direct measurements of the ion dynamics of 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide in an operating EDLC with electrodes composed of porous nanosized carbide-derived carbons (CDCs) and nonporous onion-like carbons (OLCs) with the use of in situ infrared spectroelectrochemistry. For CDC electrodes, IL ions (both cations and anions) were directly observed entering and exiting CDC nanopores during charging and discharging of the EDLC. Conversely, for OLC electrodes, IL ions were observed in close proximity to the OLC surface without any change in the bulk electrolyte concentration during charging and discharging of the EDLC. This provides experimental evidence that charge is stored on the surface of OLCs in OLC EDLCs without long-range ion transport through the bulk electrode. In addition, for CDC EDLCs with mixed electrolytes of IL and propylene carbonate (PC), the IL ions were observed entering and exiting CDC nanopores, while PC entrance into the nanopores was IL concentration dependent. This work provides direct experimental confirmation of EDLC charging mechanisms that previously were restricted to computational simulations and theories. The experimental measurements presented here also provide deep insights into the molecular level transport of IL ions in EDLC electrodes that will impact the design of the electrode materials' structure for electrical energy storage.

Preparation, characterization and application of urease nanoparticles for construction of an improved potentiometric urea biosensor.

PubMed

Jakhar, Seema; Pundir, C S

2018-02-15

The nanoparticles (NPs) aggregates of commercial urease from jack beans (Canavalia ensiformis) were prepared by desolvation and glutaraldehyde crosslinking and functionalized by cysteamine dihydrochloride. These enzyme nanoparticles (ENPs) were characterized by transmission electron microscopy (TEM), UV and Fourier transform infrared (FTIR) spectroscopy. The TEM images of urease NPs showed their size in the range, 18-100nm with an average of 51.2nm. The ENPs were more active and stable with a longer shelf life than native enzyme molecules. The ENPs were immobilized onto chitosan (CHIT) activated nitrocellulose (NC) membrane via glutaraldehyde coupling with 32.22% retention of initial activity of free ureaseNPs with a conjugation yield of 1.63mg/cm 2 . This NC membrane was mounted at the lower/sensitive end of the ammonium ion selective electrode (AISE) with O-ring and then electrode was connected to a digital pH meter to construct a potentiometric urea biosensor. The biosensor exhibited optimum response within 10s at pH 5.5and 40°C. The biosensor was employed for measurement of potentiometric determination of urea in sera of apparently healthy and persons suffering from kidney disorders. The biosensor displayed a low detection limit of 1µM/L with a wide working range of 2-80µM/L (0.002-0.08mM) and sensitivity of 23mV/decade. The analytical recovery of added urea in serum was 106.33%. The within and between-batch coefficient of variations (CVs) of present biosensor were 0.18% and 0.32% respectively. There was a good correlation (r = 0.99) between sera urea values obtained by reference method (Enzymic colorimetric kit method) and the present biosensor. The biosensor had negligible interference from Na + ,K + ,NH +4 and Ca 2+ but Mg 2+ ,Cu 2+ and ascorbic acid but had slight interference, which was overcome by specific ion selective electrode. The ENPs bound NC membrane was used maximally 8-9 times per day over a period of 180 days, when stored in 0.01M sodium acetate buffer pH 5.5 at 4°C. Copyright © 2017 Elsevier B.V. All rights reserved.

Relationship between pore size and reversible and irreversible immobilization of ionic liquid electrolytes in porous carbon under applied electric potential

DOE PAGES

Mahurin, Shannon M.; Mamontov, Eugene; Thompson, Matthew W.; ...

2016-10-04

Transport of electrolytes in nanoporous carbon-based electrodes largely defines the function and performance of energy storage devices. Here, using molecular dynamics simulation and quasielastic neutron scattering, we investigate the microscopic dynamics of a prototypical ionic liquid electrolyte, [emim][Tf 2N], under applied electric potential in carbon materials with 6.7 nm and 1.5 nm pores. The simulations demonstrate the formation of dense layers of counter-ions near the charged surfaces, which is reversible when the polarity is reversed. In the experiment, the ions immobilized near the surface manifest themselves in the elastic scattering signal. The experimentally observed ion immobilization near the wall ismore » fully reversible as a function of the applied electric potential in the 6.7 nm, but not in the 1.5 nm nanopores. In the latter case, remarkably, the first application of the electric potential leads to apparently irreversible immobilization of cations or anions, depending on the polarity, near the carbon pore walls. This unexpectedly demonstrates that in carbon electrode materials with the small pores, which are optimal for energy storage applications, the polarity of the electrical potential applied for the first time after the introduction of an ionic liquid electrolyte may define the decoration of the small pore walls with ions for prolonged periods of time and possibly for the lifetime of the electrode.« less

Sodium Sulfur Battery Cell Experiment (NaSBE)

NASA Technical Reports Server (NTRS)

Garner, J. Christopher

1997-01-01

The Ford Motor Company published papers describing new types of secondary battery comprised of: solid, sodium ion conducting electrolyte; liquid metal electrode; redox electrode; operating temperature between 300 and 400 deg. C; specific energy of 150 Wh/kg; and a nominal voltage of 2.0 V.

Polymers for new battery technologies.

NASA Astrophysics Data System (ADS)

Singh, Mohit

2009-03-01

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

Calixarene-Mediated Liquid-Membrane Transport of Choline Conjugates

PubMed Central

Adhikari, Birendra Babu; Fujii, Ayu

2015-01-01

A series of supramolecular calixarenes efficiently transport distinct molecular species through a liquid membrane when attached to a receptor-complementary choline handle. Calix-[6]arene hexacarboxylic acid was highly effective at transporting different target molecules against a pH gradient. Both carboxylic- and phosphonic-acid-functionalized calix[4]arenes effect transport without requiring a pH or ion gradient. NMR binding studies, two-phase solvent extraction, and three-phase transport experiments reveal the necessary and subtle parameters to effect the transport of molecules attached to a choline “handle”. On the other hand, rescorin[4]arene cavitands, which have similar guest recognition profiles, did not transport guest molecules. These developments reveal new approaches towards attempting synthetic-receptor-mediated selective small-molecule transport in vesicular and cellular systems. PMID:26161034

Anomalous or regular capacitance? The influence of pore size dispersity on double-layer formation

NASA Astrophysics Data System (ADS)

Jäckel, N.; Rodner, M.; Schreiber, A.; Jeongwook, J.; Zeiger, M.; Aslan, M.; Weingarth, D.; Presser, V.

2016-09-01

The energy storage mechanism of electric double-layer capacitors is governed by ion electrosorption at the electrode surface. This process requires high surface area electrodes, typically highly porous carbons. In common organic electrolytes, bare ion sizes are below one nanometer but they are larger when we consider their solvation shell. In contrast, ionic liquid electrolytes are free of solvent molecules, but cation-anion coordination requires special consideration. By matching pore size and ion size, two seemingly conflicting views have emerged: either an increase in specific capacitance with smaller pore size or a constant capacitance contribution of all micro- and mesopores. In our work, we revisit this issue by using a comprehensive set of electrochemical data and a pore size incremental analysis to identify the influence of certain ranges in the pore size distribution to the ion electrosorption capacity. We see a difference in solvation of ions in organic electrolytes depending on the applied voltage and a cation-anion interaction of ionic liquids in nanometer sized pores.

Probing nanoscale ion dynamics in ultrathin films of polymerized ionic liquids by broadband dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Sangoro, Joshua; Heres, Maximilian; Cosby, Tyler

Continuous progress in energy storage and conversion technologies necessitates novel experimental approaches that can provide fundamental insights regarding the impact of reduced dimensions on the functional properties of materials. In this talk, a nondestructive experimental approach to probe nanoscale ion dynamics in ultrathin films of polymerized ionic liquids over a broad frequency range spanning over six orders of magnitude by broadband dielectric spectroscopy will be presented. The approach involves using an electrode configuration with lithographically patterned silica nanostructures, which allow for an air gap between the confined ion conductor and one of the electrodes. It is observed that the characteristic ion dynamics rates significantly slow down with decreasing film thicknesses above the calorimetric glass transition of the bulk polymer. However, the mean rates remain bulk-like at lower temperatures. These results highlight the increasing influence of the polymer/substrate interactions with decreasing film thickness on ion dynamics. The authors gratefully acknowledge the National Science Foundation for financial support through the Polymers Program award DMR-1508394.

Mask-less deposition of Au-SnO2 nanocomposites on CMOS MEMS platform for ethanol detection.

PubMed

Santra, S; Sinha, A K; De Luca, A; Ali, S Z; Udrea, F; Guha, P K; Ray, S K; Gardner, J W

2016-03-29

Here we report on the mask-less deposition of Au-SnO2 nanocomposites with a silicon-on-insulator (SOI) complementary metal oxide semiconductor (CMOS) micro electro mechanical system (MEMS) platform through the use of dip pen nanolithography (DPN) to create a low-cost ethanol sensor. MEMS technology is used in order to achieve low power consumption, by the employment of a membrane structure formed using deep reactive ion etching technique. The device consists of an embedded tungsten micro-heater with gold interdigitated electrodes on top of the SOI membrane. The tungsten micro-heater is used to raise the membrane temperature up to its operating temperature and the electrodes are used to measure the resistance of the nanocomposite sensing layer. The CMOS MEMS devices have high electro-thermal efficiency, with 8.2 °C temperature increase per mW power of consumption. The sensing material (Au-SnO2 nanocomposite) was synthesised starting from SnO nanoplates, then Au nanoparticles were attached chemically to the surface of SnO nanoplates, finally the mixture was heated at 700 °C in an oven in air for 4 h. This composite material was sonicated for 2 h in terpineol to make a viscous homogeneous slurry and then 'written' directly across the electrode area using the DPN technique without any mask. The devices were characterised by exposure to ethanol vapour in humid air in the concentration range of 100-1000 ppm. The sensitivity varied from 1.2 to 0.27 ppm(-1) for 100-1000 ppm of ethanol at 10% relative humid air. Selectivity measurements showed that the sensors were selective towards ethanol when they were exposed to acetone and toluene.

Mask-less deposition of Au-SnO2 nanocomposites on CMOS MEMS platform for ethanol detection

NASA Astrophysics Data System (ADS)

Santra, S.; Sinha, A. K.; De Luca, A.; Ali, S. Z.; Udrea, F.; Guha, P. K.; Ray, S. K.; Gardner, J. W.

2016-03-01

Here we report on the mask-less deposition of Au-SnO2 nanocomposites with a silicon-on-insulator (SOI) complementary metal oxide semiconductor (CMOS) micro electro mechanical system (MEMS) platform through the use of dip pen nanolithography (DPN) to create a low-cost ethanol sensor. MEMS technology is used in order to achieve low power consumption, by the employment of a membrane structure formed using deep reactive ion etching technique. The device consists of an embedded tungsten micro-heater with gold interdigitated electrodes on top of the SOI membrane. The tungsten micro-heater is used to raise the membrane temperature up to its operating temperature and the electrodes are used to measure the resistance of the nanocomposite sensing layer. The CMOS MEMS devices have high electro-thermal efficiency, with 8.2 °C temperature increase per mW power of consumption. The sensing material (Au-SnO2 nanocomposite) was synthesised starting from SnO nanoplates, then Au nanoparticles were attached chemically to the surface of SnO nanoplates, finally the mixture was heated at 700 °C in an oven in air for 4 h. This composite material was sonicated for 2 h in terpineol to make a viscous homogeneous slurry and then ‘written’ directly across the electrode area using the DPN technique without any mask. The devices were characterised by exposure to ethanol vapour in humid air in the concentration range of 100-1000 ppm. The sensitivity varied from 1.2 to 0.27 ppm-1 for 100-1000 ppm of ethanol at 10% relative humid air. Selectivity measurements showed that the sensors were selective towards ethanol when they were exposed to acetone and toluene.

A selective iodide ion sensor electrode based on functionalized ZnO nanotubes.

PubMed

Ibupoto, Zafar Hussain; Khun, Kimleang; Willander, Magnus

2013-02-04

In this research work, ZnO nanotubes were fabricated on a gold coated glass substrate through chemical etching by the aqueous chemical growth method. For the first time a nanostructure-based iodide ion selective electrode was developed. The ZnO nanotubes were functionalized with miconazole ion exchanger and the electromotive force (EMF) was measured by the potentiometric method. The iodide ion sensor exhibited a linear response over a wide range of concentrations (1 × 10-6 to 1 × 10-1 M) and excellent sensitivity of -62 ± 1 mV/decade. The detection limit of the proposed sensor was found to be 5 × 10-7 M. The effects of pH, temperature, additive, plasticizer and stabilizer on the potential response of iodide ion selective electrode were also studied. The proposed iodide ion sensor demonstrated a fast response time of less than 5 s and high selectivity against common organic and the inorganic anions. All the obtained results revealed that the iodide ion sensor based on functionalized ZnO nanotubes may be used for the detection of iodide ion in environmental water samples, pharmaceutical products and other real samples.

A Selective Iodide Ion Sensor Electrode Based on Functionalized ZnO Nanotubes

PubMed Central

Ibupoto, Zafar Hussain; Khun, Kimleang; Willander, Magnus

2013-01-01

In this research work, ZnO nanotubes were fabricated on a gold coated glass substrate through chemical etching by the aqueous chemical growth method. For the first time a nanostructure-based iodide ion selective electrode was developed. The ZnO nanotubes were functionalized with miconazole ion exchanger and the electromotive force (EMF) was measured by the potentiometric method. The iodide ion sensor exhibited a linear response over a wide range of concentrations (1 × 10−6 to 1 × 10−1 M) and excellent sensitivity of −62 ± 1 mV/decade. The detection limit of the proposed sensor was found to be 5 × 10−7 M. The effects of pH, temperature, additive, plasticizer and stabilizer on the potential response of iodide ion selective electrode were also studied. The proposed iodide ion sensor demonstrated a fast response time of less than 5 s and high selectivity against common organic and the inorganic anions. All the obtained results revealed that the iodide ion sensor based on functionalized ZnO nanotubes may be used for the detection of iodide ion in environmental water samples, pharmaceutical products and other real samples. PMID:23385412

Microfabrication and characterization of an array of dielectric elastomer actuators generating uniaxial strain to stretch individual cells

NASA Astrophysics Data System (ADS)

Akbari, S.; Shea, H. R.

2012-04-01

Cells regulate their behavior in response to mechanical strains. Cell cultures to study mechanotransuction are typically cm2 in area, far too large to monitor single cell response. We have developed an array of dielectric elastomer microactuators as a tool to study mechanotransduction of individual cells. The array consists of 72 100 µm × 200 µm electroactive polymer actuators which expand uniaxially when a voltage is applied. Single cells will be attached on each actuator to study their response to periodic mechanical strains. The device is fabricated by patterning compliant microelectrodes on both sides of a 30 µm thick polydimethylsiloxane membrane, which is bonded to a Pyrex chip with 200 µm wide trenches. Low-energy metal ion implantation is used to make stretchable electrodes and we demonstrate here the successful miniaturization of such ion-implanted electrodes. The top electrode covers the full membrane area, while the bottom electrodes are 100 µm wide parallel lines, perpendicular to the trenches. Applying a voltage between the top and bottom electrodes leads to uniaxial expansion of the membrane at the intersection of the bottom electrodes and the trenches. To characterize the in-plane strain, an array of 4 µm diameter aluminum dots is deposited on each actuator. The position of each dot is tracked, allowing displacement and strain profiles to be measured as a function of voltage. The uniaxial strain reaches 4.7% at 2.9 kV with a 0.2 s response time, sufficient to stimulate most cells with relevant biological strains and frequencies.

Properties of the Nafion membrane impregnated with hydroxyl ammonium based ionic liquids

NASA Astrophysics Data System (ADS)

Garaev, Valeriy; Kleperis, Janis; Pavlovica, Sanita; Vaivars, Guntars

2012-08-01

In this work, the Nafion 112 membrane impregnated with nine various hydroxyl ammonium based ionic liquids have been investigated. The used ionic liquids were combined from hydroxyl ammonium cations (2-hydroxyethylammonium/HEA, bis(2- hydroxyethyl)ammonium/BHEA, tris(2-hydroxyethyl)ammonium/THEA) and carboxylate anions (formate, acetate, lactate). The membranes are characterized by conductivity and thermal stability measurements. It was found, that almost all composites have 10 times higher ion conductivity than a pure Nafion 112 at 90 °C in ambient environment due to the higher thermal stability. The thermal stability of Nafion membrane was increased by all studied nine ionic liquids. In this work, only biodegradable ionic liquids were used for composite preparation.

Compact ion chamber based neutron detector

DOEpatents

Derzon, Mark S.; Galambos, Paul C.; Renzi, Ronald F.

2015-10-27

A directional neutron detector has an ion chamber formed in a dielectric material; a signal electrode and a ground electrode formed in the ion chamber; a neutron absorbing material filling the ion chamber; readout circuitry which is electrically coupled to the signal and ground electrodes; and a signal processor electrically coupled to the readout circuitry. The ion chamber has a pair of substantially planar electrode surfaces. The chamber pressure of the neutron absorbing material is selected such that the reaction particle ion trail length for neutrons absorbed by the neutron absorbing material is equal to or less than the distance between the electrode surfaces. The signal processor is adapted to determine a path angle for each absorbed neutron based on the rise time of the corresponding pulse in a time-varying detector signal.

Lithium-Sulfur Batteries: from Liquid to Solid Cells?

DOE PAGES

Lin, Zhan; Liang, Chengdu

2014-11-11

Lithium-sulfur (Li-S) batteries supply a theoretical specific energy 5 times higher than that of lithium-ion batteries (2,500 vs. ~500 Wh kg-1). However, the insulating properties and polysulfide shuttle effects of the sulfur cathode and the safety concerns of the lithium anode in liquid electrolytes are still key limitations to practical use of traditional Li-S batteries. In this review, we start with a brief discussion on fundamentals of Li-S batteries and key challenges associated with the conventional liquid cells. Then, we introduce the most recent progresses in the liquid systems, including the sulfur positive electrodes, the lithium negative electrodes, and themore » electrolytes and binders. We discuss the significance of investigating electrode reaction mechanisms in liquid cells using in-situ techniques to monitor the compositional and morphological changes. By moving from the traditional liquid cells to recent solid cells, we discuss the importance of this game-changing shift with positive advances in both solid electrolytes and electrode materials. Finally, the opportunities and perspectives for future research on Li-S batteries are presented.« less

Computer Simulations of Ion Transport in Polymer Electrolyte Membranes.

PubMed

Mogurampelly, Santosh; Borodin, Oleg; Ganesan, Venkat

2016-06-07

Understanding the mechanisms and optimizing ion transport in polymer membranes have been the subject of active research for more than three decades. We present an overview of the progress and challenges involved with the modeling and simulation aspects of the ion transport properties of polymer membranes. We are concerned mainly with atomistic and coarser level simulation studies and discuss some salient work in the context of pure binary and single ion conducting polymer electrolytes, polymer nanocomposites, block copolymers, and ionic liquid-based hybrid electrolytes. We conclude with an outlook highlighting future directions.

Capacitive mixing with electrodes of the same kind for energy production from salinity differences

NASA Astrophysics Data System (ADS)

Marino, M.; Kozynchenko, O.; Tennison, S.; Brogioli, D.

2016-03-01

The capacitive mixing technique is aimed at producing renewable energy from salinity differences, for example between sea and river water. The technique makes use of two electrodes that modify their potential in opposite directions when the concentration of the solution in which they are immersed is changed, as a consequence of the dynamics of the electric double layer which forms in the ionic solution. Unfortunately, it is difficult to find two electrodes presenting both optimal performances and opposite potential variations. In order to overcome this problem, we present here a cell scheme with electrodes of the same kind (and thus identical dependence of potential on concentration) which can be operated with a CapMix cycle; it is based on a concentration cell with identical electrodes dipped into two compartments separated by a non-perm-selective porous diaphragm. Thanks to the cyclic operation, the actual cell voltage rise and the power production are close to the values obtained with the traditional scheme, or even higher, depending on the features of the ion transport in the liquid junction region. We present an experimental demonstration of the working principles and we study the power production and energy efficiency in the light of the theory of ion transport in fluids. We show that our technique is competitive with respect to the other CapMix techniques, with the relevant advantage that we make use of only one kind of electrode.

Capacitive mixing with electrodes of the same kind for energy production from salinity differences.

PubMed

Marino, M; Kozynchenko, O; Tennison, S; Brogioli, D

2016-03-23

The capacitive mixing technique is aimed at producing renewable energy from salinity differences, for example between sea and river water. The technique makes use of two electrodes that modify their potential in opposite directions when the concentration of the solution in which they are immersed is changed, as a consequence of the dynamics of the electric double layer which forms in the ionic solution. Unfortunately, it is difficult to find two electrodes presenting both optimal performances and opposite potential variations. In order to overcome this problem, we present here a cell scheme with electrodes of the same kind (and thus identical dependence of potential on concentration) which can be operated with a CapMix cycle; it is based on a concentration cell with identical electrodes dipped into two compartments separated by a non-perm-selective porous diaphragm. Thanks to the cyclic operation, the actual cell voltage rise and the power production are close to the values obtained with the traditional scheme, or even higher, depending on the features of the ion transport in the liquid junction region. We present an experimental demonstration of the working principles and we study the power production and energy efficiency in the light of the theory of ion transport in fluids. We show that our technique is competitive with respect to the other CapMix techniques, with the relevant advantage that we make use of only one kind of electrode.

Dielectrophoresis-based particle sensor using nanoelectrode arrays

NASA Technical Reports Server (NTRS)

Arumugam, Prabhu U. (Inventor); Li, Jun (Inventor); Cassell, Alan M. (Inventor)

2009-01-01

A method for concentrating or partly separating particles of a selected species from a liquid or fluid containing these particles and flowing in a channel, and for determining if the selected species particle is present in the liquid or fluid. A time varying electrical field E, having a root-mean-square intensity E.sup.2.sub.rms with a non-zero gradient in a direction transverse to the liquid or fluid flow direction, is produced by a nanostructure electrode array, with a very high magnitude gradient near exposed electrode tips. A dielectrophoresis force causes the selected particles to accumulate near the electrode tips, if the medium and selected particles have substantially different dielectric constants. An insulating material surrounds most of each of the nanostructure electrodes, and a region of the insulating material surface is functionalized to promote attachment of the selected species particles to the surface. An electrical property value Z(meas) is measured at the functionalized surface and is compared with a reference value Z(ref) to determine if the selected species particles are attached to the functionalized surface.

Ultrathin and Ion-Selective Janus Membranes for High-Performance Osmotic Energy Conversion.

PubMed

Zhang, Zhen; Sui, Xin; Li, Pei; Xie, Ganhua; Kong, Xiang-Yu; Xiao, Kai; Gao, Longcheng; Wen, Liping; Jiang, Lei

2017-07-05

The osmotic energy existing in fluids is recognized as a promising "blue" energy source that can help solve the global issues of energy shortage and environmental pollution. Recently, nanofluidic channels have shown great potential for capturing this worldwide energy because of their novel transport properties contributed by nanoconfinement. However, with respect to membrane-scale porous systems, high resistance and undesirable ion selectivity remain bottlenecks, impeding their applications. The development of thinner, low-resistance membranes, meanwhile promoting their ion selectivity, is a necessity. Here, we engineered ultrathin and ion-selective Janus membranes prepared via the phase separation of two block copolymers, which enable osmotic energy conversion with power densities of approximately 2.04 W/m 2 by mixing natural seawater and river water. Both experiments and continuum simulation help us to understand the mechanism for how membrane thickness and channel structure dominate the ion transport process and overall device performance, which can serve as a general guiding principle for the future design of nanochannel membranes for high-energy concentration cells.

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions.

PubMed

Burt, Ryan; Breitsprecher, Konrad; Daffos, Barbara; Taberna, Pierre-Louis; Simon, Patrice; Birkett, Greg; Zhao, X S; Holm, Christian; Salanne, Mathieu

2016-10-06

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.

Composite Polymer-Garnet Solid State Electrolytes

NASA Astrophysics Data System (ADS)

Villa, Andres; Oduncu, Muhammed R.; Scofield, Gregory D.; Marinero, Ernesto E.; Forbey, Scott

Solid-state electrolytes provide a potential solution to the safety and reliability issues of Li-ion batteries. We have synthesized cubic-phase Li7-xLa3Zr2-xBixO12 compounds utilizing inexpensive, scalable Sol-gel synthesis and obtained ionic conductivities 1.2 x 10-4 S/cm at RT in not-fully densified pellets. In this work we report on the fabrication of composite polymer-garnet ceramic particle electrolytes to produce flexible membranes that can be integrated with standard battery electrodes without the need for a separator. As a first step we incorporated the ceramic particles into polyethylene oxide polymers (PEO) to form flexible membranes. Early results are encouraging yielding ionic conductivity values 1.0 x 10-5 S/cm at RT. To increment the conductivity in the membranes, we are optimizing amongst other: the ceramic particle size distribution and weight load, the polymer molecular weight and chemical composition and the solvated Li-salt composition and content. Unhindered ion transport across interfaces between the composites and the battery electrode materials is paramount for battery performance. To this end, we are investigating the effect of interface morphology, its atomic composition and exploring novel electrode structures that facilitate ionic transport.

Current status of environmental, health, and safety issues of lithium ion electric vehicle batteries

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

Vimmerstedt, L.J.; Ring, S.; Hammel, C.J.

The lithium ion system considered in this report uses lithium intercalation compounds as both positive and negative electrodes and has an organic liquid electrolyte. Oxides of nickel, cobalt, and manganese are used in the positive electrode, and carbon is used in the negative electrode. This report presents health and safety issues, environmental issues, and shipping requirements for lithium ion electric vehicle (EV) batteries. A lithium-based electrochemical system can, in theory, achieve higher energy density than systems using other elements. The lithium ion system is less reactive and more reliable than present lithium metal systems and has possible performance advantages overmore » some lithium solid polymer electrolyte batteries. However, the possibility of electrolyte spills could be a disadvantage of a liquid electrolyte system compared to a solid electrolyte. The lithium ion system is a developing technology, so there is some uncertainty regarding which materials will be used in an EV-sized battery. This report reviews the materials presented in the open literature within the context of health and safety issues, considering intrinsic material hazards, mitigation of material hazards, and safety testing. Some possible lithium ion battery materials are toxic, carcinogenic, or could undergo chemical reactions that produce hazardous heat or gases. Toxic materials include lithium compounds, nickel compounds, arsenic compounds, and dimethoxyethane. Carcinogenic materials include nickel compounds, arsenic compounds, and (possibly) cobalt compounds, copper, and polypropylene. Lithiated negative electrode materials could be reactive. However, because information about the exact compounds that will be used in future batteries is proprietary, ongoing research will determine which specific hazards will apply.« less

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium-Sulfur Batteries.

PubMed

Ward, Ashleigh L; Doris, Sean E; Li, Longjun; Hughes, Mark A; Qu, Xiaohui; Persson, Kristin A; Helms, Brett A

2017-05-24

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device's active materials when they enter the membrane's pore. This transformation has little influence on the membrane's ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development.

Polymer gel electrolytes for application in aluminum deposition and rechargeable aluminum ion batteries

DOE PAGES

Sun, Xiao -Guang; Fang, Youxing; Jiang, Xueguang; ...

2015-10-22

Polymer gel electrolyte using AlCl3 complexed acrylamide as functional monomer and ionic liquids based on acidic mixture of 1-ethyl-3-methylimidazolium chloride (EMImCl) and AlCl 3 as plasticizer has been successfully prepared for the first time by free radical polymerization. Aluminum deposition is successfully obtained with a polymer gel membrane contianing 80 wt% ionic liquid. As a result, the polymer gel membranes are also good candidates for rechargeable aluminum ion batteries.

Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s.

PubMed

Xu, Weinan; Ledin, Petr A; Shevchenko, Valery V; Tsukruk, Vladimir V

2015-06-17

Branched polyelectrolytes with cylindrical brush, dendritic, hyperbranched, grafted, and star architectures bearing ionizable functional groups possess complex and unique assembly behavior in solution at surfaces and interfaces as compared to their linear counterparts. This review summarizes the recent developments in the introduction of various architectures and understanding of the assembly behavior of branched polyelectrolytes with a focus on functional polyelectrolytes and poly(ionic liquid)s with responsive properties. The branched polyelectrolytes and poly(ionic liquid)s interact electrostatically with small molecules, linear polyelectrolytes, or other branched polyelectrolytes to form assemblies of hybrid nanoparticles, multilayer thin films, responsive microcapsules, and ion-conductive membranes. The branched structures lead to unconventional assemblies and complex hierarchical structures with responsive properties as summarized in this review. Finally, we discuss prospectives for emerging applications of branched polyelectrolytes and poly(ionic liquid)s for energy harvesting and storage, controlled delivery, chemical microreactors, adaptive surfaces, and ion-exchange membranes.

Coating and functionalization of high density ion track structures by atomic layer deposition

NASA Astrophysics Data System (ADS)

Mättö, Laura; Szilágyi, Imre M.; Laitinen, Mikko; Ritala, Mikko; Leskelä, Markku; Sajavaara, Timo

2016-10-01

In this study flexible TiO2 coated porous Kapton membranes are presented having electron multiplication properties. 800 nm crossing pores were fabricated into 50 μm thick Kapton membranes using ion track technology and chemical etching. Consecutively, 50 nm TiO2 films were deposited into the pores of the Kapton membranes by atomic layer deposition using Ti(iOPr)4 and water as precursors at 250 °C. The TiO2 films and coated membranes were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray reflectometry (XRR). Au metal electrode fabrication onto both sides of the coated foils was achieved by electron beam evaporation. The electron multipliers were obtained by joining two coated membranes separated by a conductive spacer. The results show that electron multiplication can be achieved using ALD-coated flexible ion track polymer foils.

Device and method for the measurement of gas permeability through membranes

DOEpatents

Agarwal, Pradeep K.; Ackerman, John; Borgialli, Ron; Hamann, Jerry; Muknahalliptna, Suresh

2006-08-08

A device for the measuring membrane permeability in electrical/electrochemical/photo-electrochemical fields is provided. The device is a permeation cell and a tube mounted within the cell. An electrode is mounted at one end of the tube. A membrane is mounted within the cell wherein a corona is discharged from the electrode in a general direction toward the membrane thereby generating heated hydrogen atoms adjacent the membrane. A method for measuring the effects of temperature and pressure on membrane permeability and selectivity is also provided.

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

Pasaribu, Marvin H., E-mail: marvin-shady88@yahoo.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id

Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li{sup +} ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anionmore » metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10{sup −2} S cm{sup −1} for chitosan to 1.30 × 10{sup −2} S cm{sup −1} for chitosan with EMImBF4/Li{sup +}, and this result was supported by analysis the surface morphology (SEM)« less

Advanced Supported Liquid Membranes for Carbon Dioxide Control in Extravehicular Activity Applications

NASA Technical Reports Server (NTRS)

Gleason, Kevin J. (Inventor); Cowley, Scott W. (Inventor); Wickham, David T. (Inventor)

2015-01-01

There is disclosed a portable life support system with a component for removal of at least one selected gas. In an embodiment, the system includes a supported liquid membrane having a first side and a second side in opposition to one another, the first side configured for disposition toward an astronaut and the second side configured for disposition toward a vacuum atmosphere. The system further includes an ionic liquid disposed between the first side and the second side of the supported liquid membrane, the ionic liquid configured for removal of at least one selected gas from a region housing the astronaut adjacent the first side of the supported liquid membrane to the vacuum atmosphere adjacent the second side of the supported liquid membrane. Other embodiments are also disclosed.

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface.

PubMed

Yu, Chuang; Ganapathy, Swapna; Eck, Ernst R H van; Wang, Heng; Basak, Shibabrata; Li, Zhaolong; Wagemaker, Marnix

2017-10-20

Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode-electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte-electrode interface design for future all-solid-state batteries.

Integrated Arrays of Ion-Sensitive Electrodes

NASA Technical Reports Server (NTRS)

Buehler, Martin; Kuhlman, Kimberly

2003-01-01

The figure depicts an example of proposed compact water-quality sensors that would contain integrated arrays of ion-sensitive electrodes (ISEs). These sensors would serve as electronic "tongues": they would be placed in contact with water and used to "taste" selected dissolved ions (that is, they would be used to measure the concentrations of the ions). The selected ions could be any or all of a variety of organic and inorganic cations and anions that could be regarded as contaminants or analytes, depending on the specific application. In addition, some of the ISEs could be made sensitive to some neutral analytes

Experimental Study of Heating of a Liquid Cathode and Transfer of Its Components into the Gas Phase under the Action of a DC Discharge

NASA Astrophysics Data System (ADS)

Sirotkin, N. A.; Titov, V. A.

2018-04-01

An atmospheric-pressure dc discharge in air ( i = 10-50 mA) with metal and liquid electrolyte electrodes was studied experimentally. An aqueous solution of sodium chloride (0.5 mol/L) was used as the cathode or anode. The electric field strength in the plasma and the cathode (anode) voltage drops were obtained from the measured dependences of the discharge voltage on the electrode gap length. The gas temperature was deduced from the spectral distribution of nitrogen emission in the band N2( C 3Π u → B 3Π g , 0-2). The time dependences of the temperatures of the liquid electrolyte electrodes during the discharge and in its afterglow, as well as the evaporation rate of the solution, were determined experimentally. The contributions of ion bombardment and heat flux from the plasma to the heating of the liquid electrode and transfer of solvent (water) into the gas phase are discussed using the experimental data obtained.

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

PubMed

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

2017-12-19

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

Exhaustive thin-layer cyclic voltammetry for absolute multianalyte halide detection.

PubMed

Cuartero, Maria; Crespo, Gastón A; Ghahraman Afshar, Majid; Bakker, Eric

2014-11-18

Water analysis is one of the greatest challenges in the field of environmental analysis. In particular, seawater analysis is often difficult because a large amount of NaCl may mask the determination of other ions, i.e., nutrients, halides, and carbonate species. We demonstrate here the use of thin-layer samples controlled by cyclic voltammetry to analyze water samples for chloride, bromide, and iodide. The fabrication of a microfluidic electrochemical cell based on a Ag/AgX wire (working electrode) inserted into a tubular Nafion membrane is described, which confines the sample solution layer to less than 15 μm. By increasing the applied potential, halide ions present in the thin-layer sample (X(-)) are electrodeposited on the working electrode as AgX, while their respective counterions are transported across the perm-selective membrane to an outer solution. Thin-layer cyclic voltammetry allows us to obtain separated peaks in mixed samples of these three halides, finding a linear relationship between the halide concentration and the corresponding peak area from about 10(-5) to 0.1 M for bromide and iodide and from 10(-4) to 0.6 M for chloride. This technique was successfully applied for the halide analysis in tap, mineral, and river water as well as seawater. The proposed methodology is absolute and potentially calibration-free, as evidenced by an observed 2.5% RSD cell to cell reproducibility and independence from the operating temperature.

Enhanced Monitoring of Nanosecond Electric Pulse-Evoked Membrane Conductance Changes in Whole-Cell Patch Clamp Experiments.

PubMed

Yoon, Jihwan; Leblanc, Normand; Zaklit, Josette; Vernier, P Thomas; Chatterjee, Indira; Craviso, Gale L

2016-10-01

Patch clamp electrophysiology serves as a powerful method for studying changes in plasma membrane ion conductance induced by externally applied high-intensity nanosecond electric pulses (NEPs). This paper describes an enhanced monitoring technique that minimizes the length of time between pulse exposure and data recording in a patch-clamped excitable cell. Whole-cell membrane currents were continuously recorded up to 11 ms before and resumed 8 ms after delivery of a 5-ns, 6 MV/m pulse by a pair of tungsten rod electrodes to a patched adrenal chromaffin cell maintained at a holding potential of -70 mV. This timing was achieved by two sets of relay switches. One set was used to disconnect the patch pipette electrode from the pre-amplifier and connect it to a battery to maintain membrane potential at -70 mV, and also to disconnect the reference electrode from the amplifier. The other set was used to disconnect the electrodes from the pulse generator until the time of NEP/sham exposure. The sequence and timing of both sets of relays were computer-controlled. Using this procedure, we observed that a 5-ns pulse induced an instantaneous inward current that decayed exponentially over the course of several minutes, that a second pulse induced a similar response, and that the current was carried, at least in part, by Na + . This approach for characterizing ion conductance changes in an excitable cell in response to NEPs will yield information essential for assessing the potential use of NEP stimulation for therapeutic applications.

Molecular transport properties through carbon nanotube membrane

NASA Astrophysics Data System (ADS)

Majumder, Mainak

Molecular transport through hollow cores of crystalline carbon nanotubes (CNTs) are of considerable interest from the fundamental and application point of view. This dissertation focuses on understanding molecular transport through a membrane platform consisting of open ended CNTs with ˜ 7 nm core diameter and ˜ 1010 CNTs/cm2 encapsulated in an inert polymer matrix. While ionic diffusion through the membrane is close to bulk diffusion expectations, gases and liquids were respectively observed to be transported ˜ 10 times faster than Knudsen diffusion and ˜ 10000--100000 times faster than hydrodynamic flow predictions. This phenomenon has been attributed to the non-interactive and frictionless graphitic interface. Functionalization of the CNT tips was observed to change selectivity and flux through the CNT membranes with analogy to 'gate-keeper' functionality in biological membranes. An electro-chemical diazonium grafting chemistry was utilized for enhancing the functional density on the CNT membranes. A strategy to confine the reactions at the CNT tips by a fast flowing liquid column was also designed. Characterization using electrochemical impedance spectroscopy and dye assay indicated ˜ 5--6 times increase in functional density. Electrochemical impedance spectroscopy experiments on CNT membrane/electrode functionalized with charged macro-molecules showed voltage-controlled conformational change. Similar chemistry has been applied for realizing 'voltage-gated' transport channels with potential application in trans-dermal drug delivery. Electrically-facilitated transport (a geometry in which an electric field gradient acts across the membrane) through the CNT and functionalized CNT membranes was observed to be electrosmotically controlled. Finally, a simulation framework based on continuum electrostatics and finite elements has been developed to further the understanding of transport through the CNT membranes. KEYWORDS: carbon nanotube membrane, nano-scale hydrodynamics, diazonium grafting, voltage-gated membrane, finite element analysis

High energy density redox flow device

DOEpatents

Chiang, Yet -Ming; Carter, W. Craig; Duduta, Mihai; Limthongkul, Pimpa

2015-10-06

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

High energy density redox flow device

DOEpatents

Chiang, Yet-Ming; Carter, William Craig; Duduta, Mihai; Limthongkul, Pimpa

2014-05-13

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

Ionic polymer metal composites with nanoporous carbon electrodes

NASA Astrophysics Data System (ADS)

Palmre, Viljar; Brandell, Daniel; Mäeorg, Uno; Torop, Janno; Volobujeva, Olga; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2010-04-01

Ionic Polymer Metal Composites (IPMCs) are soft electroactive polymer materials that bend in response to the voltage stimulus (1 - 4 V). They can be used as actuators or sensors. In this paper, we introduce two new highly-porous carbon materials for assembling high specific area electrodes for IPMC actuators and compare their electromechanical performance with recently reported IPMCs based on RuO2 electrodes. We synthesize ionic liquid (Emi-Tf) actuators with either Carbide-Derived Carbon (CDC) (derived from TiC) or coconut shell based activated carbon electrodes. The carbon electrodes are applied onto ionic liquid-swollen Nafion membranes using the direct assembly process. Our results show that actuators assembled with CDC electrodes have the greatest peak-to-peak strain output, reaching up to 20.4 mɛ (equivalent to >2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also revealed significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium–Sulfur Batteries

PubMed Central

2017-01-01

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium–sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development. PMID:28573201

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.

Low-Pressure, Field-Ionizing Mass Spectrometer

NASA Technical Reports Server (NTRS)

Hartley, Frank; Smith, Steven

2009-01-01

A small mass spectrometer utilizing a miniature field ionization source is now undergoing development. It is designed for use in a variety of applications in which there are requirements for a lightweight, low-power-consumption instrument that can analyze the masses of a wide variety of molecules and ions. The device can operate without need for a high-vacuum, carrier-gas feed radioactive ionizing source, or thermal ionizer. This mass spectrometer can operate either in the natural vacuum of outer space or on Earth at any ambient pressure below 50 torr (below about 6.7 kPa) - a partial vacuum that can easily be reached by use of a small sampling pump. This mass spectrometer also has a large dynamic range - from singly charged small gas ions to deoxyribonucleic acid (DNA) fragments larger than 104 atomic mass units - with sensitivity adequate for detecting some molecules and ions at relative abundances of less than one part per billion. This instrument (see figure) includes a field ionizer integrated with a rotating-field mass spectrometer (RFMS). The field ionizer effects ionization of a type characterized as "soft" in the art because it does not fragment molecules or initiate avalanche arcing. What makes the "soft" ionization mode possible is that the distance between the ionizing electrodes is less than mean free path for ions at the maximum anticipated operating pressure, so that the ionizer always operates on the non-breakdown side of the applicable Paschen curve (a standard plot of breakdown potential on the ordinate and pressure electrode separation on the abscissa). The field ionizer in this instrument is fabricated by micromachining a submicron-thick membrane out of an electrically nonconductive substrate, coating the membrane on both sides to form electrodes, then micromachining small holes through the electrodes and membrane. Because of the submicron electrode separation, even a potential of only 1 V applied between the electrodes gives rise to an electric field with a strength of in excess of a megavolt per meter strong enough to ionize any gas molecules passing through the holes. An accelerator grid and an electrostatic deflector focus the ions from the field ionizer into the rotating-field cell of the RFMS. The potentials applied to the electrodes of the cell to generate the rotating electric field typically range from 1 to 13 V. The ions travel in well-defined helices within this cell, after which they are collected in a Faraday cup. The mass of most of the molecules reaching the Faraday cup decreases with increasing frequency of rotation of the electric field in the cell. Therefore, the frequency of rotation of the electric field is made to vary in order to scan through a desired range of ion masses: For example, lightweight gas molecules are scanned at frequencies in the megahertz range, while DNA and other large organic molecules are scanned at kilohertz frequencies.

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

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

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge.

PubMed

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D; Boettcher, Shannon W

2015-08-04

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg(-1) based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30-50 Wh kg(-1) is possible with optimization.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge

PubMed Central

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D.; Boettcher, Shannon W.

2015-01-01

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg−1 based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30–50 Wh kg−1 is possible with optimization. PMID:26239891

ToF-SIMS observation for evaluating the interaction between amyloid β and lipid membranes.

PubMed

Aoyagi, Satoka; Shimanouchi, Toshinori; Kawashima, Tomoko; Iwai, Hideo

2015-04-01

The adsorption behaviour of amyloid beta (Aβ), thought to be a key peptide for understanding Alzheimer's disease, was investigated by means of time-of-flight secondary ion mass spectrometry (ToF-SIMS). Aβ aggregates depending on the lipid membrane condition though it has not been fully understood yet. In this study, Aβ samples on different lipid membranes, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), were observed with ToF-SIMS and the complex ToF-SIMS data of the Aβ samples was interpreted using data analysis techniques such as principal component analysis (PCA), gentle-SIMS (G-SIMS) and g-ogram. DOPC and DMPC are liquid crystal at room temperature, while DPPC is gel at room temperature. As primary ion beams, Bi3(+) and Ar cluster ion beams were used and the effect of an Ar cluster ion for evaluating biomolecules was also studied. The secondary ion images of the peptide fragment ions indicated by G-SIMS and g-ogram were consistent with the PCA results. It is suggested that Aβ is adsorbed homogeneously on the liquid-crystalline-phase lipid membranes, while it aggregates along the lipid on the gel-phase lipid membrane. Moreover, in the results using the Ar cluster, the influence of contamination was reduced.

Theoretical Study of Molecular Transport Through a Permeabilized Cell Membrane in a Microchannel.

PubMed

Mahboubi, Masoumeh; Movahed, Saeid; Hosseini Abardeh, Reza; Hoshyargar, Vahid

2017-06-01

A two-dimensional model is developed to study the molecular transport into an immersed cell in a microchannel and to investigate the effects of finite boundary (a cell is suspended in a microchannel), amplitude of electric pulse, and geometrical parameter (microchannel height and size of electrodes) on cell uptake. Embedded electrodes on the walls of the microchannel generate the required electric pulse to permeabilize the cell membrane, pass the ions through the membrane, and transport them into the cell. The shape of electric pulses is square with the time span of 6 ms; their intensities are in the range of 2.2, 2.4, 2.6, 3 V. Numerical simulations have been performed to comprehensively investigate the molecular uptake into the cell. The obtained results of the current study demonstrate that calcium ions enter the cell from the anodic side (the side near positive electrode); after a while, the cell faces depletion of the calcium ions on a positive electrode-facing side within the microchannel; the duration of depletion depends on the amplitude of electric pulse and geometry that lasts from microseconds to milliseconds. By keeping geometrical parameters and time span constant, increment of a pulse intensity enhances molecular uptake and rate of propagation inside the cell. If a ratio of electrode size to cell diameter is larger than 1, the transported amount of Ca 2+ into the cell, as well as the rate of propagation, will be significantly increased. By increasing the height of the microchannel, the rate of uptake is decreased. In an infinite domain, the peak concentration becomes constant after reaching the maximum value; this value depends on the intra-extracellular conductivity and diffusion coefficient of interior and exterior domains of the cell. In comparison, the maximum concentration is changed by geometrical parameters in the microchannel. After reaching the maximum value, the peak concentration reduces due to the depletion of Ca 2+ ions within the microchannel. Electrophoretic velocity has a significant effect on the cell uptake.

Dye-sensitized solar cells using ionic liquids as redox mediator

NASA Astrophysics Data System (ADS)

Denizalti, Serpil; Ali, Abdulrahman Khalaf; Ela, Çağatay; Ekmekci, Mesut; Erten-Ela, Sule

2018-01-01

In this research, the influence of ionic liquid on the conversion efficiency, incident photons to converted electrons (IPCE) and performance of fabricated solar cell was investigated using various ionic liquids. Ionic liquids with different substituents and ions were prepared and used as redox mediators in dye-sensitized solar cells (DSSCs). Ionic liquids were characterized 1H and 13C NMR spectra. We practically investigated the performance of ionic liquid salts were used as the mobile ions and found that the efficiencies of DSSCs were increased up to 40% comparing commercial electrolyte system. The ionic liquid compounds were incorporated in DSSCs to obtain an efficient charge transfer, solving the corrosion problem of platinum layer in counter electrode compared to commercial electrolyte.

Local Area Water Removal Analysis of a Proton Exchange Membrane Fuel Cell under Gas Purge Conditions

PubMed Central

Lee, Chi-Yuan; Lee, Yu-Ming; Lee, Shuo-Jen

2012-01-01

In this study, local area water content distribution under various gas purging conditions are experimentally analyzed for the first time. The local high frequency resistance (HFR) is measured using novel micro sensors. The results reveal that the liquid water removal rate in a membrane electrode assembly (MEA) is non-uniform. In the under-the-channel area, the removal of liquid water is governed by both convective and diffusive flux of the through-plane drying. Thus, almost all of the liquid water is removed within 30 s of purging with gas. However, liquid water that is stored in the under-the-rib area is not easy to remove during 1 min of gas purging. Therefore, the re-hydration of the membrane by internal diffusive flux is faster than that in the under-the-channel area. Consequently, local fuel starvation and membrane degradation can degrade the performance of a fuel cell that is started from cold. PMID:22368495

Local area water removal analysis of a proton exchange membrane fuel cell under gas purge conditions.

PubMed

Lee, Chi-Yuan; Lee, Yu-Ming; Lee, Shuo-Jen

2012-01-01

In this study, local area water content distribution under various gas purging conditions are experimentally analyzed for the first time. The local high frequency resistance (HFR) is measured using novel micro sensors. The results reveal that the liquid water removal rate in a membrane electrode assembly (MEA) is non-uniform. In the under-the-channel area, the removal of liquid water is governed by both convective and diffusive flux of the through-plane drying. Thus, almost all of the liquid water is removed within 30 s of purging with gas. However, liquid water that is stored in the under-the-rib area is not easy to remove during 1 min of gas purging. Therefore, the re-hydration of the membrane by internal diffusive flux is faster than that in the under-the-channel area. Consequently, local fuel starvation and membrane degradation can degrade the performance of a fuel cell that is started from cold.

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

Hu, Michael Z.; Engtrakul, Chaiwat; Bischoff, Brian L.

A new class of inorganic-based membranes, i.e., High-Performance Architectured Surface Selective (HiPAS) membranes, is introduced to provide high perm-selective flux by exploiting unique separation mechanisms induced by superhydrophobic or superhydrophilic surface interactions and confined capillary condensation in enlarged membrane pores (~8 nm). The super-hydro-tunable HiPAS membranes were originally developed for the purpose of bio-oil/biofuel processing to achieve selective separations at higher flux relative to size selective porous membranes (e.g., inorganic zeolite-based membranes) and better high-temperature tolerance than polymer membranes (>250 C) for hot vapor processing. Due to surface-enhanced separation selectivity, HiPAS membranes can thus possibly enable larger pores to facilitatemore » large-flux separations by increasing from sub-nanometer pores to mesopores (2-50 nm) for vapor phase or micron-scale pores for liquid phase separations. In this paper, we describe an innovative membrane concept and a materials synthesis strategy to fabricate HiPAS membranes, and demonstrate selective permeation in both vapor- and liquid-phase applications. High permeability and selectivity were demonstrated using surrogate mixtures, such as ethanol-water, toluene-water, and toluene-phenol-water. The overall membrane evaluation results show promise for the future processing of biomass pyrolysis and upgraded product vapors and condensed liquid bio-oil intermediates.« less

Proton exchange membrane fuel cells for space and electric vehicle applications: From basic research to technology development

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Mukerjee, Sanjeev; Parthasarathy, A.; CesarFerreira, A.; Wakizoe, Masanobu; Rho, Yong Woo; Kim, Junbom; Mosdale, Renaut A.; Paetzold, Ronald F.; Lee, James

1994-01-01

The proton exchange membrane fuel cell (PEMFC) is one of the most promising electrochemical power sources for space and electric vehicle applications. The wide spectrum of R&D activities on PEMFC's, carried out in our Center from 1988 to date, is as follows (1) Electrode Kinetic and Electrocatalysis of Oxygen Reduction; (2) Optimization of Structures of Electrodes and of Membrane and Electrode Assemblies; (3) Selection and Evaluation of Advanced Proton Conducting Membranes and of Operating Conditions to Attain High Energy Efficiency; (4) Modeling Analysis of Fuel Cell Performance and of Thermal and Water Management; and (5) Engineering Design and Development of Multicell Stacks. The accomplishments on these tasks may be summarized as follows: (1) A microelectrode technique was developed to determine the electrode kinetic parameters for the fuel cell reactions and mass transport parameters for the H2 and O2 reactants in the proton conducting membrane. (2) High energy efficiencies and high power densities were demonstrated in PEMFCs with low platinum loading electrodes (0.4 mg/cm(exp 2) or less), advanced membranes and optimized structures of membrane and electrode assemblies, as well as operating conditions. (3) The modeling analyses revealed methods to minimize mass transport limitations, particularly with air as the cathodic reactant; and for efficient thermal and water management. (4) Work is in progress to develop multi-kilowatt stacks with the electrodes containing low platinum loadings.

Orthogonal Injection Ion Funnel Interface Providing Enhanced Performance for Selected Reaction Monitoring-Triple Quadrupole Mass Spectrometry

PubMed Central

Chen, Tsung-Chi; Fillmore, Thomas L.; Prost, Spencer A.; Moore, Ronald J.; Ibrahim, Yehia M.; Smith, Richard D.

2016-01-01

The electrodynamic ion funnel facilitates efficient focusing and transfer of charged particles in the higher-pressure regions (e.g., ion source interfaces) of mass spectrometers, thus providing increased sensitivity. An “off-axis” ion funnel design has been developed to reduce the source contamination and interferences from, e.g. ESI droplet residue and other poorly focused neutral or charged particles with very high mass-to-charge ratios. In this study, a dual ion funnel interface consisting of an orthogonal higher pressure electrodynamic ion funnel (HPIF) and an ion funnel trap combined with a triple quadrupole mass spectrometer was developed and characterized. An orthogonal ion injection inlet and a repeller plate electrode was used to direct ions to an ion funnel HPIF at a pressure of 9–10 Torr. Key factors for the HPIF performance characterized included the effects of RF amplitude, the DC gradient, and operating pressure. Compared to the triple quadrupole standard interface more than 4-fold improvement in the limit of detection for the direct quantitative MS analysis of low abundance peptides was observed. The sensitivity enhancement in liquid chromatography selected reaction monitoring (LC-SRM) analyses of low-abundance peptides spiked into a highly complex mixture was also compared with that obtained using both a commercial S-lens interface and an in-line dual-ion funnel interface. PMID:26107611

Binder-free Si nanoparticle electrode with 3D porous structure prepared by electrophoretic deposition for lithium-ion batteries.

PubMed

Yang, Yang; Chen, Dingqiong; Liu, Bo; Zhao, Jinbao

2015-04-15

A binder-free silicon (Si) based electrode for lithium-ion battery was fabricated in an organic solvent through one-step electrophoretic deposition (EPD). The nanosized Si and acetylene black (AB) particles were bonded tightly together to form a homogeneous co-deposited film with 3D porous structure through the EPD process. The 3D porous structure provides buffer spaces to alleviate the mechanical stress due to silicon volume change during the cycling and improves lithium-ion conductivity by shortening ion diffusion length and better ion conducting pathway. The electrode prepared with 5 s deposition duration shows the best cycling performance among electrodes fabricated by EPD method, and thus, it was selected to be compared with the silicon electrode prepared by the conventional method. Our results demonstrate that the Si nanoparticle electrode prepared through EPD exhibits smaller cycling capacity decay rate and better rate capability than the electrode prepared by the conventional method.

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

PubMed

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

2017-04-01

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

Capillary-valve-based fabrication of ion-selective membrane junction for electrokinetic sample preconcentration in PDMS chip.

PubMed

Liu, Vincent; Song, Yong-Ak; Han, Jongyoon

2010-06-07

In this paper, we report a novel method for fabricating ion-selective membranes in poly(dimethylsiloxane) (PDMS)/glass-based microfluidic preconcentrators. Based on the concept of capillary valves, this fabrication method involves filling a lithographically patterned junction between two microchannels with an ion-selective material such as Nafion resin; subsequent curing results in a high aspect-ratio membrane for use in electrokinetic sample preconcentration. To demonstrate the concentration performance of this high-aspect-ratio, ion-selective membrane, we integrated the preconcentrator with a surface-based immunoassay for R-Phycoerythrin (RPE). Using a 1x PBS buffer system, the preconcentrator-enhanced immunoassay showed an approximately 100x improvement in sensitivity within 30 min. This is the first time that an electrokinetic microfluidic preconcentrator based on ion concentration polarization (ICP) has been used in high ionic strength buffer solutions to enhance the sensitivity of a surface-based immunoassay.

Soft actuator based on Kraton with GO/Ag/Pani composite electrodes for robotic applications

NASA Astrophysics Data System (ADS)

Khan, Ajahar; Kant Jain, Ravi; Banerjee, Priyabrata; Inamuddin; Asiri, Abdullah M.

2017-11-01

In this work, electrochemically-driven Kraton/graphene oxide/Ag/polyaniline (Kraton/GO/Ag/Pani) polymer composite based ionic polymer metal composite (IPMC) was fabricated as a soft actuator. Silver nanopowder with polyaniline coating used as an electrode material is a novel approach in the fabrication of IPMC, which gives new opportunities for development of the electrode on ionic polymer actuator surfaces directly without electroless plating of Pt or Au metal. The Kraton/GO/Ag/Pani membrane showed much higher water-uptake (WU), ion exchange capacity (IEC), proton conductivity than those of several reported IPMC membranes. The enhanced actuation performance indicates that the Kraton/GO/Ag/Pani is a better alternative to the highly expensive commercialized IPMC actuator.

Method and apparatus for determining the hydraulic conductivity of earthen material

DOEpatents

Sisson, James B.; Honeycutt, Thomas K.; Hubbell, Joel M.

1996-01-01

An earthen material hydraulic conductivity determining apparatus includes, a) a semipermeable membrane having a fore earthen material bearing surface and an opposing rear liquid receiving surface; b) a pump in fluid communication with the semipermeable membrane rear surface, the pump being capable of delivering liquid to the membrane rear surface at a plurality of selected variable flow rates or at a plurality of selected variable pressures; c) a liquid reservoir in fluid communication with the pump, the liquid reservoir retaining a liquid for pumping to the membrane rear surface; and d) a pressure sensor in fluid communication with the membrane rear surface to measure pressure of liquid delivered to the membrane by the pump. Preferably, the pump comprises a pair of longitudinally opposed and aligned syringes which are operable to simultaneously fill one syringe while emptying the other. Methods of determining the hydraulic conductivity of earthen material are also disclosed.

Method and apparatus for determining the hydraulic conductivity of earthen material

DOEpatents

Sisson, J.B.; Honeycutt, T.K.; Hubbell, J.M.

1996-05-28

An earthen material hydraulic conductivity determining apparatus includes: (a) a semipermeable membrane having a fore earthen material bearing surface and an opposing rear liquid receiving surface; (b) a pump in fluid communication with the semipermeable membrane rear surface, the pump being capable of delivering liquid to the membrane rear surface at a plurality of selected variable flow rates or at a plurality of selected variable pressures; (c) a liquid reservoir in fluid communication with the pump, the liquid reservoir retaining a liquid for pumping to the membrane rear surface; and (d) a pressure sensor in fluid communication with the membrane rear surface to measure pressure of liquid delivered to the membrane by the pump. Preferably, the pump comprises a pair of longitudinally opposed and aligned syringes which are operable to simultaneously fill one syringe while emptying the other. Methods of determining the hydraulic conductivity of earthen material are also disclosed. 15 figs.

A review of thermal performance improving methods of lithium ion battery: Electrode modification and thermal management system

NASA Astrophysics Data System (ADS)

Zhao, Rui; Zhang, Sijie; Liu, Jie; Gu, Junjie

2015-12-01

Lithium ion (Li-ion) battery has emerged as an important power source for portable devices and electric vehicles due to its superiority over other energy storage technologies. A mild temperature variation as well as a proper operating temperature range are essential for a Li-ion battery to perform soundly and have a long service life. In this review paper, the heat generation and dissipation of Li-ion battery are firstly analyzed based on the energy conservation equations, followed by an examination of the hazardous effects of an above normal operating temperature. Then, advanced techniques in respect of electrode modification and systematic battery thermal management are inspected in detail as solutions in terms of reducing internal heat production and accelerating external heat dissipation, respectively. Specifically, variable parameters like electrode thickness and particle size of active material, along with optimization methods such as coating, doping, and adding conductive media are discussed in the electrode modification section, while the current development in air cooling, liquid cooling, heat pipe cooling, and phase change material cooling systems are reviewed in the thermal management part as different ways to improve the thermal performance of Li-ion batteries.

Hepatitis C virus p7 mediates membrane-to-membrane adhesion.

PubMed

Lee, Gi Young; Lee, Sora; Lee, Hye-Ra; Yoo, Young Do

2016-09-01

Viroporin p7 of the hepatitis C virus (HCV) acts as an ion channel for pH equilibration to stabilize HCV particles; most studies of p7 have focused on this role. However, pH equilibration by p7 via its ion channel activity does not fully explain the importance of p7 in HCV particle production. Indeed, several researchers have suggested p7 to have an unidentified ion channel-independent function. Here, we show that p7 has a novel role as a lipid raft adhesion factor, which is independent of its ion channel activity. We found that p7 targets not only the liquid-disordered (Ld) phase, but also the negatively-charged liquid-ordered (Lo) phase that can be represented as a lipid raft. p7 clusters at the phase boundary of the neutral Ld phase and the negatively-charged Lo phase. Interestingly, p7 targeting the Lo phase facilitates membrane-to-membrane adhesion, and this activity is not inhibited by p7 ion channel inhibitors. Our results demonstrated that HCV p7 has dual roles as a viroporin and as a lipid raft adhesion factor. This ion channel-independent function of p7 might be an attractive target for development of anti-HCV compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Towards High-Performance Aqueous Sodium-Ion Batteries: Stabilizing the Solid/Liquid Interface for NASICON-Type Na2 VTi(PO4 )3 using Concentrated Electrolytes.

PubMed

Zhang, Huang; Jeong, Sangsik; Qin, Bingsheng; Vieira Carvalho, Diogo; Buchholz, Daniel; Passerini, Stefano

2018-04-25

Aqueous Na-ion batteries may offer a solution to the cost and safety issues of high-energy batteries. However, substantial challenges remain in the development of electrode materials and electrolytes enabling high performance and long cycle life. Herein, we report the characterization of a symmetric Na-ion battery with a NASICON-type Na 2 VTi(PO 4 ) 3 electrode material in conventional aqueous and "water-in-salt" electrolytes. Extremely stable cycling performance for 1000 cycles at a high rate (20 C) is found with the highly concentrated aqueous electrolytes owing to the formation of a resistive but protective interphase between the electrode and electrolyte. These results provide important insight for the development of aqueous Na-ion batteries with stable long-term cycling performance for large-scale energy storage. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolyte Structure near Electrode Interfaces in Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Lordi, Vincenzo; Ong, Mitchell; Verners, Osvalds; van Duin, Adri; Draeger, Erik; Pask, John

2014-03-01

The performance of lithium-ion secondary batteries (LIBs) is strongly tied to electrochemistry and ionic transport near the electrode-electrolyte interface. Changes in ion solvation near the interface affect ion conductivity and also are associated with the formation and evolution of solid-electrolyte interphase (SEI) layers, which impede transport but also passivate the interface. Thus, understanding these effects is critical to optimizing battery performance. Here we present molecular dynamics (MD) simulations of typical organic liquid LIB electrolytes in contact with graphite electrodes to understand differences in molecular structure and solvation near the interface compared to the bulk electrolyte. Results for different graphite terminations are presented. We compare the results of density-functional based MD to the empirical reactive forcefield ReaxFF and the non-reactive, non-polarizable COMPASS forcefield. Notable differences in the predictive power of each of these techniques are discussed. Prepared by LLNL under Contract DE-AC52-07NA27344.

Photoinitiated Bottom-Up Click Synthesis of Ion-Containing Networks as Hydroxide Exchange Membranes

NASA Astrophysics Data System (ADS)

Tibbits, Andrew Charles

Fuel cells are energy conversion devices which directly convert chemical energy into electrical energy and environmentally friendly byproducts (i.e., water) with potential versatility for transportation and portable applications. Hydroxide exchange membrane fuel cells (HEMFCs) have the potential to decrease the overall fuel cell cost through the utilization of non-precious metal catalysts such as nickel and silver as opposed to platinum which is used by the current standard technology, proton exchange membrane fuel cells (PEMFCs). However, substantial improvements in thermal and alkaline stability, hydroxide conductivity, mechanical flexibility, and processing are needed to create a competitive membrane for HEMFC applications. Regardless of the type of membrane, the high water uptake that is typically associated with increased ionic conductivity is problematic and can result in the dissolution of the membrane during fuel cell operation. Covalent crosslinking of the membrane is an approach which has been effectively applied to reduce water uptake without a significant compromise of the hydroxide conductivity. The synthesis and processing of membrane materials is vastly simplified by using click polymerization schemes. Click chemistry is a collection of organic chemical reactions that are rapid, selective, and high yielding. One of the most versatile and facile click reactions is the thiol-ene reaction, which is the radical-mediated addition reaction between a thiol (an -SH group) and an 'ene' (an electron rich vinyl group, C=C) in the presence of a photoinitiator and light. The click attributes of the thiol-ene reaction enables potential of "bottom-up" design of ion-containing polymers via a single step photoinitiated crosslinking reaction with precise control over structure and physicochemical properties not only for fuel cell membranes but also for a range of other applications including separations, sensors, flexible electronics, and coatings. However, a fundamental understanding of the formation and properties of ion-containing thiol-ene materials and their implementation as hydroxide exchange membranes is largely absent from the current literature. The work described herein will highlight the versatility of click reactions, primarily the thiol-ene reaction, for fabrication of ion-containing networks with tunable properties based on the rational design and synthesis of photopolymerizable ionic liquid comonomers with an emphasis on applicability for HEMFC applications. The role of ionic liquid monomer structure on the kinetics and mechanism of thiol-ene ionic network formation and the subsequent properties (i.e., ion conductive, thermomechanical, and structural) will be elucidated to establish a guided framework for click ionic material development. This framework will be directed onto the development of alkaline stable hydroxide-conductive membranes for fuel cell applications as well as the incorporation of catalytic nanoparticles into a photocrosslinkable formulation as a self-standing catalyst layer. Finally, novel approaches to membrane fabrication will be implemented to build on the foundational studies that will simultaneously enhance the ionic conductivity and mechanical properties of the ion-containing polymer materials: these approaches include the synthesis and crosslinking of photopolymerizable cationic surfactants for microphase separated membranes as well as the first "bottom-up" ion-containing polymer synthesized from the photoinitiated copper-catalyzed azide-alkyne cycloaddition (photo-CuAAC) reaction which exhibits enhanced processability and hydroxide conductivity (>50 mS/cm).

Time-dependent deformation of polymer network in polymer-stabilized cholesteric liquid crystals (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lee, Kyung Min; Tondiglia, Vincent P.; Bunning, Timothy J.; White, Timothy J.

2017-02-01

Recently, we reported direct current (DC) field controllable electro-optic (EO) responses of negative dielectric anisotropy polymer stabilized cholesteric liquid crystals (PSCLCs). A potential mechanism is: Ions in the liquid crystal mixtures are trapped in/on the polymer network during the fast photopolymerization process, and the movement of ions by the application of the DC field distorts polymer network toward the negative electrode, inducing pitch variation through the cell thickness, i.e., pitch compression on the negative electrode side and pitch expansion on positive electrode side. As the DC voltage is directly applied to a target voltage, charged polymer network is deformed and the reflection band is tuned. Interestingly, the polymer network deforms further (red shift of reflection band) with time when constantly applied DC voltage, illustrating DC field induced time dependent deformation of polymer network (creep-like behavior). This time dependent reflection band changes in PSCLCs are investigated by varying the several factors, such as type and concentration of photoinitiators, liquid crystal monomer content, and curing condition (UV intensity and curing time). In addition, simple linear viscoelastic spring-dashpot models, such as 2-parameter Kelvin and 3-parameter linear models, are used to investigate the time-dependent viscoelastic behaviors of polymer networks in PSCLC.

Analytical application of solid contact ion-selective electrodes for determination of copper and nitrate in various food products and drinking water.

PubMed

Wardak, Cecylia; Grabarczyk, Malgorzata

2016-08-02

A simple, fast and cheap method for monitoring copper and nitrate in drinking water and food products using newly developed solid contact ion-selective electrodes is proposed. Determination of copper and nitrate was performed by application of multiple standard additions technique. The reliability of the obtained results was assessed by comparing them using the anodic stripping voltammetry or spectrophotometry for the same samples. In each case, satisfactory agreement of the results was obtained, which confirms the analytical usefulness of the constructed electrodes.

Ruggedized downhole tool for real-time measurements and uses thereof

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

Hess, Ryan Falcone; Lindblom, Scott C.; Yelton, William G.

The present invention relates to ruggedized downhole tools and sensors, as well as uses thereof. In particular, these tools can operate under extreme conditions and, therefore, allow for real-time measurements in geothermal reservoirs or other potentially harsh environments. One exemplary sensor includes a ruggedized ion selective electrode (ISE) for detecting tracer concentrations in real-time. In one embodiment, the ISE includes a solid, non-conductive potting material and an ion selective material, which are disposed in a temperature-resistant electrode body. Other electrode configurations, tools, and methods are also described.

PEMFC development at Asahi Glass Co., Ltd.

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

Yoshitake, M.; Yanagisawa, E.; Naganuma, T.

2000-07-01

Perfluorinated ion exchange membranes were studied and the membrane technology for PEMFC has been developed. Thermal stability, mechanical strength, water content, AC specific resistance and gas permeability were measured. The influence of membrane thickness on gas permeability and the influence of incorporation of cations on water content and AC specific resistance of Flemion{reg_sign} and Nafion{reg_sign}117 were estimated. Gas permeation rates of the membranes decreased in inverse proportion to the increase of the membrane thickness and gas permeability coefficients were nearly constant and independent of the thickness. Hydrogen permeation rates of Flemion S at 70 C were converted to 2.1 mA/cm{supmore » 2} as current density. Flemion R-electrode assembly showed to maintain stable performance for over 3,500 hr. Furthermore, it was found that usage of thinner membranes of one with higher ion-exchange capacity gave not only lower internal cell voltage but also higher IR-free cell voltage. PTFE-yarn embedded type membrane (Flemion Mc and Sc) and PTFE-fibril dispersed type (Flemion Rf2) was examined to afford improvement in mechanical strength at moist and high temperature atmosphere. Flemion Sc (80{micro}m) was examined to give high cell performance of 0.67V at 0.5A/cm2, 80 C, 1 ata. Flemion Mc-electrode assembly was examined to keep stable performance during the life test of over 1,500 hr.« less

Large enhancement of capacitance driven by electrostatic image forces

NASA Astrophysics Data System (ADS)

Loth, Matthew Scott

The purpose of this thesis is to examine the role of electrostatic images in determining the capacitance and the structure of the electrostatic double layer (EDL) formed at the interface of a metal electrode and an electrolyte. Current mean field theories, and the majority of simulations, do not account for ions to form image charges in the metal electrodes and claim that the capacitance of the double layer cannot be larger than that of the Helmholtz capacitor, whose width is equal to the radius of an ion. However, in some experiments, and simulations where the images are included, the apparent width of the capacitor is substantially smaller. Monte Carlo simulations are used to examine the interface between a metal electrode and a room temperature ionic liquid (RTIL) modeled by hard spheres (the "restricted primitive model"). Image charges for each ion are included in the simulated electrode. At moderately low temperatures the capacitance of the metal/RTIL interface is so large that the effective thickness of the electrostatic double-layer is up to 3 times smaller than the ion radius. To interpret these results, an approach is used that is based on the interaction between discrete ions and their image charges, which therefore goes beyond the mean-field approximation. When a voltage is applied across the interface, the strong image attraction causes counterions to condense onto the metal surface to form compact ion-image dipoles. These dipoles repel each other to form a correlated liquid. When the surface density of these dipoles is low, the insertion of an additional dipole does not require much energy. This leads to a large capacitance C that decreases monotonically with voltage V, producing a "bell-shaped" C( V) curve. In the case of a semi-metal electrode, the finite screening radius of the electrode shifts the reflection plane for image charges to the interior of the electrode resulting in a "camel-shaped" C(V) curve, which is parabolic near V = 0, reaches a maximum and then decreases. These predictions are in qualitative agreement with experiment. A similarly simple model is employed to simulate the EDL of superionic crystals. In this case only small cations are mobile and other ions form an oppositely charged background. Simulations show an effective thickness of the EDL that may be 3 times smaller than the ion radius. The weak repulsion of ion-image dipoles again plays a central role in determining the capacitance in this theory, which is in reasonable agreement with experiment. Finally, the problem of a strongly charged, insulating macroion in a dilute solution of multivalent counterions is considered. While an ideal conductor does not exist in the problem, and no images are explicitly included, simulations demonstrate that adsorbed counterions form a strongly correlated liquid of at the surface of the macroion and acts as an effective metal surface. In fact, the surface screens the electric field of distant ions with a negative screening radius. The simulation results serve to confirm existing non-mean-field theories.

Novel Organic Membrane-based Thin-film Microsensors for the Determination of Heavy Metal Cations

PubMed Central

Arida, Hassan A.; Kloock, Joachim P.; Schöning, Michael J.

2006-01-01

A first step towards the fabrication and electrochemical evaluation of thin-film microsensors based on organic PVC membranes for the determination of Hg(II), Cd(II), Pb(II) and Cu(II) ions in solutions has been realised. The membrane-coating mixture used in the preparation of this new type of microsensors is incorporating PVC as supporting matrix, o-nitrophenyloctylether (o-NPOE) as solvent mediator and a recently synthesized Hg[dimethylglyoxime(phene)]2+ and Bis-(4-hydroxyacetophenone)-ethylenediamine as electroactive materials for Hg(II) and Cd(II), respectively. A set of three commercialised ionophores for Cd(II), Pb(II) and Cu(II) has been also used for comparison. Thin-film microsensors based on these membranes showed a Nernstian response of slope (26-30 mV/dec.) for the respective tested cations. The potentiometric response characteristics (linear range, pH range, detection limit and response time) are comparable with those obtained by conventional membranes as well as coated wire electrodes prepared from the same membrane. The realisation of the new organic membrane-based thin-film microsensors overcomes the problem of an insufficient selectivity of solid-state-based thin-film sensors.

Membrane-spacer assembly for flow-electrode capacitive deionization

NASA Astrophysics Data System (ADS)

Lee, Ki Sook; Cho, Younghyun; Choo, Ko Yeon; Yang, SeungCheol; Han, Moon Hee; Kim, Dong Kook

2018-03-01

Flow-electrode capacitive deionization (FCDI) is a desalination process designed to overcome the limited desalination capacity of conventional CDI systems due to their fixed electrodes. Such a FCDI cell system is comprised of a current collector, freestanding ion-exchange membrane (IEM), gasket, and spacer for flowing saline water. To simplify the cell system, in this study we combined the membrane and spacer into a single unit, by coating the IEM on a porous ceramic structure that acts as the spacer. The combination of membrane with the porous structure avoids the use of costly freestanding IEM. Furthermore, the FCDI system can be readily scaled up by simply inserting the IEM-coated porous structures in between the channels for flow electrodes. However, coating the IEM on such porous ceramic structures can cause a sudden drop in the treatment capacity, if the coated IEM penetrates the ceramic pores and prevents these pores from acting as saline flow channels. To address this issue, we blocked the larger microscale pores on the outer surface with SiO2 and polymeric multilayers. Thus, the IEM is coated only onto the top surface of the porous structure, while the internal pores remain empty to function as water channels.

Ionic liquids and their solid-state analogues as materials for energy generation and storage

NASA Astrophysics Data System (ADS)

Macfarlane, Douglas R.; Forsyth, Maria; Howlett, Patrick C.; Kar, Mega; Passerini, Stefano; Pringle, Jennifer M.; Ohno, Hiroyuki; Watanabe, Masayoshi; Yan, Feng; Zheng, Wenjun; Zhang, Shiguo; Zhang, Jie

2016-02-01

Salts that are liquid at room temperature, now commonly called ionic liquids, have been known for more than 100 years; however, their unique properties have only come to light in the past two decades. In this Review, we examine recent work in which the properties of ionic liquids have enabled important advances to be made in sustainable energy generation and storage. We discuss the use of ionic liquids as media for synthesis of electromaterials, for example, in the preparation of doped carbons, conducting polymers and intercalation electrode materials. Focusing on their intrinsic ionic conductivity, we examine recent reports of ionic liquids used as electrolytes in emerging high-energy-density and low-cost batteries, including Li-ion, Li-O2, Li-S, Na-ion and Al-ion batteries. Similar developments in electrolyte applications in dye-sensitized solar cells, thermo-electrochemical cells, double-layer capacitors and CO2 reduction are also discussed.

Giga-ohm seals on intracellular membranes: a technique for studying intracellular ion channels in intact cells.

PubMed

Jonas, E A; Knox, R J; Kaczmarek, L K

1997-07-01

A method is outlined for obtaining giga-ohm seals on intracellular membranes in intact cells. The technique employs a variant of the patch-clamp technique: a concentric electrode arrangement protects an inner patch pipette during penetration of the plasma membrane, after which a seal can be formed on an internal organelle membrane. Using this technique, successful recordings can be obtained with the same frequency as with conventional patch clamping. To localize the position of the pipette within cells, lipophilic fluorescent dyes are included in the pipette solution. These dyes stain the membrane of internal organelles during seal formation and can then be visualized by video-enhanced or confocal imaging. The method can detect channels activated by inositol trisphosphate, as well as other types of intracellular membrane ion channel activity, and should facilitate studies of internal membranes in intact neurons and other cell types.

Solid state proton and electron mediating membrane and use in catalytic membrane reactors

DOEpatents

White, James H.; Schwartz, Michael; Sammells, Anthony F.

1998-01-01

This invention provides catalytic proton and electron mediating membranes useful in catalytic reactors. The membranes have an oxidation and a reduction surface and comprise a single-phase mixed metal oxide material of the formula: AB.sub.1-x B'.sub.x O.sub.3-y wherein A is selected from Ca, Sr or Ba ions; B is selected from Ce, Tb, Pr, or Th ions; B' is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Ga, or In ions, or combinations thereof; and x is greater than or equal to 0.02 and less than or equal to 0.5. The membranes can further comprise a catalyst on either the oxidation or reduction surface, or both. Membranes include those which are fabricated-by combining powders of metal oxides or metal carbonates of metal A ion, metal B ion and metal B' ion such that the stoichiometric ratio A:B:B' is 1:1-x:x where 0.2.ltoreq..times.0.5, repeatedly calcining and milling the combined powders until a single-phase material is obtained and pressing and sintering the singlephase material to obtain a membrane.

Solid state proton and electron mediating membrane and use in catalytic membrane reactors

DOEpatents

White, J.H.; Schwartz, M.; Sammells, A.F.

1998-10-13

This invention provides catalytic proton and electron mediating membranes useful in catalytic reactors. The membranes have an oxidation and a reduction surface and comprise a single-phase mixed metal oxide material of the formula: AB{sub 1{minus}x}B{prime}{sub x}O{sub 3{minus}y} wherein A is selected from Ca, Sr or Ba ions; B is selected from Ce, Tb, Pr, or Th ions; B{prime} is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Ga, or In ions, or combinations thereof; and x is greater than or equal to 0.02 and less than or equal to 0.5. The membranes can further comprise a catalyst on either the oxidation or reduction surface, or both. Membranes include those which are fabricated by combining powders of metal oxides or metal carbonates of metal A ion, metal B ion and metal B{prime} ion such that the stoichiometric ratio A:B:B{prime} is 1:1{minus}x:x where 0.2{<=}{times}0.5, repeatedly calcining and milling the combined powders until a single-phase material is obtained and pressing and sintering the single phase material to obtain a membrane. 6 figs.

Spontaneous hybrids of graphene and carbon nanotube arrays at the liquid-gas interface for Li-ion battery anodes.

PubMed

Kim, Hyeri; Kim, Jongsoon; Jeong, Hee-Sung; Kim, Hyungsub; Lee, Hoyeon; Ha, Jae-Min; Choi, Sung-Min; Kim, Tae-Ho; Nah, Yoon-Chae; Shin, Tae Joo; Bang, Joona; Satija, Sushil K; Koo, Jaseung

2018-05-17

We demonstrate that hybrid structures of graphene and single-walled carbon nanotubes (SWNTs) are precisely controlled at the liquid-gas interface. The functionalized SWNT Langmuir monolayers anchor single-layer graphene nanosheets (GNSs) suspended in water via Coulomb interaction at the interface. This GNS/SWNT hybrid multilayer electrode can be a promising anode material for Li-ion batteries, offering high specific capacity, outstanding power capability, and excellent cyclability.

Orthogonal Injection Ion Funnel Interface Providing Enhanced Performance for Selected Reaction Monitoring-Triple Quadrupole Mass Spectrometry

DOE PAGES

Chen, Tsung-Chi; Fillmore, Thomas L.; Prost, Spencer A.; ...

2015-06-24

The electrodynamic ion funnel facilitates efficient focusing and transfer of charged particles in the higher pressure regions (e.g. ion source interfaces) of mass spectrometers, and thus providing increased sensitivity. An “off-axis” ion funnel design has been developed to reduce the source contamination and interferences from, e.g. ESI droplet residue and other poorly focused neutral or charged particles with very high mass-to charge ratios. In this study a dual ion funnel interface consisting of an orthogonal higher pressure electrodynamic ion funnel (HPIF) and an ion funnel trap combined with a triple quadruple mass spectrometer was developed and characterized. An orthogonal ionmore » injection inlet and a repeller plate electrode was used to direct ions to an ion funnel HPIF at 9-10 Torr pressure. Several critical factors for the HPIF were characterized, including the effects of RF amplitude, DC gradient and operating pressure. Compared to the triple quadrupole standard interface more than 4-fold improvement in the limit of detection for the direct quantitative MS analysis of low abundance peptides was observed. Lastly, the sensitivity enhancement in liquid chromatography selected reaction monitoring (SRM) analyses of low abundance peptides spiked into a highly complex mixture was also compared with that obtained using a both commercial s-lens interface and a in-line dual ion funnel interface.« less

Nafion-coating of the electrodes improves the flow-stability of the Ag/SiO2/Ag2O electroosmotic pump.

PubMed

Shin, Woonsup; Zhu, Enhua; Nagarale, Rajaram Krishna; Kim, Chang Hwan; Lee, Jong Myung; Shin, Samuel Jaeho; Heller, Adam

2011-06-15

When a current or a voltage is applied across the ceramic membrane of the nongassing Ag/Ag(2)O-SiO(2)-Ag/Ag(2)O pump, protons produced in the anodic reaction 2Ag(s) + H(2)O → Ag(2)O(s) + 2H(+) + 2e(-) are driven to the cathode, where they are consumed by the reaction Ag(2)O(s) + H(2)O + 2e(-) → 2Ag(s) + 2 OH(-). The flow of water is induced by momentum transfer from the electric field-driven proton-sheet at the surface of the ceramic membrane. About 10(4) water molecules flowed per reacted electron. Because dissolved ions decrease the field at the membrane surface, the flow decreases upon increasing the ionic strength. For this reason Ag(+) ions introduced through the anodic reaction and by dissolution of Ag(2)O decrease the flow. Their accumulation is reduced by applying Nafion-films to the electrodes. The 20 μL min(-1) flow rate of 6 mm i.d. pumps with Nafion coated electrodes operate daily for 5 min at 1 V for 1 month, for 70 h when the pump is pulsed for 30 s every 30 min, and for 2 h when operating continuously.

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

Phenytoin speciation with potentiometric and chronopotentiometric ion-selective membrane electrodes.

PubMed

Jansod, Sutida; Afshar, Majid Ghahraman; Crespo, Gastón A; Bakker, Eric

2016-05-15

We report on an electrochemical protocol based on perm-selective membranes to provide valuable information about the speciation of ionizable drugs, with phenytoin as a model example. Membranes containing varying amounts of tetradodecylammonium chloride (TDDA) were read out at zero current (potentiometry) and with applied current techniques (chronopotentiometry). Potentiometry allows one to assess the ionized form of phenytoin (pKa~8.2) that corresponds to a negatively monocharged ion. A careful optimization of the membrane components resulted in a lower limit of detection (~1.6 µM) than previous reports. Once the pH (from 9 to 10) or the concentration of albumin is varied in the sample (from 0 to 30 g L(-1)), the potentiometric signal changes abruptly as a result of reducing/increasing the ionized concentration of phenytoin. Therefore, potentiometry as a single technique is by itself not sufficient to obtain information about the concentration and speciation of the drug in the system. For this reason, a tandem configuration with chronopotentiometry as additional readout principle was used to determine the total and ionized concentration of phenytoin. In samples containing excess albumin the rate-limiting step for the chronopotentiometry readout appears to be the diffusion of ionized phenytoin preceded by comparatively rapid deprotonation and decomplexation reactions. This protocol was applied to measure phenytoin in pharmaceutical tables (100mg per tablet). This tandem approach can likely be extended to more ionizable drugs and may eventually be utilized in view of pharmacological monitoring of drugs during the delivery process. Copyright © 2015 Elsevier B.V. All rights reserved.

Lattice model of ionic liquid confined by metal electrodes

NASA Astrophysics Data System (ADS)

Girotto, Matheus; Malossi, Rodrigo M.; dos Santos, Alexandre P.; Levin, Yan

2018-05-01

We study, using Monte Carlo simulations, the density profiles and differential capacitance of ionic liquids confined by metal electrodes. To compute the electrostatic energy, we use the recently developed approach based on periodic Green's functions. The method also allows us to easily calculate the induced charge on the electrodes permitting an efficient implementation of simulations in a constant electrostatic potential ensemble. To speed up the simulations further, we model the ionic liquid as a lattice Coulomb gas and precalculate the interaction potential between the ions. We show that the lattice model captures the transition between camel-shaped and bell-shaped capacitance curves—the latter characteristic of ionic liquids (strong coupling limit) and the former of electrolytes (weak coupling). We observe the appearance of a second peak in the differential capacitance at ≈0.5 V for 2:1 ionic liquids, as the packing fraction is increased. Finally, we show that ionic size asymmetry decreases substantially the capacitance maximum, when all other parameters are kept fixed.

Potentiometric Zinc Ion Sensor Based on Honeycomb-Like NiO Nanostructures

PubMed Central

Abbasi, Mazhar Ali; Ibupoto, Zafar Hussain; Hussain, Mushtaque; Khan, Yaqoob; Khan, Azam; Nur, Omer; Willander, Magnus

2012-01-01

In this study honeycomb-like NiO nanostructures were grown on nickel foam by a simple hydrothermal growth method. The NiO nanostructures were characterized by field emission electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) techniques. The characterized NiO nanostructures were uniform, dense and polycrystalline in the crystal phase. In addition to this, the NiO nanostructures were used in the development of a zinc ion sensor electrode by functionalization with the highly selective zinc ion ionophore 12-crown-4. The developed zinc ion sensor electrode has shown a good linear potentiometric response for a wide range of zinc ion concentrations, ranging from 0.001 mM to 100 mM, with sensitivity of 36 mV/decade. The detection limit of the present zinc ion sensor was found to be 0.0005 mM and it also displays a fast response time of less than 10 s. The proposed zinc ion sensor electrode has also shown good reproducibility, repeatability, storage stability and selectivity. The zinc ion sensor based on the functionalized NiO nanostructures was also used as indicator electrode in potentiometric titrations and it has demonstrated an acceptable stoichiometric relationship for the determination of zinc ion in unknown samples. The NiO nanostructures-based zinc ion sensor has potential for analysing zinc ion in various industrial, clinical and other real samples. PMID:23202217

Superhydrophobic and superhydrophilic surface-enhanced separation performance of porous inorganic membranes for biomass-to-biofuel conversion applications

DOE PAGES

Hu, Michael Z.; Engtrakul, Chaiwat; Bischoff, Brian L.; ...

2016-11-14

A new class of inorganic-based membranes, i.e., High-Performance Architectured Surface Selective (HiPAS) membranes, is introduced to provide high perm-selective flux by exploiting unique separation mechanisms induced by superhydrophobic or superhydrophilic surface interactions and confined capillary condensation in enlarged membrane pores (~8 nm). The super-hydro-tunable HiPAS membranes were originally developed for the purpose of bio-oil/biofuel processing to achieve selective separations at higher flux relative to size selective porous membranes (e.g., inorganic zeolite-based membranes) and better high-temperature tolerance than polymer membranes (>250 C) for hot vapor processing. Due to surface-enhanced separation selectivity, HiPAS membranes can thus possibly enable larger pores to facilitatemore » large-flux separations by increasing from sub-nanometer pores to mesopores (2-50 nm) for vapor phase or micron-scale pores for liquid phase separations. In this paper, we describe an innovative membrane concept and a materials synthesis strategy to fabricate HiPAS membranes, and demonstrate selective permeation in both vapor- and liquid-phase applications. High permeability and selectivity were demonstrated using surrogate mixtures, such as ethanol-water, toluene-water, and toluene-phenol-water. The overall membrane evaluation results show promise for the future processing of biomass pyrolysis and upgraded product vapors and condensed liquid bio-oil intermediates.« less

Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

DOE PAGES

Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun; ...

2017-04-27

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

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

Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

A novel polymer inclusion membranes based optode for sensitive determination of Al³⁺ ions.

PubMed

Suah, Faiz Bukhari Mohd; Ahmad, Musa; Heng, Lee Yook

2015-06-05

A novel approach for the determination of Al(3+) from aqueous samples was developed using an optode membrane produced by physical inclusion of Al(3+) selective reagent, which is morin into a plasticized poly(vinyl chloride). The inclusion of Triton X-100 was found to be valuable and useful for enhancing the sorption of Al(3+) ions from liquid phase into the membrane phase, thus increasing the intensity of optode's absorption. The optode showed a linear increase in the absorbance at λ(max)=425 nm over the concentration range of 1.85×10(-6)-1.1×10(-4) mol L(-1) (0.05-3 μg mL(-1)) of Al(3+) ions in aqueous solution after 5 min. The limit of detection was determined to be 1.04×10(-6) mol L(-1) (0.028 μg mL(-1)). The optode developed in the present work was easily prepared and found to be stable, has good mechanical strength, sensitive and reusable. In addition, the optode was tested for Al(3+) determination in lake water, river water and pharmaceutical samples, which the result was satisfactory. Copyright © 2015 Elsevier B.V. All rights reserved.

A lithium ion battery using an aqueous electrolyte solution

PubMed Central

Chang, Zheng; Li, Chunyang; Wang, Yanfang; Chen, Bingwei; Fu, Lijun; Zhu, Yusong; Zhang, Lixin; Wu, Yuping; Huang, Wei

2016-01-01

Energy and environmental pollution have become the two major problems in today’s society. The development of green energy storage devices with good safety, high reliability, high energy density and low cost are urgently demanded. Here we report on a lithium ion battery using an aqueous electrolyte solution. It is built up by using graphite coated with gel polymer membrane and LISICON as the negative electrode, and LiFePO4 in aqueous solution as the positive electrode. Its average discharge voltage is up to 3.1 V and energy density based on the two electrode materials is 258 Wh kg−1. It will be a promising energy storage system with good safety and efficient cooling effects. PMID:27328707

Rechargeable lithium-ion cell

DOEpatents

Bechtold, Dieter; Bartke, Dietrich; Kramer, Peter; Kretzschmar, Reiner; Vollbert, Jurgen

1999-01-01

The invention relates to a rechargeable lithium-ion cell, a method for its manufacture, and its application. The cell is distinguished by the fact that it has a metallic housing (21) which is electrically insulated internally by two half shells (15), which cover electrode plates (8) and main output tabs (7) and are composed of a non-conductive material, where the metallic housing is electrically insulated externally by means of an insulation coating. The cell also has a bursting membrane (4) which, in its normal position, is located above the electrolyte level of the cell (1). In addition, the cell has a twisting protection (6) which extends over the entire surface of the cover (2) and provides centering and assembly functions for the electrode package, which comprises the electrode plates (8).

Dynamic NMR studies of polymer electrolyte materials for application to lithium-ion batteries and fuel cells

NASA Astrophysics Data System (ADS)

Khalfan, Amish N.

This dissertation investigates the structural and dynamical properties of polymer electrolyte materials for applications to lithium-ion batteries and fuel cells. The nuclear magnetic resonance (NMR) technique was used to characterize these materials. NMR aids in understanding the local environments of nuclei and the mobility of a molecular/ionic species. Five research projects were carried out, and they have been outlined in this work. NASA has developed rod-coil block copolymers for use as electrolytes in lithium-ion batteries. The copolymers exhibit a microphase separation within their structure leading to the formation of ionically conducting channels. We studied ion transport properties of the copolymers, and determined the predominant mechanism for transport to occur in the amorphous phase. Seven gel polymer electrolytes, each containing a mixture of LiBETI salt and organic solvents, were studied. Two of them incorporated BMI (1-n-butyl-3-methylimidazolium) ionic liquid. Ionic liquids are room temperature molten salts. BMI had been thought to enhance ion mobility. However, the BMI component was observed to restrict ion mobility. Gel polymer electrolytes containing LiTFSI salt and P13TFSI ionic liquid with or without the inclusion of ethylene carbonate (EC) were studied for application to lithium metal/air batteries, which have high theoretical energy densities. The addition of EC was found to improve lithium ion transport. The gels with EC therefore prove to be favorable for use as electrolytes in lithium metal/air batteries. Highly sulfonated poly(arylenethioethersulfone) (SPTES) membranes were examined for use in direct methanol fuel cells (DMFCs) as an alternative to the Nafion membrane. DMFCs use methanol as a fuel instead of reformed hydrogen as in conventional proton exchange membrane fuel cells. Compared to Nafion, the SPTES membranes were shown to retain water better at high temperatures and yield lower methanol diffusion. SPTES membranes with the addition of fluorine groups (6F-SPTES) were also studied, and these membranes had been thought to show an improvement in water transport properties over SPTES. However, water diffusion studies of the 6F-SPTES membranes revealed the fluorinated membranes to be unfavorable. The morphology of the FSPTES is suspected to be more susceptible to the loss of bound water at higher temperatures than SPTES.

High energy density redox flow device

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

Carter, W. Craig; Chiang, Yet-Ming; Duduta, Mihai

2017-04-04

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % ofmore » the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.« less

A reusable device for electrochemical applications of hydrogel supported black lipid membranes.

PubMed

Mech-Dorosz, Agnieszka; Heiskanen, Arto; Bäckström, Sania; Perry, Mark; Muhammad, Haseena B; Hélix-Nielsen, Claus; Emnéus, Jenny

2015-02-01

Black lipid membranes (BLMs) are significant in studies of membrane transport, incorporated proteins/ion transporters, and hence in construction of biosensor devices. Although BLMs provide an accepted mimic of cellular membranes, they are inherently fragile. Techniques are developed to stabilize them, such as hydrogel supports. In this paper, we present a reusable device for studies on hydrogel supported (hs) BLMs. These are formed across an ethylene tetrafluoroethylene (ETFE) aperture array supported by the hydrogel, which is during in situ polymerization covalently "sandwiched" between the ETFE substrate and a gold electrode microchip, thus allowing direct electrochemical studies with the integrated working electrodes. Using electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy and contact angle measurements, we demonstrate the optimized chemical modifications of the gold electrode microchips and plasma modification of the ETFE aperture arrays facilitating covalent "sandwiching" of the hydrogel. Both fluorescence microscopy and EIS were used to demonstrate the induced spontaneous thinning of a deposited lipid solution, leading to formation of stabilized hsBLMs on average in 10 min. The determined specific membrane capacitance and resistance were shown to vary in the range 0.31-0.49 μF/cm(2) and 45-65 kΩ cm(2), respectively, corresponding to partially solvent containing BLMs with an average life time of 60-80 min. The characterized hsBLM formation and devised equivalent circuit models lead to a schematic model to illustrate lipid molecule distribution in hydrogel-supported apertures. The functionality of stabilized hsBLMs and detection sensitivity of the platform were verified by monitoring the effect of the ion transporter valinomycin.

Poly(aniline) nanowires in sol-gel coated ITO: A pH-responsive substrate for planar supported lipid bilayers

PubMed Central

Ge, Chenhao; Orosz, Kristina S.; Armstrong, Neal R.; Saavedra, S. Scott

2011-01-01

Facilitated ion transport across an artificial lipid bilayer coupled to a solid substrate is a function common to several types of bioelectronic devices based on supported membranes, including biomimetic fuel cells and ion channel biosensors. Described here is fabrication of a pH-sensitive transducer composed of a porous sol-gel layer derivatized with poly(aniline) (PANI) nanowires grown from an underlying planar indium-tin oxide (ITO) electrode. The upper sol-gel surface is hydrophilic, smooth, and compatible with deposition of a planar supported lipid bilayer (PSLB) formed via vesicle fusion. Conducting tip AFM was used to show that the PANI wires are connected to the ITO, which convert this electrode into a potentiometric pH sensor. The response to changes in the pH of the buffer contacting the PANI nanowire/sol-gel/ITO electrode is blocked by the very low ion permeability of the overlying, fluid PSLB. The feasibility of using this assembly to monitor facilitated proton transport across the PSLB was demonstrated by doping the membrane with lipophilic ionophores that respond to a transmembrane pH gradient, which produced an apparent proton permeability several orders of magnitude greater than values measured for undoped lipid bilayers. PMID:21707069

Carbon Dioxide Gas Sensors and Method of Manufacturing and Using Same

NASA Technical Reports Server (NTRS)

Liu, Chung Chiun (Inventor); Ward, Benjamin J. (Inventor); Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor)

2011-01-01

A gas sensor includes a substrate and a pair of interdigitated metal electrodes selected from the group consisting of Pt, Pd, Au, Ir, Ag, Ru, Rh, In, and Os. The electrodes each include an upper surface. A first solid electrolyte resides between the interdigitated electrodes and partially engages the upper surfaces of the electrodes. The first solid electrolyte is selected from the group consisting of NASICON, LISICON, KSICON, and .beta.''-Alumina (beta prime-prime alumina in which when prepared as an electrolyte is complexed with a mobile ion selected from the group consisting of Na.sup.+, K.sup.+, Li.sup.+, Ag.sup.+, H.sup.+, Pb.sup.2+, Sr.sup.2+ or Ba.sup.2+). A second electrolyte partially engages the upper surfaces of the electrodes and engages the first solid electrolyte in at least one point. The second electrolyte is selected from the group of compounds consisting of Na.sup.+, K.sup.+, Li.sup.+, Ag.sup.+, H.sup.+, Pb.sup.2+, Sr.sup.2+ or Ba.sup.2+ ions or combinations thereof.

A voltammetric method for Fe(iii) in blood serum using a screen-printed electrode modified with a Schiff base ionophore.

PubMed

Mittal, Susheel K; Rana, Sonia; Kaur, Navneet; Banks, Craig E

2018-05-23

Herein, a potent electrochemical ionophore (SMS-2) based on a Schiff base has been used for the modification of a screen-printed electrode (SPE). The modified disposable electrode can selectively detect ferric ions in an aqueous medium. Redox behavior of the proposed strip was characterized using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Incorporation of the ligand in the ink of the SPE enhanced the analytical performance of the electrode, and its surface modification was confirmed by SEM and EDX analysis. Shifting/quenching of the cathodic peak potential of the ionophore after binding with Fe(iii) ions was used to detect and measure the ferric ion concentration. This sensor can identify Fe(iii) in the detection range from 0.625 μM to 7.5 μM. The modified SPE can selectively detect ferric ions in the presence of many other interfering ions and has been successfully used to determine the Fe(iii) content in blood serum samples. The metal-ionophore complex structure was optimized using DFT calculations to study the energetics of the metal-ionophore interactions.

Behaviour of tetraalkylammonium ions in high-field asymmetric waveform ion mobility spectrometry.

PubMed

Aksenov, Alexander A; Kapron, James T

2010-05-30

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an ion-filtering technique recently adapted for use with liquid chromatography/mass spectrometry (LC/MS) to remove interferences during analysis of complex matrices. This is the first systematic study of a series of singly charged tetraalkylammonium ions by FAIMS-MS. The compensation voltage (CV) is the DC offset of the waveform which permits the ion to emerge from FAIMS and it was determined for each member of the series under various conditions. The electrospray ionization conditions explored included spray voltage, vaporizer temperature, and sheath and auxiliary gas pressure. The FAIMS conditions explored included carrier gas flow rate, electrode temperature and composition of the carrier gas. Optimum desolvation was achieved using sufficient carrier gas (flow rate > or = 2 L/min) to ensure stable response. Low-mass ions (m/z 100-200) are more susceptible to changes in electrode temperature and gas composition than high mass ions (m/z 200-700). As a result of this study, ions are reliably analyzed using standard FAIMS conditions (dispersion voltage -5000 V, carrier gas flow rate 3 L/min, 50% helium/50%nitrogen, inner electrode temperature 70 degrees C and outer electrode temperature 90 degrees C). Variation of FAIMS conditions may be of great use for the separation of very low mass tetraalkylammonium (TAA) ions from other TAA ions. The FAIMS conditions do not appear to have a major effect on higher mass ions. Copyright 2010 John Wiley & Sons, Ltd.

Stacked vapor fed amtec modules

DOEpatents

Sievers, Robert K.

1989-01-01

The present invention pertains to a stacked AMTEC module. The invention includes a tubular member which has an interior. The member is comprised of a ion conductor that substantially conducts ions relative to electrons, preferably a beta"-alumina solid electrolyte, positioned about the interior. A porous electrode for conducting electrons and allowing sodium ions to pass therethrough, and wherein electrons and sodium ions recombine to form sodium is positioned about the beta"-alumina solid electrolyte. The electrode is operated at a temperature and a pressure that allows the recombined sodium to vaporize. Additionally, an outer current collector grid for distributing electrons throughout the porous electrode is positioned about and contacts the porous electrode. Also included in the invention is transporting means for transporting liquid sodium to the beta"-alumina solid electrolyte of the tubular member. A transition piece is positioned about the interior of the member and contacts the transporting means. The transition piece divides the member into a first cell and a second cell such that each first and second cell has a beta"-alumina solid electrolyte, a first and second porous electrode and a grid. The transition piece conducts electrons from the interior of the tubular member. There is supply means for supplying sodium to the transporting means. Preferably the supply means is a shell which surrounds the tubular member and is operated at a temperature such that the vaporized sodium condenses thereon. Returning means for returning the condensed sodium from the shell to the transporting means provides a continuous supply of liquid sodium to the transporting means. Also, there are first conducting means for conducting electric current from the transition piece which extends through the shell, and second conducting means for conducting electric current to the grid of the first cell which extends through the shell.

A Novel Charged Medium Consisting of Gas-Liquid Interfacial Plasmas

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

Kaneko, Toshiro; Hatakeyama, Rikizo

Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we succeed in creating the reactive gas (plasmas)--liquid (ionic liquids) interfacial field under a low gas pressure condition, where the plasma ion behavior can be controlled. The effects of the plasma ion irradiation on the liquid medium are quantitatively revealed for the first time. In connection with the plasma ion irradiation, the potential structure and optical emission properties of the gas-liquid interfacial plasma are investigated by changing a polarity of the electrode in the liquid to evaluate the plasma-liquid interactions. Thesemore » results would contribute to synthesizing the metal nanoparticles with carbon nanotubes as a template in the ionic liquid. It is found that the high density, mono-dispersed, and isolated metal nanoparticles are synthesized between or inside the carbon nanotubes by controlling the gas-liquid interfacial plasmas. Furthermore, we can form novel nano-bio composite materials, such as DNA encapsulated carbon nanotubes using the plasma ion irradiation method in an electrolyte plasma with DNA, and demonstrate modifications of the electrical properties of the carbon nanotubes depending on the kinds of encapsulated DNA for the first time.« less

Pseudocapacitive Desalination of Brackish Water and Seawater with Vanadium-Pentoxide-Decorated Multiwalled Carbon Nanotubes.

PubMed

Lee, Juhan; Srimuk, Pattarachai; Aristizabal, Katherine; Kim, Choonsoo; Choudhury, Soumyadip; Nah, Yoon-Chae; Mücklich, Frank; Presser, Volker

2017-09-22

A hybrid membrane pseudocapacitive deionization (MPDI) system consisting of a hydrated vanadium pentoxide (hV 2 O 5 )-decorated multi-walled carbon nanotube (MWCNT) electrode and one activated carbon electrode enables sodium ions to be removed by pseudocapacitive intercalation with the MWCNT-hV 2 O 5 electrode and chloride ion to be removed by non-faradaic electrosorption of the porous carbon electrode. The MWCNT-hV 2 O 5 electrode was synthesized by electrochemical deposition of hydrated vanadium pentoxide on the MWCNT paper. The stable electrochemical operating window for the MWCNT-hV 2 O 5 electrode was between -0.5 V and +0.4 V versus Ag/AgCl, which provided a specific capacity of 44 mAh g -1 (corresponding with 244 F g -1 ) in aqueous 1 m NaCl. The desalination performance of the MPDI system was investigated in aqueous 200 mm NaCl (brackish water) and 600 mm NaCl (seawater) solutions. With the aid of an anion and a cation exchange membrane, the MPDI hybrid cell was operated from -0.4 to +0.8 V cell voltage without crossing the reduction and oxidation potential limit of both electrodes. For the 600 mm NaCl solution, the NaCl salt adsorption capacity of the cell was 23.6±2.2 mg g -1 , which is equivalent to 35.7±3.3 mg g -1 normalized to the mass of the MWCNT-hV 2 O 5 electrode. Additionally, we propose a normalization method for the electrode material with faradaic reactions based on sodium uptake capacities. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of cerium-composite polymer-electrolyte membranes during and after accelerated oxidative-stability test

NASA Astrophysics Data System (ADS)

Shin, Dongwon; Han, Myungseong; Shul, Yong-Gun; Lee, Hyejin; Bae, Byungchan

2018-02-01

The oxidative stability of membranes constructed from a composite of pristine sulfonated poly(arylene ether sulfone) and cerium was investigated by conducting an accelerated oxidative-stability test at the open-circuit voltage (OCV). The membranes were analyzed in situ through OCV and impedance measurements, cyclic voltammetry, and linear-sweep voltammetry to monitor the electrochemical properties during the stability test. Although the high-frequency resistance of a composite membrane was slightly higher than that of a pristine membrane because of the exchange of protons from the sulfonic acid with cerium ions, the composite membrane maintained its potential for much longer than the pristine membrane. The effect of the cerium ions as radical scavengers was confirmed by analyzing the drain water and chemical structure after operation. These post-operation analyses confirmed that cerium ions improved the oxidative stability of the hydrocarbon-based polymer during fuel-cell operation. It is clear that the cerium-based radical scavengers prevented chemical degradation of the polymer membrane as well as the electrode in terms of hydrogen cross-over, polymer-chain scission, and the electrochemical surface area, while they rarely diffused outward from the membrane.

Scalable Graphene-Based Membranes for Ionic Sieving with Ultrahigh Charge Selectivity.

PubMed

Hong, Seunghyun; Constans, Charlotte; Surmani Martins, Marcos Vinicius; Seow, Yong Chin; Guevara Carrió, Juan Alfredo; Garaj, Slaven

2017-02-08

Nanostructured graphene-oxide (GO) laminate membranes, exhibiting ultrahigh water flux, are excellent candidates for next generation nanofiltration and desalination membranes, provided the ionic rejection could be further increased without compromising the water flux. Using microscopic drift-diffusion experiments, we demonstrated the ultrahigh charge selectivity for GO membranes, with more than order of magnitude difference in the permeabilities of cationic and anionic species of equivalent hydration radii. Measuring diffusion of a wide range of ions of different size and charge, we were able to clearly disentangle different physical mechanisms contributing to the ionic sieving in GO membranes: electrostatic repulsion between ions and charged chemical groups; and the compression of the ionic hydration shell within the membrane's nanochannels, following the activated behavior. The charge-selectivity allows us to rationally design membranes with increased ionic rejection and opens up the field of ion exchange and electrodialysis to the GO membranes.

Design, Fabrication and Characterization of an In Silico Cell Physiology lab for Bio Sensing Applications

NASA Astrophysics Data System (ADS)

Haque, A. ul; Rokkam, M.; DeCarlo, A. R.; Wereley, S. T.; Wells, H. W.; McLamb, W. T.; Roux, S. J.; Irazoqui, P. P.; Porterfield, D. M.

2006-04-01

In this paper, we report the design, fabrication and characterization of an In Silico cell physiology biochip for measuring Ca2+ ion concentrations and currents around single cells. This device has been designed around specific science objectives of measuring real time multidimensional calcium flux patterns around sixteen Ceratopteris richardii fern spores in microgravity flight experiments and ground studies. The sixteen microfluidic cell holding pores are 150 by 150 µm each and have 4 Ag/AgCl electrodes leading into them. An SU-8 structural layer is used for insulation and packaging purposes. The In Silico cell physiology lab is wire bonded on to a custom PCB for easy interface with a state of the art data acquisition system. The electrodes are coated with a Ca2+ ion selective membrane based on ETH-5234 ionophore and operated against an Ag/AgCl reference electrode. Initial characterization results have shown Nernst slopes of 30mv/decade that were stable over a number of measurement cycles. While this work is focused on technology to enable basic research on the Ceratopteris richardii spores, we anticipate that this type of cell physiology lab-on-a-chip will be broadly applied in biomedical and pharmacological research by making minor modifications to the electrode material and the measurement technique. Future applications include detection of glucose, hormones such as plant auxin, as well as multiple analyte detection on the same chip.

Microfluidic array platform for simultaneous lipid bilayer membrane formation.

PubMed

Zagnoni, M; Sandison, M E; Morgan, H

2009-01-01

In recent years, protein array technologies have found widespread applications in proteomics. However, new methods for high-throughput analysis of protein-protein and protein-compound interactions are still required. In this paper, an array of lipid bilayer membranes formed within a microfluidic system with integrated electrodes is presented. The system is comprised of three layers that are clamped together, thus rendering the device cleanable and reusable. The device microfluidics enable the simultaneous formation of an array of lipid bilayers using a previously developed air-exposure technique, thereby avoiding the need to manually form individual bilayers. The Ag/AgCl electrodes allow for ion channel measurements, each of the sites being independently addressable. Typically, a 50% yield in simultaneous lipid bilayer formation over 12 sites was obtained and ion channel recordings have been acquired over multiple sites. This system has great potential for the development of an automatable platform of suspended lipid bilayer arrays.